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Electrochemical Membranes Doped with Pd-based Catalysts. 2. 3 ... §Department of Chemical Engineering, University of Illinois at Chicago, 810 S. Clin...
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Electrocatalytic Reduction of Nitrate using Magnéli Phase TiO Reactive Electrochemical Membranes Doped with Pd-based Catalysts Pralay Gayen, Jason Spataro, Sumant M Avasarala, Abdul-Mehdi S. Ali, Jose M Cerrato, and Brian P. Chaplin Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.8b03038 • Publication Date (Web): 24 Jul 2018 Downloaded from http://pubs.acs.org on July 26, 2018

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Environmental Science & Technology

Electrocatalytic Reduction of Nitrate using Magnéli Phase TiO2 Reactive Electrochemical Membranes Doped with Pd-based Catalysts

1 2 3 4

Pralay Gayen§, Jason Spataro§, Sumant Avasarala†, Abdul-Mehdi Ali ‡, José M. Cerrato† and

5

Brian P. Chaplin§*

6 7

§

Department of Chemical Engineering, University of Illinois at Chicago, 810 S. Clinton St., Chicago, IL 60607

8 9



Department of Civil Engineering, MSC01 1070, University of New Mexico, Albuquerque, NM 87131

10 11



Department of Earth and Planetary Sciences, MSC03 2040, University of New Mexico, Albuquerque, New Mexico 87131

12 13 14 15 16 17

*Corresponding

author at: Department of Chemical Engineering, University of Illinois at Chicago, Chicago, IL 60607, USA E-mail address: [email protected] (Brian P. Chaplin) Phone No.: +13129960288

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Abstract

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This research focused on synthesis, characterization, and application of point-of-use catalytic

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reactive electrochemical membranes (REMs) for electrocatalytic NO3- reduction. Deposition of

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Pd-Cu and Pd-In catalysts to the REMs produced catalytic REMs (i.e., Pd-Cu/REM and Pd-

22

In/REM) that were active for NO3- reduction. Optimal performance was achieved with a Pd-

23

Cu/REM and upstream counter electrode, which reduced NO3- from 1.0 mM to below the EPAs

24

regulatory MCL (700 µM) in a single pass through the REM (residence time ~ 2 s), obtaining

25

product selectivity of < 2% towards NO2-/NH3. Nitrate reduction was not affected by dissolved

26

oxygen and carbonate species and only slightly decreased in a surface water sample due to Ca2+

27

and Mg2+ scaling. Energy consumption to treat surface water was 1.1 to 1.3 kWh mol-1 for 1 mM

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NO3- concentrations, and decreased to 0.19 and 0.12 kWh mol-1 for 10 and 100 mM NaNO3

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solutions, respectively. Electrocatalytic reduction kinetics were shown to be an order of

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magnitude higher than catalytic NO3- reduction kinetics. Conversion of up to 67% of NO3-, with

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low NO2- (0.7—11 µM) and NH3 formation (< 10 µM), and low energy consumption obtained in

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this study suggest that Pd-Cu/REMs are a promising technology for distributed water treatment.

33

Keywords: Electrocatalyst, Reactive Electrochemical Membrane, Magnéli Phase TiO2

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Environmental Science & Technology

1.0 Introduction

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Distributed water treatment systems are common in developing countries, rural areas, and in

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emergency situations.1-5 They have also been proposed as sustainable solutions for decentralized

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water treatment in urban areas, as they can utilize alternative water sources and avoid the

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expense of large water distribution systems.6 Developing point-of-use (POU) technologies for

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distributed water treatment becomes challenging when the water contains poorly adsorbable

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organic and inorganic contaminants, such as trace organics and oxyanions (e.g., NO3-),

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respectively. POU reverse osmosis (RO) systems are often necessary to achieve the desired water

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quality, but suffer from low water recovery (~50%), short membrane life due to fouling, and

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concentrate management issues.4 When NO3- is of primary concern,7 POU ion exchange is often

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used, but results in a concentrated brine that is difficult or unsustainable to discharge.2,8

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Ideally, a single POU treatment technology should provide the desired water quality by

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removal of various classes of water contaminants. However, only RO treatment can accomplish

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this task. Due to the short-comings of RO treatment mentioned above, other approaches have

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been investigated, and electrochemical technologies are being researched as POU treatment

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devices.9-11 Electrochemical technologies can efficiently oxidize various organic contaminants12

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and reduce NO3-.13 However, until recently mass transport limitations in electrochemical cells

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have prevented the possibility of single pass electrochemical treatment.14 Recent work has shown

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that porous flow-through electrodes can enhance mass transport rates by over an order of

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magnitude relative to traditional parallel plate electrochemical cells, which allows

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electrochemical POU water treatment devices to achieve the desired water quality in a single

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pass through the electrode, with residence times on the order of seconds.14

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Recent work on porous flow-through electrodes for water treatment has primarily utilized

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carbon nanotube (CNT) electrochemical filters and substoichiometric TiO2 reactive

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electrochemical membranes (REMs) for the oxidation of organic contaminants15-22 and filtration

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and inactivation of pathogens.23,24 Though select reduction reactions have been investigated (e.g.,

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nitrobenzene, Cr(VI)),25,26 these flow-through electrochemical cells have not been investigated

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for NO3- reduction, nor is there a clear understanding of the effects of solution conditions on

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electrocatalytic NO3- reduction. Successful electrochemical NO3- reduction coupled with

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electrochemical oxidation would allow development of POU devices that are capable of

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removing major classes of water contaminants present in rural and developing areas (i.e.,

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pathogens, organic contaminants, and nitrate).

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The purpose of this study was to determine the feasibility of REMs for nitrate removal via

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electrochemical reduction. Known catalysts for nitrate reduction (i.e., Pd-Cu and Pd-In)27 were

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deposited on sub-stoichiometric TiO2 microfiltration REMs. For the first time, these catalytic

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REMs were characterized and studied for NO3- reduction and product selectivity in flow-through

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mode. To provide insight into system performance, various operating conditions were

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investigated including electrode placement, flow rate, electrode potential, NO3- concentration,

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and reactor number. Different solution conditions were tested to determine the effects of

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dissolved oxygen, carbonate species, and natural water constituents present in surface water on

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NO3- reduction and product selectivity. The REM performance was evaluated in terms of nitrate

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conversion, product selectivity, and energy consumption. A kinetic model was used to interpret

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the experimental data and determine rate constants for electrochemical NO3- reduction and

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compare them to those for catalytic reduction.

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2.0 Materials and Methods

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2.1 Reagents. Chemicals were reagent grade and purchased from Sigma-Aldrich and Fisher

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Scientific. Gases (purity of 99.999%) were obtained from Praxair. Solutions were prepared using

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Type I water (> 18.2 MΩ.cm at 25°C) obtained from a Barnstead NANOpure system (Thermo

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Scientific).

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2.2 Powder Catalyst Preparation. The TiO2 powder was reduced to a Magnéli phase titanium

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suboxide (TinO2n−1) (n = 4, 6) at 1050 °C under flowing H2 gas in a tube furnace (OTF-1200X,

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MTI) for 6 hours. A 2 wt% Pd catalyst with a 2:1 molar ratio of Pd to promoter metal (M = Cu or

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In) were deposited on 2.5 g of TinO2n−1 powder using the incipient wetness method. Details are

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provided in the Supporting Information (SI).

