Binding Energy Optimization Strategy Inducing Enhanced Catalytic

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Binding Energy Optimization Strategy Inducing Enhanced Catalytic Performance on MIL-100(FeNi) to Directly Catalyze Water Oxidation Changqing Li, Yiwen Liu, Guo Wang, Lihao Guan, and Yuqing Lin ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.9b00264 • Publication Date (Web): 29 Mar 2019 Downloaded from http://pubs.acs.org on April 1, 2019

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ACS Sustainable Chemistry & Engineering

Binding Energy Optimization Strategy Inducing Enhanced Catalytic Performance on MIL-100(FeNi) to Directly Catalyze Water Oxidation Changqing Li1, Yiwen Liu1, Guo Wang, Lihao Guan, and Yuqing Lin*

Department of Chemistry, Capital Normal University, 105 North Road of Western Third Ring, Haidian District, Beijing 100048, China

1

The two authors contributed equally to this paper.

Corresponding author Tel.: +86 1068903047; Fax:+86 1068903047 *E-mail: [email protected]. 1

ACS Paragon Plus Environment

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ABSTRACT Metal-organic frameworks (MOFs) are recently reported with promising perspective to directly catalyze oxygen evolution reaction (OER), while their wide applications are generally limited by its unsatisfied catalytic activity and stability during the reaction process. Herein, we synthesized a Fe and Ni based bimetallic MOFs on 3D nickel foam (NF), i.e. MIL-100(FeNi)/NF via a solvothermal process to directly serve as highly-efficient OER electrocatalysts. The obtained MIL-100(FeNi)/NF requires a low overpotential of 243 mV to deliver the current density of 100 mA cm-2 under a small Tafel slope value of 30.4 mV dec-1. Density functional theory (DFT) calculations reveal that the metal-metal coupling effect plays a crucial role in determining the pronounced OER performance of the formed MIL-100(FeNi). Hopefully, the synthetic strategy and proposed model of bimetallic electrocatalysts (MIL-100(FeNi)) could simulate the exploration of more novel bimetallic or multi-metallic MOFs towards energy storage/conversion application.

Keywords: Metal-organic frameworks, Bimetallic, Electrocatalyst, Nanosphere, Oxygen evolution reaction.

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INTRODUCTION The water splitting is deemed as a viable energy acquisition mode to obtain highlyefficient, clean and sustainable hydrogen energy, which could greatly alleviate the upcoming energy crisis.1,2 However, the sluggish anodic oxygen evolution reaction (OER) on water splitting requires the involvement of active catalysts to accelerate the reaction and minimize the overpotential. To date, the ruthenium and iridium-based noble metal materials are widely accepted as active catalysts towards OER,3 while their high cost, poor stability, and low storage limits the large-scale application of these noble metal based catalysts towards energy conversion and storage field.4 Thus, exploring highlyactive and cost-effective catalysts for OER are highly demanded.3 Recently, earth-abundant transition metal-based materials are widely cultivated as potential OER catalysts.5,6 Representative materials existed in the form of transition metal oxides,7 metal selenides,8 sulfides,9 hydroxides,10 borides,11 and chalcogenides6 have been extensively explored as excellent OER electrocatalysts. Importantly, metalorganic frameworks (MOFs) possesses multiple merits including the well-defined crystalline nature, tunable composition, structure diversity as well as high surface area are widely adopted as versatile precursors to synthesize aforementioned transition metal-based OER catalysts through a high-temperature calcination process.12-14 Nevertheless, the pyrolysis process would unavoidably lead the loss of intrinsic active sites in MOFs,12-15 which thus calls for the development of more advanced method or robust MOFs to address the knotty predicament.

Interestingly, taking the advantages

of homogeneous and heterogeneous catalysts from the structural view, MOFs can be directly utilized to catalyze OER without a high-temperature treatment.16 Furthermore, a bimetal or multi-metal coupling effect can greatly improve the lower catalytic activity on MOFs.17-20 Therefore, Lang reported the tri-metallic MOFs (Fe/Ni/Co(Mn)-(MIL53)) with superior activity and stability as efficient OER cataltsts.21 In spite that those works have realized the directly promising application of MOFs in catalyzing OER,

