Pyrolyzed Triazine-Based Nanoporous Frameworks Enable

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Pyrolyzed Triazine-based Nanoporous Frameworks Enable Electrochemical CO2 Reduction in Water Xiang Zhu, Chengcheng Tian, Haihong Wu, Yanyan He, Lin He, Hai Wang, Xiaodong Zhuang, Honglai Liu, Chungu Xia, and Sheng Dai ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b13110 • Publication Date (Web): 28 Nov 2018 Downloaded from http://pubs.acs.org on November 30, 2018

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ACS Applied Materials & Interfaces

Pyrolyzed Triazine-based Nanoporous Frameworks Enable Electrochemical CO2 Reduction in Water Xiang Zhu,1,2,4*,‡ Chengcheng Tian,2, ‡ Haihong Wu,1 Yanyan He,3 Lin He,1,* Hai Wang,4 Xiaodong Zhuang,5 Honglai Liu3, Chungu Xia1 and Sheng Dai2,* 1State

Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of

Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, China 2 Chemical 3

Science Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA

School of Chemistry and Chemical Engineering, East China University of Science and

Technology, Shanghai 200230, China 4 Department 5

of chemistry, Texas A&M University, College Station, TX, 77840, USA

School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai

200240, China

KEYWORDS porous organic polymers, conjugated triazine frameworks, sacrificial synthesis, pyridinic N-doped sites, electrochemical CO2 reduction, high CO Faradaic efficiency

ACS Paragon Plus Environment

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ABSTRACT The first study of rational synthesis of triazine-based nanoporous frameworks as electrocatalysts for CO2 reduction reaction (CO2RR) was presented. The resulting optimized framework with rich pyridinic nitrogen-containing sites can selectively reduce CO2 to CO in water with a high Faradaic efficiency of ca. 82% under a moderate overpotential of 560 mV. The key of our success lies in the use of pyridine-based backbones as sacrificial groups inside the triazine framework for in situ generation of CO2RR-active pyridinic N-doped sites during the high-temperature ZnCl2-promoted polymerization process. We anticipate that this study may facilitate new possibilities for the development of porous organic polymers for electrochemical conversion of CO2.

INTRODUCTION Porous organic polymers (POPs) are a group of new advanced porous materials with high stabilities, which can be designed for task-specific applications, including gas adsorption and catalysis.1-8 The past few years have seen a great research effort in rational design and preparation of POPs for the capture and conversion of carbon dioxide (CO2) owing to the high atmospheric CO2 levels and the global urgent need for energy productivity.9, 10 Among various methods, the electrochemical conversion of CO2 to value-added chemicals by using water as a reaction medium represents a promising solution towards a carbon-neutral society.11-22 Yaghi and his co-workers pioneered the first use of crystalline POPs (covalent organic frameworks, COFs) for high-performance electrocatalytic CO2 reduction reaction (CO2RR),23, 24 and the key of their success lies in the installation of CO2RR-active cobalt porphyrin sites within the architecture of the polymeric backbones.25 Despite the fact that a wide variety of POPs have been well


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developed, the construction of POPs for successful electrochemical CO2RR is challenging and remains rare, mainly due to the lack of active sites and the intrinsic sluggish reaction kinetics of the CO2RR and competitive hydrogen evolution from water. Conjugated triazine frameworks (CTFs), emerged as a subclass of POPs, possess excellent porosity, great stability and intrinsic rich doping of nitrogen (N) atoms and have been widely 26-37

studied as potential candidates for a number of applications.

Nevertheless, the

straightforward use of metal-free CTFs as electrode materials for the electrocatalytic reduction of CO2 has never been realized. Indeed, CTFs may present a potential compelling choice for their following attributions: (i) they are N-enriched organic polymers and built from either a lowtemperature trimerization38-40 or high-temperature ZnCl241,

42/P

43-promoted

2O5

ionothermal

process, which gives rises to forming CO2RR-active N-doped sites through modulated polymerization processes. It has been well documented that the incorporation of pyridinic Ndoped sites into carbonaceous materials (such as carbon nanotubes and graphene foam) provides a facile means to decrease the free energy for electrochemical CO2 reduction;44-46 (ii) the intrinsic high porosity is an advantage as it can maximize the density of active sites and afford fast transport of substrates to those active sites. In this context, we hypothesized that imparting triazine-based porous frameworks with rich accessible CO2RR-active pyridinic N-doped sites could enable their electrocatalytic conversion of CO2. Herein, we report a rational synthesis of a pyrolyzed porous triazine-linked framework (TTF) exhibiting high electrocatalytic activity towards the conversion of CO2 to CO in water for the first time, with a peak Faradaic efficiency up to ca. 82% at a moderate overpotential of 560 mV. The critical development is the fabrication of pyridine-based backbones as sacrificial groups for in situ generation of CO2RR-active pyridinic N-doped sites during the high-temperature


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ZnCl2-promoted polymerization process. As confirmed by both electrochemical and physicochemical characterizations, the existence of pyridine linkers within the CTF framework plays a crucial role in achieving such a promising catalytic performance. We hoped that our study could inspire the development of porous triazine-based frameworks for electrochemical CO2 reduction.