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2.3 Catalyst Loaded REM Preparation. Magnéli phase REMs were synthesized from

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Magnéli phase powder, according to a recently described method.21 The prepared pellet was

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defined as the “REM”. Catalysts were deposited on the REMs using the incipient wetness

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method, with the same catalyst loadings as the powders. Details are provided in the SI.

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2.4 Batch Nitrate Reduction Experiments. Nitrate reduction experiments were performed in a

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batch system using Pd-Cu/TinO2n-1, Pd-Cu/TiO2, and Pd-In/TinO2n-1 powders (0.67 g/L). The

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solution was purged with H2 and CO2 at flow rates of 85 and 15 mL min-1, respectively, for the

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duration of the experiment. Samples were taken at consistent time intervals, filtered, and

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analyzed by ion chromatography (IC, Dionex ICS-2100).

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2.5 Flow-through Nitrate Reduction Experiments. Electrocatalytic NO3- reduction was

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performed with the REM, Pd-Cu/REM, and Pd-In/REM in a flow-through reactor, which is

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described in the SI (Figure S-1). Two flow modes were investigated, referred to as cathode-

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anode and anode-cathode flow modes (SI, Figure S-1). The cathode-anode flow mode had a

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downstream counter electrode, and solution flowed from REM cathode to anode. The anode-

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cathode flow mode had an upstream counter electrode, and the flow was reversed.

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Electrocatalytic NO3- reduction experiments were performed under different solution conditions,

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including Ar- and air-saturated water, 10 mM NaHCO3 buffer (pH = 8.2), and in a surface water

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sample (pH = 8.1). Reduction experiments were conducted using either a NaNO3 (1 to 100 mM)

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or NaNO2 (1 mM) feed solution. Most experiments used a feed NaNO3 concentration of 1 mM,

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as this is a typical concentration found in NO3- contaminated drinking water sources, which

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ranges from 0.7 to 1.6 mM.28 Flow rates between 0.2 and 1.8 mL min-1 were used, which

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corresponded to surface area-normalized membrane fluxes (J) of 240 to 2160 L m-2 h-1 (LMH).

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Catalytic NO3- and NO2- reduction experiments were performed with Pd-Cu/REM in anode-

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cathode flow mode with 1.0 atm H2 purging and with J between 240 and 2160 LMH, in order to

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assess catalytic reduction in the absence of an applied electrode potential. More details of

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reduction experiments are provided in the SI.

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2.6 Membrane Characterization. The REM, Pd-Cu/REM, Pd-In/REM, and TinO2n-1 powder

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were characterized by X-ray diffraction (XRD, Siemens D-5000) with a Cu X-ray tube (40 kV

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and 25 mA). Scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM/EDS)

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were used for imaging and elemental analyses, and X-ray mapping was performed using electron

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microprobe at the University of New Mexico (UNM). Bulk elemental concentrations of the

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metals were determined by an acid digestion method and subsequent elemental analyses using

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inductively coupled plasma –optical emission spectrometry (ICP-OES) at UNM. Additional

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details are provided in the supporting information (SI).

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Through plane electrical conductivity (σ) was determined using electrochemical impedance

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spectroscopy with an amplitude of ±7 mV about the open circuit potential (OCP) and a

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frequency range of 0.5 to 100 kHz using a Gamry Reference 600 potentiostat/galvanostat

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(Warminster, PA). Values for σ were calculated according equation (1).

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x (1) ARREM RREM is the measured resistance (ohm) of the pellet, A is the cross-sectional area (1 cm2) and x is

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the thickness (0.25 cm).

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s=

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2.7 Analytical Methods. Concentrations of NO3-, NO2-, NH3OH+, and NH4+ were determined

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using ion chromatography (IC, Dionex ICS-2100). The pH was measured using a meter and

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probe (PC2700, Oakton). Chemical oxygen demand (COD) was measured by Hach method

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8000. Total nitrogen (N) was determined through oxidative digestion of dissolved nitrogen

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species, excluding dissolved N2, to NO3- followed by IC detection.29

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2.8 Product Selectivity, Current Efficiency, and Energy Calculations. The selectivity of NO3reduction (Si) was calculated by equation (2): !" (%) = '" (

(),+

0 1(),-.0 ,,-./ /

∗ 100

(2)

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where species i is NO2-, NH3, N2O, or N2, vi is the stoichiometric coefficient (e.g., moles of i per

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mole of NO3- degraded), and C f , NO - and C p , NO- are feed and permeate concentrations (mol m-3) of

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NO3-, respectively. The apparent N2 selectivity was calculated assuming that it represented the

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gap in the N-mass balance, as other soluble products were not detected (e.g., NH3OH+). Total N

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analysis of gas-tight, acidified permeate samples was performed immediately after collection,

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both with and without a CO2 pre-purge, and the difference between these measurements was used

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to estimate N2O production. This approach was deemed reasonable since electrochemical NO3-

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reduction results in mainly NO2-, NH3, N2, N2O, and NH3OH+.13

3

3

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Current efficiency (CE) was calculated using the following equation:

CE (%) =

JFz (C f , NO - - C p , NO - ) 3

3

j

´100

(3)

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where z is the moles of electrons transferred per moles of reactant, F is the Faraday constant

156

(96485 C mol-1), and j is current density (A cm-2). Experiments were performed at room

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temperature (21 ± 1 °C). Values for z were determined based on the observed product

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distributions.

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Energy consumption (EC) (kWh mol-1) was calculated according to the following equation:

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EC = 10−3 *

Vcell I Q(C f ,NO− − C p,NO− ) 3

(4)

3

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where, Vcell is cell potential (V), I is the current (A), and Q is the volumetric permeate flow rate

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(m3 h-1). The electrical energy per order (EEO) metric was also calculated, which is a measure of

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the electric energy (kWh m−3) needed to reduce the NO3- concentration by 1 order of

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magnitude.30

165

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EEO = 10−3 *

Vcell I ⎡C − ⎤ f ,NO3 ⎥ Q *log ⎢ ⎢C − ⎥ ⎣ p,NO3 ⎦

(5)

3.0 Results and Discussion

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3.1 Materials Characterization. Bulk elemental compositions of the Pd-Cu/REM and Pd-

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In/REM samples provided molar ratios of Pd:Cu = 2.0 ± 0.2 and Pd:In = 2.2 ± 0.1, respectively,

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which were similar to the expected molar ratio (2:1). The pore radius of the REMs was

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determined as 0.46 ± 0.04, 0.40 ± 0.02, and 0.44 ± 0.03 µm for the REM, Pd-Cu/REM, and Pd-

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In/REM, respectively, indicating that the pore size did not change significantly as a result of

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catalyst deposition (SI, Figure S-2).

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The XRD data for the TinO2n-1 powder, REM, Pd-Cu/REM, and Pd-In/REM are shown in

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Figure 1 along with the XRD characteristic peaks for Ti4O7, Ti5O9, Ti6O11, Pd, Cu, and In. The

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XRD data for the TinO2n-1 powder contained characteristic peaks representative of Ti4O7 (10-2),

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(104), (120), (2-13) and (1-20) crystal faces, with minor amounts of Ti5O9 (10-2) and Ti6O11 ((1-

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21) and (101)). The TinO2n-1 REM contained additional peaks for Ti4O7 (1-22), (10-4), and (200)

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crystal faces. The XRD data for Pd-Cu/REM and Pd-In/REM were similar to the TinO2n-1

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powder, with additional peaks for Pd(111), Pd(200), Cu(111), and Cu(200) for Pd-Cu/REM and

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Pd(111), Pd(200), In(111), In(200), and In(002) for Pd-In/REM. Significant peaks were not

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detected for CuO, Cu2O, In2O3, PdO, or PdO2, which indicated that the catalyst precursors were

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predominately reduced to their metallic oxidation states (Figure 1). Peaks suggested that Pd, Cu,

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and In were present as separate phases and alloys were not formed, which was consistent with

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the low temperature synthesis methods.