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exploring novel MOFs and proposing relevant catalytic mechanism on MOFs still remains great challenge. MIL-n (Material of Institute Lavoisier) series MOFs with interesting breathing effect ensuring the enhanced chemical stability toward catalysis field.16,20 Among the MIL-n series MOFs, MIL-100(Fe) constructed by 1,3,5-benzenetricarboxylic acid (BTC) and FeO6 octahedrons not only possesses flexible structure, but also can realize improved stability owing to the existence of high valence metal ions, in which the reversible redox reaction between Fe2+ and Fe3+ could ensure MIL-100(Fe) MOFs as promising candidate towards cathode catalyst.19 Besides that, it was reported the FeNibased catalysts have the state-of-the-art catalytic capability,22 and the FeO6 octahedrons in MIL-100(Fe) can be partially replaced by NiO6 to achieve the integral enhanced performance. Herein, we incorporates a solvothermal route to in-situ develop MIL-100(FeNi) materials, i.e. MIL-100(FeNi)/NF on the surface of 3D nickel foam, as illustrated in Scheme 1. The Ni foam substrate also provides higher electrical conductivity and relatively high specific surface areas to the formed MIL-100(FeNi)/NF electrode for the enhanced mass transport ability. Those factors enable MIL-100(FeNi)/NF with pronounced OER catalytic performance in terms of a higher current density of 100 mA cm-2 could be achieved at a low overpotential 243 mV. Meanwhile, the MIL100(FeNi)/NF also possesses a lower Tafel slope value of 30.4 mV dec-1 as well as satisfied stability in OER catalysis process.

Scheme 1. Synthetic process of MIL-100(FeNi)/NF. 4


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RESULTS AND DISCUSSION Investigation of Morphology and Structure on MIL-100(FeNi). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) technique were introduced to acquire the morphology information of MIL100(FeNi)/NF (Figure 1). As demonstrated in Figure 1a, MIL-100(FeNi)/NF possessed regular nanospheres morphology on Ni foam substrate. Energy dispersive spectroscopy (EDS) analysis in Figure 1e suggested that MIL-100(FeNi) mainly had C, O, Fe, and Ni constitutional elements in surface without other ingredients (Figure S5, Supporting Information). Also, the element ratio measured by EDS revealed that MIL-100(FeNi) had the Fe and Ni atom ratio of around 1:4. Meanwhile, the element mapping images on MIL-100(FeNi) indicated four constitutional elements were uniformly distributed across the entire MIL-100(FeNi) surfaces.

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Figure 1. a) High-magnification SEM image, b) TEM image, c) HRTEM image and d) the corresponding SAED pattern of MIL-100(FeNi)/NF, e) STEM-EDS elemental mapping images of MIL-100(FeNi)/NF before OER.

High-resolution transmission electron microscopy (HRTEM) and corresponding selected-area electron diffraction (SAED) was introduced to further evaluate the morphological and structural character of MIL-100(FeNi)/NF (Figure 1c, d). As can be seen from the HRTEM, the 0.801 nm lattice fringe of MIL-100(FeNi) was assigned to the (248) plane of MIL-100 series composites, which clearly indicated the crystalline property of MIL-100(FeNi). Meanwhile, the SAED pattern (Figure 1d) also confirmed the polycrystalline characters in as-prepared MIL-100(FeNi).17,27

FT-IR, Raman

spectra (Figure S6-7), PXRD pattern (Figure S8), and XPS (Figure S9) also confirmed the successful synthesis of as prepared MIL-100(FeNi). Electrochemical Evaluation of Water Oxidation performance. The electrocatalytic OER performance of MIL-100(FeNi)/NF were measured by applying representative polarization curves in 1.0 M KOH alkaline media. The scan rate was lower to 1 mV s-1 to realize the steady state for accurate analysis. The electrochemical performance of MIL-100(Ni)/NF, MIL-100(Fe)/NF, BTC/NF, RuO2/NF and Ni foam was also evaluated for comparison. As shown in Figure 2a, the Ni foam had the lowest catalytic current density on the whole potential window, which revealed a decrepit OER ability on comparing with other samples. While the electrochemical activity comparison between the MIL-100(FeNi)/NF, MIL-100(Ni)/NF, MIL-100(Fe)/NF, BTC/NF and RuO2/NF electrode clearly indicated that the bimetallic MIL-100(FeNi) possessed the best OER electrocatalytic activity than that of the monometallic Ni and Fe based materials and the benchmark RuO2 catalysts. Therefore, we proposed that the introduction of the Fe atoms to partially substitute the Ni atom in MIL-100(Ni) forming the bimetallic MIL-100(FeNi)/NF was crucial in obtaining the significant OER performance concerning its higher current density and lower onset potential. 6


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Meanwhile, the MIL-100(FeNi)/NF had the Ni redox peak shifted to higher potential compared with the MIL-100(Ni)/NF sample, which suggested the coordination environment change of Ni atom in as prepared MIL-100(FeNi)/NF sample.28 The Tafel plots deduced from the polarization curves was fitted to probe the reaction kinetics information of MIL-100(FeNi)/NF, MIL-100(Ni)/NF, MIL-100(Fe)/NF, BTC/NF, RuO2/NF and bare Ni foam towards OER process. As Figure 2b displayed, the MIL100(FeNi)/NF had the most desirable OER reaction kinetics concerning its lowest Tafel slope value of 30.4 mV dec-1, which was much lower than that of other compared materials, including MIL-100(Ni)/NF (48.7 mV dec-1), MIL-100(Fe)/NF (53.3 mV dec1),