EXPERIMENTAL SECTION Pyridine-linked conjugated triazine framework was synthesized by a previously reported ZnCl2catalyzed polymerization method.41 A mixture of 2,6-dicyanopyridine (258 mg) and ZnCl2 (2.72 g) was added into a quartz ampoule inside a glove box. The ampoule was then evacuated, vacumm-sealed, and then heated at 400 °C for 40 h. The resulting black powder was subsequently ground and washed thoroughly with water, dilute HCl, and acetone. The desired product was dried in an oven at 120 °C. Pyrolyzed triazine-based framework (TTF-1) was prepared under a higher temperature29: A mixture of 2,6-dicyanopyridine (258 mg) and ZnCl2 (2.72 g) was added into a quartz ampoule inside a glove box. The ampoule was then evacuated, vacumm-sealed, and then heated at 600 °C for 40 h. TTF-2 was obtained through the similar route. 1,3-dicyanobenzene (256 mg) and ZnCl2 (2.72 g) were employed for the polymerization at 600 °C (40 h).


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RESULTS AND DISCUSSION As shown in Scheme 1, we first prepared the desired pyridine-linked CTF as a sacrificial network at 400 °C based on a known ZnCl2-promoted synthesis approach.26, 42 Detailed synthesis information can be found in the supporting information. 2,6-pyridinedicarbonitrile monomer was rationally used, as we expected that the trimerization condensation at a higher temperature (> 400 °C) would afford in situ conversion of pyridine-based backbones to demanded CO2RRactive N-doped sites due to the inevitable partial carbonization. 37 Incorporation of these desired pyridine rings inside the framework was successfully confirmed by the solid state

13C

NMR

(Figure S1), with the peaks at ca. 120, 138 and 150 ppm attributable to the aromatic carbons in the pyridine ring.42, 47 The signal at ca. 172 ppm originates from the existence of triazine ring. The content of zinc inside the network was examined by the inductively coupled plasma (ICP) mass spectrometry, where 2.8 wt% of zinc was determined. The electrocatalytic CO2RR on the as-prepared framework was subsequently evaluated in a standard two-compartment electrochemical cell.48 Pyridine-linked CTF was sonicated into a mixture of ethanol, Nafion solution and Ketjen black to form a homogeneous ink. The sample ink was dropped on a glassy carbon electrode ensuring a loading density of 1 mg cm-2. Detailed information is provided in the supporting information. Unfortunately, no catalytic activity was obtained (Figure 2c). This result matches well with Kamiya’s recent result,49 where a similar pyridine-linked CTF material was studied as a novel porous support for the immobilization of CO2RR-active metal species (Co, Ni and Cu) for electrocatalytic converting CO2 to CO.


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Scheme 1. Synthetic route of sacrificial pyridine-linked conjugated triazine framework and thermally-treated triazine-based framework (TTF-1).

We then attempted the polymerization process at a much higher temperature of 600 °C (Scheme 1), in an effort to create task-specific CO2RR-active N-doped sites on the surface of the triazine-based material. It should be noted that such high polymerization temperatures (from 400 to 700 °C) have been extensively employed for the construction of CTFs with larger porosity and better conductivity, as a way to improve their gas separation and catalysis performance.50-56 No signals belonging to a pyridine ring was detected in the solid-state NMR, indicating that this


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functional group was decomposed (Figure S2),57 putatively in situ forming N-doped sites in the final material. Unfortunately, the precise location of these N-doped sites can hardly be determined by NMR technique owing to the amorphous structure of the final material and the nature of the synthesis (Figure S3).

28, 29

Furthermore, it has been widely accepted that triazine

motifs could be maintained and partial thermal carbonization can not be avoided under such a high-temperature condition.28, 50, 51, 58 We therefore performed x-ray photoelectron spectroscopy (XPS) to study surface features on the thermally-treated triazine-based framework (TTF-1). Different Cl XPS results were observed. Pyridine-linked CTF shows only inorganic Cl species, which could arise from the remaining ZnCl2 catalyst. However, organic Cl species were found on the surface of TTF-1. We reasoned that ZnCl2 may react with the as-synthesized triazine-linked frameworks under this higher temperature, thus leading to partial carbonization of the organic network. N-doped sties were therefore determined where TTF-1 exhibits an exceptionally high N content of 13.8 at% as anticipated. Pyridinic (398.7 eV, 34.4 %) and pyrrolic (400.4 eV, 34.8 %) nitrogen were the two major different nitrogen species identified by XPS (Figure 1).59 Elemental mapping at the microstructural level by transmission electron microscopy (TEM) with energy dispersive X-ray spectrometry (EDS) further confirms the existence of nitrogen (Figure S4). Accordingly, these CO2RR-active pyridinic N-doped sites could help to improve the electrochemical conversion of CO2 on TTF-1.