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The through plane conductivity was measured as s = 785 ± 15 S m-1 for REM, s = 835 ± 21

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for Pd-Cu/REM, and s = 824 ± 12 S m-1 for Pd-In/REM. The increases in s values were

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attributed to the highly conductive Pd, Cu, and In metals. The measured s values were similar to

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that reported for a Ti4O7 ultrafiltration REM.19

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SEM analysis of the REM showed a porous structure with particle size of ~2 µm (SI, Figure

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S-3). The SEM/EDS results of the Pd-M/REMs showed fairly uniform distribution of the catalyst

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metals on the planar surface and a high spatial correlation between Pd and M (SI, Figure S-4).

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Analyses using SEM/EDS on vertical cross sections of the Pd-M/REM samples determined that

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the catalyst metals penetrated to approximate depths of 420 µm for Pd and 400 µm for Cu for the

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Pd-Cu/REM, and 900 µm for Pd and 800 µm for In for the Pd-In/REM (Figure 2). The

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differences in penetration depths were likely affected by the deposition of Cu0 onto the REM at

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OCP conditions (reaction (6)), followed by a galvanic replacement reaction that deposited Pd0

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(reaction (7)). Once the Pd is deposited on the REM, it will further enhance Cu0 deposition via a

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electroless deposition method,31,32 and this process will inhibit the transport of both metals. By

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contrast, the redox potential for the deposition of In3+ is much more negative (reaction (8)) and

200

not feasible at the measured OCP (Eocp = 0.3 V/SHE). Therefore, deposition onto the REM

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support was likely controlled by weaker physisorption interactions and thus the metals were able

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to penetrate to a further depth into the pellet.

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Cu2+ + 2e- à Cu0

E0 = 0.34 V/SHE

(6)

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Cu0 + Pd2+ à Cu2+ + Pd0

Erxn = 0.61 V/SHE

(7)

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In3+ + 3e- à In0

E0 = -0.34 V/SHE

(8)

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3.2 Catalytic Nitrate Reduction. Batch experiments for catalytic NO3- reduction were

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conducted with Pd-Cu/TinO2n-1, Pd-Cu/TiO2, and Pd-In/TinO2n-1 powders in the presence of H2 as

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a reductant. The relevant half reactions during NO3- reduction are as follows:13,27

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>?1@

6781 + :; 7 + 2= 1 A⎯⎯C 67;1 + 27: 1 >?1@

210

6781 + 2.5:; 7 + 4= 1 A⎯⎯C 0.56; 7 + 57: 1

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6781 + 3:; 7 + 5= 1 A⎯⎯C 0.56; + 67: 1

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6781 + 6:; 7 + 8= 1 A⎯⎯C 6:8 + 97: 1

>?1@

>?1@

(9) (10) (11) (12)

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Pseudo first-order rate constants for up to 50% conversion were fit to the NO3- concentration

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versus time profiles (SI, Figure S-5). The catalyst metal normalized NO3- reduction kinetics were

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higher for Pd-Cu/TinO2n-1 (3.6 ± 0.2 L gmetal-1 min-1) than for Pd-In/TinO2n-1 (1.4 ± 0.2 L gmetal-1

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min-1) and Pd-Cu/TiO2 (0.9 ± 0.1 L gmetal-1 min-1) (Figure S-5). The 2.7-fold increase in rate

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constant for Pd-Cu/TinO2n-1 over Pd-Cu/TiO2 was unexpected since the surface area of the

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TinO2n-1 catalyst was 7.0 times less (e.g., 1.2 m2 g-1 (TinO2n-1) versus 8.4 m2 g-1 (TiO2)). The

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increase in reactivity was attributed to oxygen vacancies in the TinO2n-1 support, which created

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Ti3+ sites that reduced Pd and Cu to their metallic states during reaction and thus increased

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catalytic turnover.33

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The measured rate constants for Pd-Cu/TinO2n-1 (3.6 ± 0.2 L gmetal-1 min-1) and Pd-In/TinO2n-1

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(1.4 ± 0.2 L gmetal-1 min-1) were comparable to literature values (Pd-Cu: 0.1 – 5.1 L gmetal-1 min-1

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and Pd-In: 1.7 – 7.6 L gmetal-1 min-1).27,34 However, due to the low specific surface area of the

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TinO2n-1 powder support (1.2 m2 g-1) compared to that of typical catalyst supports (~100-200 m2

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g-1), these rate constants would be much higher if compared on a surface area normalized basis.

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However, catalytic metal dispersion is rarely reported and therefore a comparison on a surface

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area basis was not made.

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The maximum NO2- concentrations during the batch experiments were 25 ± 4 µM and 47 ± 2

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µM for the Pd-Cu/TinO2n-1 and Pd-In/TinO2n-1 catalyst, respectively (SI, Figure S-5b). The NO2-

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concentration remained below the U.S. EPA’s maximum contaminant level (MCL) for drinking

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water of 70 µM for both catalysts.7 The final !KLM0 values were 4.2 ± 0.2% for Pd-In/TinO2n-1 and

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< 5.2 x 10-3 % for Pd-Cu/TinO2n-1. The final !KN/ were 19 ± 1% for Pd-In/TinO2n-1 and 22 ± 2%

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for Pd-Cu/TinO2n-1. These results indicated that the catalysts exhibited high catalytic NO3-

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activity but substantial NH3 production.

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3.3 Electrocatalytic Nitrate Reduction. Electrochemical NO3- reduction has advantages over

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catalytic reduction, as it does not require the storage and delivery of an external electron donor

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(e.g., H2) and thus the development of compact POU treatment technologies are possible. The

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REM, Pd-Cu/REM, and Pd-In/REM were tested for electrocatalytic NO3- reduction in flow-

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through mode. Results for all experiments are summarized in Table S-1 and experiments

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conducted at a cathodic potential of -2.5 V/SHE are summarized in Table 2.

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3.3.1 Effect of Flow Direction. Experiments conducted as a function of flow direction were

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performed with Ar purging to remove dissolved oxygen. Reduction experiments for the cathode-

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anode flow mode were performed at the OCP to -3.6 V/SHE (J = 600 LMH), and experiments

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for the anode-cathode flow mode were performed at the OCP to -2.5 V/SHE (J = 600 LMH). The

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-3.6 V/SHE potential was not used for the anode-cathode flow mode due to H2 bubble formation

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at the REM surface, which resulted in increased pressure drop across the REM and large

248

fluctuations in current. The NO3- and NO2- concentration versus time profiles at different

249

potentials are summarized in Figure 3 for the anode-cathode flow mode and Figure S-6 for the

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cathode-anode flow mode.