BTC/NF (130.3 mV dec-1), RuO2/NF (207.38 mV dec-1) and bare Ni foam (124.0

mV dec-1). The calculated Cdl on all prepared samples

was depicted in Figure 2c, MIL-

100(FeNi)/NF possessed the largest Cdl value of 4.83 mF cm-2, while the MIL100(Ni)/NF, MIL-100(Fe)/NF, BTC/NF, RuO2/NF and bare Ni foam indicated lower Cdl value of 2.68 mF cm-2, 1.92 mF cm-2, 1.86 mF cm-2, 5.22 mF cm-2, 0.36 mF cm-2, respectively. The larger Cdl value indicated the existence of abundant active sites in the synergistic catalyst of MIL-100(FeNi)/NF, which was responsible for the enhanced OER performance of MIL-100(FeNi)/NF. Furthermore, electrochemical impedance spectroscopy (EIS) was conducted out to evaluate the interfacial reactions and the OER kinetics on prepared samples (Figure 2d). All tested electrodes deliver a similar series resistance value of 1.19 Ω, which referred as the RS value of the electrolyte in equivalent circuit. The charge transfer resistance (Rct) value of MIL-100(FeNi)/NF, MIL100(Ni)/NF, BTC/NF, MIL-100(Fe)/NF and bare Ni foam is 0.41Ω, 0.60 Ω, 0.75 Ω, 1.70 Ω and 2.40 Ω, respectively. The smaller semicircle diameter value of MIL100(FeNi)/NF (0.41 Ω) indicated the fast shuttling of charge transfers, which was associated with the facilitated electron transport migration between the solution and the electrode interface.26 All these results validates the excellent performance of MIL100(FeNi)/NF towards OER catalysis. 7



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Figure 2. a) Polarization curves operated at a scan rate of 1 mV s-1 with the iR compensation level of 98 %, b) Corresponding Tafel slopes, c) ECSA evaluation of MIL-100(FeNi)/NF, MIL-100(Ni)/NF, MIL-100(Fe)/NF, BTC/NF, RuO2/NF and Ni foam, d) Raw (points) and simulated (solid line) data for Nyquist plots from EIS test of MIL-100(FeNi)/NF, MIL-100(Ni)/NF, MIL-100(Fe)/NF, BTC/NF, and Ni foam.

Oxygen Evolution Reaction Mechanism and Theoretical Calculations. In order to explore more affected factors on catalytic activities of the MIL-100(Ni) and MIL100(FeNi), theoretical investigations were performed. The free energy change at 0 standard condition ΔG  ΔG |U  0, pH  0, T  298.15 K

is investigated firstly. The

values for the four steps of the MIL-100(Ni) are 0.55, 4.88, -2.46 and 1.96 eV, respectively. It can be seen that the free energy change for step (2) is the largest. Thus the step (2) is the rate-determining step. The free energy change at standard condition that

determinates

the

G 0OER  max[G 10 , G 02 , G 30 , G 04 ]

whole

oxygen

evolution

reaction

is 4.88 eV. For the MIL-100(FeNi), two cases in

which the small molecules are adsorbed on a Ni or Fe atom were considered. The free 8


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energy changes at standard condition are 1.11, 3.74, -2.31 and 2.38 eV for adsorption on a Ni atom and -1.31, 4.04, -1.29 and 3.48 eV for adsorption on a Fe atom (Figure 3). Similar to the situation for the MIL-100(Ni), the step (2) is also the rate-determining step. Moreover, the reaction is easier to occur when the small molecules are adsorbed on Ni atoms. Only the adsorption on the Ni atoms will be discussed later. The free energy change at standard condition that determinates the whole oxygen evolution reaction is 3.74 eV. Then, if we take the value 1.229 eV for U and consider the experimental pH of 14, the overpotential is 2.82 or 1.68 eV for the MIL-100(Ni) or MIL-100(FeNi). It is noted that the overpotentials are much larger than the experimental values. This is caused by the fragment model, ratio of Fe and Ni atoms, density functional theory and the lowest spin multiplicity approximation. Only the trend that the MIL-100(FeNi) has higher catalytic activity than the MIL-100(Ni) has its meaningful.

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Figure 3. a) Fragment model of MIL-100(Ni) and b) MIL-100(FeNi). c) Standard reaction free energy diagram of OER process on MIL-100(Ni) and MIL-100(FeNi) surface. The model of MIL-100(FeNi) can be obtained by replacing a Ni atom with a Fe atom.