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Nitrate conversion for both flow modes was highest for Pd-Cu/REM, followed by Pd-

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In/REM and REM (Figures 3 and S-6; Table S-1). Both catalysts showed significant

253

enhancements in NO3- conversion compared to the REM, which is consistent with LSV scans

254

that showed increased current for Pd-M/REM compared to REM in the presence of 5 mM

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NaNO3 (Figure S-7a). LSV scans also indicated that NO3- reduction became mass transport

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limited in the anode-cathode flow mode at potentials more negative than ~ -2.0 V/SHE (Figure

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S-7b). For both flow modes, the product selectivity was more favorable for the Pd-Cu/REM

258

relative to the Pd-In/REM, where the later consistently had higher selectivity towards NO2- and

259

NH3. Results for electrocatalytic NO3- reduction were similar to catalytic batch experiments that

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showed Pd-Cu was more active and selective then Pd-In.

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There were several differences in performance observed for the two flow modes. Discernable

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NO3- reduction for all REMs was observed at lower potentials for the anode-cathode flow mode

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(-0.2 V/SHE) compared to the cathode-anode flow mode (-1.2 V/SHE). Although the total

264

current was comparable at a given potential, the extent of NO3- conversion was always greater

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for the anode-cathode flow mode (Figures 3 and S-6). For example, at a potential of -2.5 V/SHE

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NO3- conversion for the Pd-Cu/REM was approximately 20% in cathode-anode flow mode and

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43% in anode-cathode flow mode (Table 2). The cathode-anode flow mode had high NO2- and

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NH3 selectivity, while the anode-cathode flow mode had primarily N2 and N2O selectivity (Table

269

S-1, Table S-2, and Table 2). At a potential of -2.5 V/SHE, NO3- selectivity for the Pd-Cu/REM

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in the cathode-anode flow mode was !KLM0 = 35%, !KN/ = 31%, !KM L = 13%, and !KM = 23%; and

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the selectivity in the anode-cathode flow mode was !KLM0 = 0.07%, !KN/ < 2.3%, !KM L = 71%,

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and !KM > 27% (Table 2).

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The higher NO3- conversion and lower NO2- formation for the anode-cathode flow mode

274

relative to the cathode-anode flow mode were attributed to the placement of the counter

275

electrode. These results were consistent with prior studies that concluded a downstream counter

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electrode (cathode-anode) resulted in lower conversion compared to an upstream counter

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electrode (anode-cathode) in the presence of a more favorable side reaction (i.e., H2 evolution).35

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In our experiments H2 production was more significant in the cathode-anode flow mode and

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inhibited electrocatalytic NO3- reduction. Another potential advantage of the anode-cathode flow

280

mode is a lowering of the local pH, which could limit mineral scaling on the cathode surface.

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The NH3 selectivity in the anode-cathode flow mode (NH3 not detected) was among the lowest

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reported selectivity for electrochemical NO3- reduction,13 which is an important requirement for

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a POU treatment technology.

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These experiments indicated that the Pd-Cu/REM operated in the anode-cathode flow mode

285

was the most active for NO3- reduction and had the highest product selectivity for N atom

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coupling (100% of detected products). At a potential of -2.5 V/SHE the permeate concentrations

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were below the EPA MCLs of 0.7 mM for NO3- and 70 µM for NO2-, and NH3 concentrations

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were always below the IC detection limit (< 10 µM), which was less than the World Health

289

Organization (WHO) limit of 30 µM. Therefore, the anode-cathode flow mode was utilized for

290

all additional experiments.

291

3.3.2 Effect of Solution Conditions. Solution conditions can have an adverse effect on both

292

catalytic NO3- reduction activity and product selectivity,27,36-39 but few studies have investigated

293

the effects of solution conditions on electrocatalytic NO3- reduction. The O2 reduction reaction

294

(ORR) occurs at similar cathodic potentials as NO3- reduction,40 and dissolved organic matter can

295

adsorb and block catalytic sites.41,42 Therefore, the effects of dissolved oxygen, bicarbonate, and

296

a surface water sample (Table 1) on NO3- reduction were investigated.

297

The results for NO3- conversion and product selectivity for both Pd-Cu/REM and Pd-In/REM

298

in the air-saturated solution were similar to the Ar-saturated solution over the same applied

299

potentials (Figure 3, Table 2, Figure S-8, and Table S-1), indicating that the ORR did not

300

compete for NO3- reduction sites. LSV scans support this result, as measured currents were

301

nearly identical for Ar-saturated and air-saturated electrolytes (SI, Figure S-9). These results are

302

attributed to the low ORR activity of the TinO2n-1 support,43 promoter metals,44,45 and the Pd

303

crystal faces observed by XRD (i.e., Pd(111) and Pd(200)).46 The lack of competition from the

304

ORR during electrocatalytic NO3- reduction with the Pd-M/REMs is a significant advantage over

305

other electrodes and catalytic systems that require deoxygenated solutions.27,38,47

306

Nitrate conversion was not significantly affected by any of the other solution conditions

307

tested compared to the Ar-saturated solution, with the exception of the surface water sample that

308

showed NO3- conversion was inhibited at -2.5 V/SHE. The NO3- conversion in the surface water

309

decreased by 1.4-fold compared to the 10 mM NaHCO3 buffer solution of similar pH at -2.5

310

V/SHE (Figure 3a and Table 2). These results were most likely caused by scaling of CaCO3(s)

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and Mg(OH)2(s) onto the catalyst surface, as the alkalinity decreased from 124 mg L-1 to 67 mg L-

312

1

313

decreased from 0.26 mM to 0.19 mM at a cathodic potential of -2.5 V/SHE. In a long-term

314

treatment application mineral scaling can be overcome by periodic reverse polarity treatments to

315

dissolve the scale. This approach has been demonstrated in other electrochemical studies.48

, Ca2+ concentration decreased from 0.88 mM to 0.66 mM, and the Mg2+ concentration

316

Product selectivities were not greatly affected by the different solution conditions (Figure 3b,

317

Table 2, and Table S-1). The NO2- and NH3 concentrations were always below the MCL and IC

318

detection limit, respectively. The Pd-Cu/REM was able to reduce NO3- from a 1 mM feed

319

concentration to below the regulatory MCL in a single pass through the REM in the anode-

320

cathode flow mode, without negative effects from dissolved oxygen and carbonate species and

321

only minor effects from constituents found in surface water (e.g., Ca2+, Mg2+). In addition, the

322

oxidation of Cl- was not observed in the surface water sample, as the anode potential was < 2.0

323

V/SHE, and Cl2, ClO3-, and ClO4- were all below the detection limits of the analytical methods of

324

0.02 mg/L, 0.9 µg L-1, and 1.0 µg L-1, respectively.

325

3.3.3 REMs in Series. Though NO3- concentrations at the most cathodic potentials tested

326

were lower than the MCL (0.7 mM), two Pd-Cu/REMs in series were used to further decrease

327

the NO3- concentration. Experiments were performed in air-saturated solutions containing 1 mM

328

NaNO3 and in either the 10 mM NaHCO3 buffer or surface water sample. Results are

329

summarized in Figure 3, Table 2, and Table S-1. The results indicated that the electrochemical

330

cells operated as approximately two first-order reactors in series, where NO3- conversion (R)

331

followed equation (13):

332

V

()

O = 1 − QR( S U ,

(13)

T

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(

where R() S is the ratio of NO3- permeate and feed concentrations for a single reactor and n is ,

T

334

the number of reactors in series. The measured NO3- conversion in the 10 mM NaHCO3 buffer

335

for two Pd-Cu/REMs in series were 20% (17%), 29% (31%), 44% (49%), and 65% (69%) at

336

cathodic potentials of -0.2, -1.2, -1.9, and -2.5 V/SHE, respectively, where values in parentheses

337

were those predicted by equation (13). In the presence of the surface water sample, the NO3-

338

conversion for two reactors in series were 14% (7.5%), 23% (25%), 36% (43%), and 51% (54%)

339

at cathodic potentials of -0.2, -1.2, -1.9, and -2.5 V/SHE, respectively (Figure 3c and Table S-1).

340

The lower NO3- conversion in the surface water sample again was most likely caused by

341

CaCO3(s) and Mg(OH)2(s) scaling, as the alkalinity decreased from 124 mg L-1 to 32 mg L-1, Ca2+

342

concentration decreased from 0.88 mM to 0.49 mM, and the Mg2+ concentration decreased from

343

0.26 mM to 0.11 mM at a cathodic potential of -2.5 V/SHE. The product selectivities were

344

similar for the one and two reactors in series operations. The effluent pH values were as high as

345

8.9 in the surface water sample (SI, Table S-1). Therefore some adjustment of pH or

346

optimization in reactor design or operation may be necessary.

347

3.4 Reactivity and Mass Transport Characterization. Electrocatalytic and catalytic NO3-

348

reduction were both tested in the Pd-Cu/REM flow-through system as a function of J (240 to

349

2160 LMH (6.7 x 10-5 to 5.4 x 10-4 m s-1)) and results are shown in Figure 4. The NO2-

350

concentrations were low for both catalytic (0.10 to 0.13 µM) and electrocatalytic (0.70 to 0.52

351

µM) NO3- reduction, and the NH3 concentrations were always below the detection limit (< 10

352

µM) (Table S-3).

353

Based on LSV data, it was determined that electrocatalytic NO3- removal was mass transport

354

limited at potentials more negative than -2.0 V/SHE (Figure S-7). Therefore, at -2.5 V/SHE

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equation (14) was used to fit the electrocatlytic NO3- reduction data in the Pd-Cu/REM flow-

356

through reactor.

357

(

R() S = exp Z− ,

[\ ]^ _

`

(14)

358

In equation (14), km is the mass transport rate constant (m s-1), a is the specific surface area (m-1),

359

and l is the reactive length (m). Values for km in packed bed electrochemical reactors have been

360

shown to follow equation (15).

361

ab = c de.88

(15)

362

where b is a proportionality constant. Values for a and l were combined with b, and equation

363

(14) was rewritten as follows,

364

(

R() S = exp Z− ,

b_ f.// _

` = exp Z−

[ghi _

`

(16)

365

where m is a proportionality constant that was determined to equal 0.0017 and yielded observed

366

rate constant (kobs) values between 7.0 x 10-5 and 1.5 x 10-4 m s-1. The model fit of equation (16)

367

to experimental data is shown in Figure 4.

368

Since the conversion of NO3- during catalytic experiments was small (< 10%) relative to the

369

stoichiometric conversion with H2 (i.e., up to 32% via reaction 11), pseudo first-order kinetics

370

were assumed and equation (16) was also used to fit the catalytic NO3- reduction data. However,

371

since catalytic NO3- removal was much lower than the mass transport limit, kobs was represented

372

by a resistance in series model that accounts for the resistances from mass transport and reaction

373

kinetics (equation 17).

374

[

ajkl = am / Z1 + [ o `

(17)

\

375

In equation (17), kr is the heterogeneous pseudo first-order reaction rate constant (m s-1). Values

376

determined for km from electrocatalytic experiments were used in equation (17) and a best fit

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value of kr = 1.1 x 10-5 m s-1 was determined by fitting equation (17) to the experimental data

378

(Figure 4a). Results indicated that the kobs values for catalytic NO3- reduction were

379

approximately an order of magnitude less than those for electrocatalytic NO3- reduction, which

380

suggested that electrocatalysis was the predominant mechanism for NO3- removal in all

381

electrochemical REM flow-through experiments, as the retention times (0.2 to 2.2 s) in the REM

382

were too short to allow for significant catalytic NO3- reduction. Identical experiments were

383

performed for NO2- reduction, and the extent of removal with respect to J were similar to those

384

for catalytic NO3- reduction (Figure S-10), which explains why only trace NO2- concentrations

385

were detected in all experiments. These results suggest that electrocatalyic reduction is a

386

promising process to achieve significant NO3- removal without significant NO2- production

387

under single pass operation. By contrast, catalytic NO3- reduction in flow-through reactors

388

require residence times that are > 40 times longer than were reported in Figure 4 for

389

electrocatalytic NO3- reduction.37

390

3.5 Technological and Environmental Implications. Sustainable POU water treatment

391

technologies need to operate with minimal energy consumption. The energy requirements were

392

calculated according to equations 4 and 5 and are reported in Table 2 and Table S-4. The EEO and

393

EC values followed the order of: REM > Pd-In/REM > Pd-Cu/REM (Table 2 and Table S-4).

394

The minimal EC and EEO values for Pd-Cu/REM (EC = 0.57 kWh mol-1; EEO = 1.1 kWh m-3) and

395

Pd-In/REM (EC = 0.89 kWh mol-1; EEO = 1.7 kWh m-3) occurred for the Ar-saturated, 1 mM

396

NaNO3 solutions operated in anode-cathode flow mode. Values approximately doubled in the air-

397

saturated surface water solution with the Pd-Cu/REM (EC = 1.1 kWh mol-1; EEO = 2.3 kWh m-3).

398

The energy consumption values were EC = 0.62 ± 0.02 kWh mol-1 and EEO = 1.1 ± 0.12 kWh m-3

399

at 1 mM NO3- concentration, EC = 0.19 ± 0.07 kWh mol-1 and EEO = 3.5 ± 0.73 kWh m-3 at 10

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mM NO3- concentration, and 0.12 ± 0.06 kWh mol-1 and EEO = 26 ± 0.73 kWh m-3 at 100 mM

401

NO3- concentration, using the Pd-Cu/REM in anode-cathode flow mode (Figure S-4).

402

Concentrated NO3- solutions showed more favorable EC values, due to increased solution

403

conductivity and a 2.3RT/F positive Nernstian shift in the redox potential for every 10-fold

404

increase in NO3- concentration. Therefore, coupling the REM system to technologies that

405

separate and concentrate NO3-, without the accumulation of chloride, may be another useful

406

application for this technology (e.g., ion exchange with NaOH regeneration). Competitive

407

technologies, such as RO treatment and ion exchange, can achieve near complete removal of

408

NO3-, with energy requirements of 0.46 kWh m-3 for RO49 and 0.06 kWh m-3 for ion exchange.50

409

However, both RO and ion exchange produce brines that require further treatment or disposal.

410

Further improvements in REM reactor design and electrode preparation will lead to reduced

411

energy consumption and more efficient utilization of the catalytic metals. For example,

412

narrowing the inter-electrode gap will reduce solution resistance and lower the overall cell

413

potential, and more efficient dispersion of the catalyst metals will allow for lower loadings of

414

precious metals.