Since the step (2) is the rate-determining step, the oxidation from *OH to *O should be important. The energy of the highest occupied molecular orbital for the MIL100(Ni) or MIL-100(FeNi) is -7.06 or -6.09 eV. An electron in an orbital with higher energy should be easier to be lost. Thus the rate-determining step (2) reaction is easier to occur for the MIL-100(FeNi) and the MIL-100(FeNi) has higher catalytic activity than the MIL-100(Ni) has. This can be explained by the different electronegativities of Fe and Ni elements. It is well known that iron is easier to be oxidized than nickel. The electronegativity of Fe is smaller than that of Ni. Low electronegativity can make the orbital energies increase. When Ni atoms in MIL-100(Ni) are partially replaced by Fe atoms to form the MIL-100(FeNi), the energy of the highest occupied molecular orbital increases, which favors the rate-determining step of *OH oxidization in MIL100(FeNi). This is the reason why the MIL-100(FeNi) has higher catalytic activity than the MIL-100(Ni). Consequently, for the first time, the experimental realities together with DFT theoretical calculation in this study described the developed MIL-100(FeNi) electrodes can effectively catalyze the water oxidation through an electrochemical route. Those high-performance catalytic behaviors can be ascribed to the inherent properties of the MIL-100(FeNi) as following: 1) rich carboxyl groups in BTC enhance the hydrophilicity and availability of OH− on the catalyst surface and improve OER activity; 2) increased electrochemically active areas, reaction sites and electron transport ability also boost electrocatalytic OER activity; 3) the formed bimetallic MIL-100(FeNi) would process a more favorable OER pathway. These clues reasonably endow MIL100(FeNi) with superior catalytic activity than the monometallic MIL-100(Ni). 10


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CONCLUSIONS In conclusion, we have developed a self-assembled route to grow MIL-100(FeNi) nanospheres on Ni foam through the solvothermal process, which can be directly employed as highly-efficient OER catalysts. The enhanced performance of MIL100(FeNi) MOFs is associated with the bimetallic synergistic effect and the optimization on the binding energy involved in OER intermediates (*O, *OH, and *OOH). The experimental studies reveals MIL-100(FeNi)/NF exhibit superior OER performance, which requires a low overpotential of 243 mV to deliver the current density of 100 mA cm-2 with a small Tafel slope of 30.4 mV dec-1 as well as impressive robust stability in alkaline media. We speculate that the present study could pave a way for the preparation of novel MOFs with high activity and stability on electrocatalytic applications.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at http://pub.acs.org Experimental section, digital graph, SEM images, EDS spectrum, FT-IR, Raman spectra, elemental mapping images, XPS spectra, LSV curve, XRD, N2 adsorption/desorption isotherms, plot of CVs, stability response of prepared materials and Table S1. (PDF)

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] (Y. Lin). # Changqing Li, Yiwen Liu contributed equally to this work and should be considered co-first authors. 11



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ORCID Yuqing Lin: 0000-0003-1501-5005

Notes The authors declare no competing financial interest.

ACKNOWLEDGEMENTS This work was financially supported by National Natural Science Foundation (21575090), High-level Teachers in Beijing Municipal Universities in the Period of 13th Five-year Plan (CIT&TCD20190330), Scientific Research Project of Beijing Educational Committee (KM201810028008), Youth Innovative Research Team of Capital Normal University and Capacity Building for Sci-Tech InnovationFundamental Scientific Research Funds (19530050179, 025185305000/195).

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10.1016/j.jhazmat.2015.01.048. (26) Liu, Yao.; Zhou, Y. R.; Zhang, J. X.; Xia, Y. Y.; Chen, T.; Zhang, S. M. Monoclinic Phase Na3Fe2(PO4)3: Synthesis, Structure, and Electrochemical Performance as Cathode Material in Sodium-Ion Batteries. ACS Sustain. Chem. Eng., 2016, 5 (2), 1306-1314, DOI 10.1021/acssuschemeng.6b01536. (27) Bae, S. H.; Kim, J. E.; Randriamahazaka, H.; Moon, S. Y.; Park, J. Y.; Oh, I. K. Electrocatalysts: Seamlessly Conductive 3D Nanoarchitecture of Core-Shell NiCo Nanowire Network for Highly Efficient Oxygen Evolution. Adv. Energy Mater., 2017, 7 (1), 1601492-1601503, DOI 10.1002/aenm.201770001. (28) Trotochaud, L.; Young, S. L.; Ranney, J. K.; Boettcher, S. W. Nickel-Iron Oxyhydroxide Oxygen-Evolution Electrocatalysts: The Role of Intentional and Incidental Iron Incorporation. J. Am. Chem. Soc., 2014, 136 (18), 6744-6753, DOI 10.1021/ja502379c.

Insert Table of Contents artwork: MIL-100(FeNi)/NF could directly serve as highly efficient OER electrocatalysts, which delivers 100 mA cm-2 at low overpotential of 243 mV.

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Binding Energy Optimization Strategy Inducing Enhanced Catalytic

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