415

Current efficiencies were also calculated based on the observed product distributions (Table

416

S-1 and Table 2). The current efficiencies were between 1.9 to 12% for the REM, 2.1 to 105%

417

for the Pd-Cu/REM, and 2.3 to 71% for the Pd-In/REM. The maximum current efficiency for Pd-

418

Cu/REM (105 ± 5.4%) was in the presence of air purging and 1 mM NaNO3. The current

419

efficiency decreased to between 51 and 52% in the presence of the 10 mM NaHCO3 or surface

420

water solutions (Table S-1 and Table 2). These results were attributed to the higher ionic

421

conductivity and proton donor ability of the HCO3- electrolyte that gave rise to increased H2

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422

evolution. The range of current efficiencies observed in this study were comparable to values

423

reported in the literature for different electrocatalysts.13

424

The selectivity towards N2O was significant for all electrocatalytic NO3- reduction

425

experiments. The formation of N2O has environmental implications as it acts as a greenhouse

426

gas.51 The reduction of N2O to N2 has been shown to occur on Pd electrocatalysts with 100%

427

selectivity.52 However, in our studies the residence time (< 2 s) in the REM reactor was too short

428

for significant conversion of N2O to N2. For the treatment of dilute NO3- solutions (mM levels)

429

the total N2O flux is small compared to natural sources. For example, assuming 100% reduction

430

of 106 L (typical of a small drinking water plant) of 1 mM NO3- solution per day to N2O would

431

account for < 0.0003% of the total estimated N2O production rate per year (3.3 x 1011 kg yr-1).53

432

However, more selective electrocatalysts or passing the permeate through an additional Pd

433

catalyst bed with a longer residence time would eliminate N2O outgassing to the atmosphere. For

434

the treatment of concentrated NO3- solutions, the produced N2O could be recovered and used as

435

an energy source, which would improve the energy efficiency of the treatment process. Such a

436

strategy has been proposed for the biological treatment of nitrogen in wastewater.54

437

Supporting Information

438

Additional experimental details, SEM/EDS analyses, catalytic batch nitrate reduction results,

439

additional REM experimental results, LSV scans, and tabulated experimental results.

440

Corresponding Author

441

*E-mail: [email protected]

442

Acknowledgements

443

We thank Dr. Yin Wang from the University of Wisconsin-Milwaukee for BET analysis.

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Funding for this work was provided by a National Science Foundation CAREER award to BPC

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(CBET-1453081).

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b)

37

448 449

450

451

42

447

47

2ϴ Ti4 O7 (30-2) Ti4 O7 (1-2-6) Ti6 O11 (1-2-11) Ti4 O7 (1-4-2) Ti4 O7 (2-42) Ti6 O11 (2-40)

25

Cu (200)

In (200)

20 Pd (200)

30 2ϴ

52

57

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Ti4O7 (02-4)

Ti4O7 (200) Ti4O7 (2 0 10) Ti4O7 (104) Ti4O7 (120)

Ti4O7 (10-4) Ti4O7 (022)

Ti4O7 (1-22) Ti6O11 (10-1) Ti4O7 (1-2-2)

Ti6O11 (1-21)

Ti4O7 (1-20)

Ti6O11 (101)

Ti5O9 (10-2)

Ti4O7 (10-2)

a)

In (111) Pd (111) Ti4 O7 (2-13) Ti4 O7 (031)

Normalized Intensity

446

Cu (111) In (002)

Normailzed Intensity

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Figures and Tables.

4

3

2 1

35

4

3

2

1

62

Figure 1. XRD data for 1) TinO2n-1 powder, 2) REM, 3) Pd-Cu/REM and 4) Pd-In/REM. The locations of the characteristic peaks for Ti4O7, Ti6O11, In, Pd, and Cu are represented by the vertical dashed lines. a) 2ϴ = 20-38 deg and b) 2ϴ = 38-52 deg.

22

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452

456

455

454

are estimated penetration depths of the catalyst metals.

g) Ti, h) O, i) Pd, and j) In in Pd-In/REM. Top surface of the pellet is the left side of the image. Solid black lines on panels d, e, i, and j

Scanning electron microscope and microprobe mapping of the vertical cross-section: b) Ti, c) O, d) Pd, and e) Cu in Pd-Cu/REM; and

Figure 2. Scanning electron microscope and microprobe image of the vertical cross-section of a) Pd-Cu/REM and f) Pd-In/REM.

453

457

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= REM-Ar = Pd-Cu/REM-Buffer-Air = Pd-Cu/REM-Air = Pd-Cu/REM-Ar

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= Pd-Cu/REM-Surface Water = Pd-Cu/REM-Series-Surface Water = Pd-Cu/REM-Series-Buffer

459

Figure 3. a) Nitrate and b) nitrite concentration profiles for REM and Pd-Cu/REM at different

460

potentials in the anode-cathode flow mode under different solution conditions. c) Nitrate and

461

d) nitrite concentration profiles for REM and two Pd-Cu/REM in series at different potentials in

462

anode-cathode mode.

463

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kobs (m s-1)

a)

1.60E-04 1.20E-04 8.00E-05

465

Nitrate (C/Co)

Catalytic

4.00E-05 0.00E+00 0.00E+00

b)

Electrocatalytic

4.00E-04 J (m s-1)

8.00E-04

1.2 1.0 0.8

MCL

0.6 0.4

Catalytic

0.2

Electrocatalytic

0.0 0.00E+00 466

4.00E-04 J (m s-1)

8.00E-04

467

Figure 4. Electrocatalytic and catalytic NO3- reduction in the Pd-Cu/REM flow-through reactor.

468

a) kobs values versus J, b) NO3- concentration versus J. The solid lines are the model fits using

469

equations 16 and 17 and the dashed horizontal line represents the MCL for NO3-.

470

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Table 1. Water quality data of the surface water sample. Sodium Potassium Calcium Magnesium Chloride Sulfate Bicarbonate Alkalinity COD pH

Filtered Surface Water 0.56 mM 0.17 mM 0.90 mM 0.25 mM 0.63 mM 0.015 mM 2.42 mM 124 mg L-1 as CaCO3 39 mg L-1 8.1

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473

Anode-Cathode/Air Purging/Surface Water

Anode-Cathode/Air Purging/Bicarbonate Buffer

Anode-Cathode/Air Purging

Anode-Cathode/Ar Purging

Cathode-Anode/Ar Purging

65 ± 1.3

32 ± 1.09

44 ± 1.4

42 ± 1.8

43 ± 2.2

20 ± 1.02

NO3Conversion (%)

0.07 ± 0.14

0.40 ± 0.06

0.07 ± 0.01

0.56 ± 0.02

0.78 ± 0.04

0.07 ± 0.02

35 ± 2.4

S(NO2-) (%)

< 1.9 ± 0.08

< 1.5 ± 0.04

< 3.1 ± 0.11

< 2.2 ± 0.07

< 2.3 ± 0.1

< 2.3 ± 0.11

31 ± 2.3

S(NH3) (%)

52 ± 0.84

43 ± 0.36

43 ± 0.32

42 ± 0.36

55 ± 0.29

70 ± 0.38

12 ± 0.09

S(N2O) (%)

47 ± 0.93

56 ± 0.94

56 ± 0.49

57 ± 0.03

43 ± 1.01

29 ± 0.72

23 ± 0.91

S(N2) (%)

8.9 ± 0.3

8.0 ± 0.2

8.8 ± 0.2

7.8 ± 0.4

9.4 ± 0.2

9.2 ± 0.1

9.8 ± 0.2

Effluent pH

35 ± 5.01

60 ± 4.2

51 ± 4.3

51 ± 2.5

106 ± 5.4

102 ± 5.7

60 ± 2.4

CE (%)

6.9 ± 0.13

3.5 ± 0.27

2.7 ± 0.17

2.3 ± 0.34

1.1 ± 0.12

1.1 ± 0.23

2.6 ± 0.06

EEO (kWh m-3)

3.7 ± 0.04

2.4 ± 0.06

1.4 ± 0.03

1.3 ± 0.08

1.06 ± 0.03

0.90 ± 0.07

1.9 ± 0.02

EC (kWh mol-1)

Table 2. Summary of results for 1 mM nitrate reduction with a Pd-Cu/REM at a cathodic potential of -2.5 V/SHE

Anode-Cathode/Air Purging/Bicarbonate Buffer/Series 51 ± 2.07

Reaction Conditions

Anode-Cathode/Air Purging/Surface Water/Series

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References

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(1) Goodrich, J. A.; Lykins, B. W.; Clark, R. M., Drinking-water from agriculturally contaminanted groundwater. Journal of Environmental Quality 1991, 20, (4), 707-717. (2) USEPA, Point-of-use or point-of-entry treatment options for small drinking water systems, Office of Water. [accessed May 15th 2018] https://www.epa.gov/sites/production/files/201509/documents/guide_smallsystems_pou-poe_june6-2006.pdf. 2006. (3) Sobsey, M. D.; Stauber, C. E.; Casanova, L. M.; Brown, J. M.; Elliott, M. A., Point of use household drinking water filtration: A practical, effective solution for providing sustained access to safe drinking water in the developing world. Environ. Sci. Technol. 2008, 42, (12), 4261-4267. (4) Peter-Varbanets, M.; Zurbrugg, C.; Swartz, C.; Pronk, W., Decentralized systems for potable water and the potential of membrane technology. Water Res. 2009, 43, (2), 245-265. (5) Loo, S. L.; Fane, A. G.; Krantz, W. B.; Lim, T. T., Emergency water supply: A review of potential technologies and selection criteria. Water Res. 2012, 46, (10), 3125-3151. (6) Larsen, A. T. U., K. M.; Lienert, J., Source separation and decentralization for wastewater management. IWA Publishing: London, 2013. (7) USEPA, National Primary Drinking Water Regulations: Contaminant specific fact sheets, inorganic chemicals, Consumer Versions, EPA 811-F-95-02C, USEPA Office of Water, Washington, D.C., October. 1995. (8) Kapoor, A.; Viraraghavan, T., Nitrate removal from drinking water - Review. Journal of Environ. Eng.-ASCE 1997, 123, (4), 371-380. (9) Butkovskyi, A.; Jeremiasse, A. W.; Leal, L. H.; van der Zande, T.; Rijnaarts, H.; Zeeman, G., Electrochemical Conversion of Micropollutants in Gray Water. Environ. Sci. Technol. 2014, 48, (3), 18931901. (10) Barazesh, J. M.; Hennebel, T.; Jasper, J. T.; Sedlak, D. L., Modular Advanced Oxidation Process Enabled by Cathodic Hydrogen Peroxide Production. Environ. Sci. Technol. 2015, 49, (12), 7391-7399. (11) Barazesh, J. M.; Prasse, C.; Wenk, J.; Berg, S.; Remucal, C. K.; Sedlak, D. L., Trace Element Removal in Distributed Drinking Water Treatment Systems by Cathodic H2O2 Production and UV Photolysis. Environ. Sci. Technol. 2018, 52, (1), 195-204. (12) Chaplin, B. P., Critical Review of Electrochemical Advanced Oxidation Processes for Water Treatment Applications. Environ. Sci.: Processes Impacts 2014, 16, (6), 1182-1203. (13) Martinez, J.; Ortiz, A.; Ortiz, I., State-of-the-art and perspectives of the catalytic and electrocatalytic reduction of aqueous nitrates. Appl. Catal. B-Environ. 2017, 207, 42-59. (14) Trellu, C.; Chaplin, B. P.; Coetsier, C.; Esmilaire, R.; Cerneaux, S.; Causserand, C.; Cretin, M., Electro-oxidation of Organic Pollutants by Reactive Electrochemical Membranes. Chemosphere 2018, 10.1016/j.chemosphere.2018.05.026. (15) Vecitis, C. D.; Gao, G.; Liu, H., Electrochemical Carbon Nanotube Filter for Adsorption, Desorption, and Oxidation of Aqueous Dyes and Anions. J. Phys. Chem. C 2011, 115, (9), 3621-3629. (16) Gao, G. D.; Vecitis, C. D., Doped Carbon Nanotube Networks for Electrochemical Filtration of Aqueous Phenol: Electrolyte Precipitation and Phenol Polymerization. ACS Appl. Mater. Inter. 2012, 4, (3), 1478-1489. (17) Zaky, A. M.; Chaplin, B. P., Porous Substoichiometric TiO2 Anodes as Reactive Electrochemical Membranes for Water Treatment. Environ. Sci. Technol. 2013, 47, (12), 6554-6563. (18) Zaky, A. M.; Chaplin, B. P., Mechanism of p-Substituted Phenol Oxidation at a Ti4O7 Reactive Electrochemical Membrane. Environ. Sci. Technol. 2014, 48, (10), 5857-5867. (19) Guo, L.; Jing, Y.; Chaplin, B. P., Development and Characterization of Ultrafiltration TiO2 Magnéli Phase Reactive Electrochemical Membranes. Environ. Sci. Technol. 2016, 50, (3), 1428-1436.

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(20) Santos, M. C.; Elabd, Y. A.; Jing, Y.; Chaplin, B. P.; Fang, L., Highly porous Ti4O7 reactive electrochemical water filtration membranes fabricated via electrospinning/electrospraying. AiChE J. 2016, 62, (2), 508-524. (21) Nayak, S.; Chaplin, B. P., Fabrication and characterization of porous, conductive, monolithic Ti4O7 electrodes. Electrochim. Acta 2018, 263, 299-310. (22) Trellu, C.; Coetsier, C.; Rouch, J. C.; Esmilaire, R.; Rivallin, M.; Cretin, M.; Causserand, C., Mineralization of organic pollutants by anodic oxidation using reactive electrochemical membrane synthesized from carbothermal reduction of TiO2. Water Res. 2018, 131, 310-319. (23) Vecitis, C. D.; Schnoor, M. H.; Rahaman, M. S.; Schiffman, J. D.; Elimelech, M., Electrochemical Multiwalled carbon nanotube filter for viral and bacterial removal and inactivation. Environ. Sci. Technol. 2011, 45, (8), 3672-3679. (24) Rahaman, M. S.; Vecitis, C. D.; Elimelech, M., Electrochemical Carbon-Nanotube Filter Performance toward Virus Removal and Inactivation in the Presence of Natural Organic Matter. Environ. Sci. Technol. 2012, 46, (3), 1556-1564. (25) Gao, G.; Zhang, Q.; Vecitis, C. D., CNT-PVDF composite flow-through electrode for single-pass sequential reduction-oxidation. J Mater. Chem. A 2014, 2, (17), 6185-6190. (26) Duan, W. Y.; Chen, G. D.; Chen, C. X.; Sanghvi, R.; Iddya, A.; Walker, S.; Liu, H. Z.; Ronen, A.; Jassby, D., Electrochemical removal of hexavalent chromium using electrically conducting carbon nanotube/polymer composite ultrafiltration membranes. J. Mem. Sci. 2017, 531, 160-171. (27) Chaplin, B. P.; Reinhard, M.; Schneider, W. F.; Schuth, C.; Shapley, J. R.; Strathmann, T. J.; Werth, C. J., Critical Review of Pd-Based Catalytic Treatment of Priority Contaminants in Water. Environ. Sci. Technol. 2012, 46, (7), 3655-3670. (28) Fewtrell, L., Drinking-water nitrate, methemoglobinemia, and global burden of disease: A discussion. Environ. Health Perspect. 2004, 112, (14), 1371-1374. (29) American Public Health Association (APHA), American Water Works Association (AWW), Water Environmental Federation (WEF). Standard Methods for the Examination of Water and Wastewater. 21 ed.; Washington, D.C., 2005. (30) Bolton, J. R.; Bircher, K. G.; Tumas, W.; Tolman, C. A., Figures-of-merit for the technical development and application of advanced oxidation technologies for both electric- and solar-driven systems - (IUPAC Technical Report). Pure Appl. Chem. 2001, 73, (4), 627-637. (31) Hidber, P. C.; Helbig, W.; Kim, E.; Whitesides, G. M., Microcontact printing of palladium colloids: Micron-scale patterning by electroless deposition of copper. Langmuir 1996, 12, (5), 1375-1380. (32) Fritz, N.; Koo, H.-C.; Wilson, Z.; Uzunlar, E.; Wen, Z.; Yeow, X.; Allen, S. A. B.; Kohl, P. A., Electroless Deposition of Copper on Organic and Inorganic Substrates Using a Sn/Ag Catalyst. J. Electrochem. Soc. 2012, 159, (6), D386-D392. (33) Kim, M.-S.; Lee, D.-W.; Chung, S.-H.; Kim, J. T.; Cho, I.-H.; Lee, K.-Y., Pd-Cu bimetallic catalysts supported on TiO2-CeO2 mixed oxides for aqueous nitrate reduction by hydrogen. J. Mol. Catal. A-Chem. 2014, 392, 308-314. (34) Guo, S. J.; Heck, K.; Kasiraju, S.; Qian, H. F.; Zhao, Z.; Grabow, L. C.; Miller, J. T.; Wong, M. S., Insights into Nitrate Reduction over Indium-Decorated Palladium Nanoparticle Catalysts. ACS Catal. 2018, 8, (1), 503-515. (35) Trainham, J. A.; Newman, J., Effect of electrode placement and finite matrix conductivity on performance of flow-through porous-electrodes. J. Electrochem. Soc. 1978, 125, (1), 58-68. (36) Chaplin, B. P.; Roundy, E.; Guy, K. A.; Shapley, J. R.; Werth, C. J., Effects of Natural Water Ions and Humic Acid on Catalytic Nitrate Reduction Kinetics Using an Alumina Supported Pd-Cu Catalyst. Environ. Sci. Technol. 2006, 40, (9), 3075-3081. (37) Wang, Y.; Qu, J. H.; Liu, H. J.; Hu, C. Z., Adsorption and reduction of nitrate in water on hydrotalcite-supported Pd-Cu catalyst. Catal. Today 2007, 126, (3-4), 476-482.

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(38) Chaplin, B. P.; Shapley, J. R.; Werth, C. J., The Selectivity and Sustainability of a Pd-In/gamma-Al2O3 Catalyst in a Packed-Bed Reactor: The Effect of Solution Composition. Catal. Letters 2009, 130, (1-2), 5662. (39) Yuranova, T.; Franch, C.; Palomares, A. E.; Garcia-Bordeje, E.; Kiwi-Minsker, L., Structured fibrous carbon-based catalysts for continuous nitrate removal from natural water. Appl. Catal. B-Environ. 2012, 123, 221-228. (40) Plumere, N., Interferences from oxygen reduction reactions in bioelectroanalytical measurements: the case study of nitrate and nitrite biosensors. Anal. Bioanal. Chem. 2013, 405, (11), 3731-3738. (41) Rajic, L.; Fallahpour, N.; Nazari, R.; Alshawabkeh, A. N., Influence of humic substances on electrochemical degradation of trichloroethylene in limestone aquifers. Electrochim. Acta 2015, 181, 123-129. (42) Fallahpour, N.; Mao, X.; Rajic, L.; Yuan, S.; Alshawabkeh, A. N., Electrochemical dechlorination of TCE in the presence of natural organic matter, metal ions and nitrates in a simulated karst aquifer. J. Environ. Chem. Eng. 2017, 5, 24-245. (43) Li, X. X.; Zhu, A. L.; Qu, W.; Wang, H. J.; Hui, R.; Zhang, L.; Zhang, J. J., Magneli phase Ti4O7 electrode for oxygen reduction reaction and its implication for zinc-air rechargeable batteries. Electrochim. Acta 2010, 55, (20), 5891-5898. (44) Wang, B., Recent development of non-platinum catalysts for oxygen reduction reaction. J. Power Sources 2005, 152, (1), 1-15. (45) Morozan, A.; Jousselme, B.; Palacin, S., Low-platinum and platinum-free catalysts for the oxygen reduction reaction at fuel cell cathodes. Energy Environ. Sci. 2011, 4, (4), 1238-1254. (46) Ge, X. M.; Sumboja, A.; Wuu, D.; An, T.; Li, B.; Goh, F. W. T.; Hor, T. S. A.; Zong, Y.; Liu, Z. L., Oxygen Reduction in Alkaline Media: From Mechanisms to Recent Advances of Catalysts. ACS Catal. 2015, 5, (8), 4643-4667. (47) Nobial, M.; Devos, O.; Mattos, O. R.; Tribollet, B., The nitrate reduction process: A way for increasing interfacial pH. J. Electroanal. Chem. 2007, 600, (1), 87-94. (48) Duan, W.; Dudchenko, A.; Mende, E.; Flyer, C.; Zhu, X.; Jassby, D., Electrochemical mineral scale prevention and removal on electrically conducting carbon nanotube - polyamide reverse osmosis membranes. Environ. Sci.-Processes & Impacts 2014, 16, (6), 1300-1308. (49) Epsztein, R.; Nir, O.; Lahav, O.; Green, M., Selective nitrate removal from groundwater using a hybrid nanofiltration-reverse osmosis filtration scheme. Chem. Eng. J. 2015, 279, 372-378. (50) Lauch, R. P.; Guter, G. A., ION-EXCHANGE FOR THE REMOVAL OF NITRATE FROM WELL WATER. J. Amer. Water Works Assoc. 1986, 78, (5), 83-88. (51) Ravishankara, A. R.; Daniel, J. S.; Portmann, R. W., Nitrous Oxide (N2O): The Dominant OzoneDepleting Substance Emitted in the 21st Century. Science 2009, 326, (5949), 123-125. (52) de Vooys, A. C. A.; van Santen, R. A.; van Veen, J. A. R., Electrocatalytic reduction of NO3- on palladium/copper electrodes. J. Mol. Catal. A-Chem. 2000, 154, (1-2), 203-215. (53) Desai, M.; Harvey, R., Inventory of US greenhouse gas emissions and sinks: 1990-2015. Clob. Chang. Biol. 2017, 15, (2009), 1-23. (54) Scherson, Y. D.; Woo, S. G.; Criddle, C. S., Production of Nitrous Oxide From Anaerobic Digester Centrate and Its Use as a co-oxidant of Biogas to Enhance Energy Recovery. Environ. Sci. Technol. 2014, 48, (10), 5612-5619.

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Table of Contents/Abstract Graphic

N2

H H

H2

Pd

NO2NO3-

H

H H

REM Cathode (+ne-)

Cu

H2 O

REM (+ne-)

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