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Figure 1. N1s XPS studies of TTF-1 (a and b) and TTF-2 (c and d).

Surface area and porosity of TTF-1 were assessed by nitrogen adsorption-desorption isotherms, which exhibited a Type I adsorption profile (Figure S5). The Brunauer-Emmett-Teller (BET) surface area and total pore volume was determined to be 1234 m2 g-1 and 0.59 cm3 g-1, respectively. The content of zinc was determined to be 2.7 wt% from the ICP measurement. Compared to that in pyridine-linked CTF, similar surface properties of zinc-based sites were observed based on the Zn 2p XPS studies (Figure S6a). In addition, highly porous nature can also be supported by the obtained large CO2 adsorption on TTF-1. It possesses a permanent CO2 uptake of 64.4 cm3 g-1 (~2.8 mmol g-1, Figure S7) based on the CO2 isotherm measurement at 298 K and 1 bar. The existence of micropores was further supported by the pore size distribution curve, which was generated from the CO2 adsorption curve at 273 K (Figure S8). It has been


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realized that highly porous structures could help to enlarge the contact surface between electrode and electrolyte, and therefore improve the charge and mass transfer. Furthermore, the hightemperature treatment (600 °C) could allow for the formation of the framework with a higher electric conductivity. The electric conductivity in TTF-1 was measured to be 3930 S m-1, which is much larger than that in pyridine-linked CTF (2910 S m-1). As a result, we believed that highly porous TTF-1 could realize electrochemical reduction CO2 to CO in water. To confirm this, the electrocatalytic CO2RR on TTF-1 was evaluated. As shown in Figure 2a, a significant increase in the linear sweep voltammetric (LSV) curve was witnessed in the CO2-saturated 0.5 M KHCO3 solution, indicating the reduction of CO2 on TTF-1.25 The cathodic current density reached 3.2 mA cm-2 at -0.8 V vs. RHE. Then, the electrolysis process at various potential from -0.38 V to -0.74 V, and the results were summarized in Figure S6. The gaseous products at each constant potential were analyzed by gas chromatography (GC), and their Faradaic efficiency (FE) was calculated, respectively. Carbon monoxide (CO) was first detected as the major reduction product accompany with the generation of H2. The FE for CO (FECO) over the applied potential range was calculated and shown in Figure 2b. As the overpotential goes higher, the FECO continuously increases and reaches the peak of ca. 82% at -0.68 V, which corresponds to a small applied overpotential (η) of 560 mV. This performance is better than that reported for nitrogen-doped carbon nanotubes (ca. 80% at -0.78 V).45 Given its metal-free nature, it is also comparable to that of a cobalt porphyrin-linked COF (90 % at -0.67 V, η = 550 mV, Table S1) and CTF-supported Ni catalyst (90 % at -0.8 V).24, 49 Despite the fact that the achieved current density on our triazine-based framework is relative low, the CO partial current density (Figure 2c) obtained for TTF-1 at ca. 0.7 V (1.2 mA cm-2) is significantly larger than that determined for CTF-supported Ni and Co based materials (less than 1.0 mA cm-2 at 0.7 V).49 A


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Tafel slop of 125 mV decade-1 was obtained (Figure S10). The electrolysis process of TTF-1 in Ar-saturated 0.5 M KHCO3 was further proceeded and no CO product was detected, excluding the possibility that CO product might originate from the carbon material besides the reduction of CO2 (Figure 2d).25 In addition, no liquid product was formed based on the chromatography analysis (Figure 3).

Figure 2. (a) LSV curves of TF in CO2/Ar-Saturated 0.5 M KHCO3; (b) CO Faradaic efficiency (FECO) of TTF-1 and TTF-2 in CO2-saturated 0.5 M KHCO3. (c) CO partial current density values of TTF-1, TTF-2 and pyridine-linked CTF. (d) CO partial current density of TTF-1 in Ar-saturated and CO2-saturated 0.5 M KHCO3. [Ink preparation: 1 mg of catalyst, 0.5 mg of Ketjenblack and 10 μL of 5 wt% Nafion solution were mixed together and dispersed in 250 uL of ethanol. The mixture was vigorously sonicated for 40 min to form a uniform ink. The ink was


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then drop cast onto a 1×1 cm2 glassy carbon electrode with a size of 1×2 cm2. The catalyst loading density was achieved to be 1 mg cm-2.]

Figure 3. The signal of ion chromatograph for standard-HCOOH (a) and sample (b).

In an effort to further identify the role of pyridine-based backbones for the successful generation of CO2RR-active TTF-1, we further prepared an analogue framework (TTF-2) under the same condition (600 °C) for comparison, using 1,3-dicyanobenzene as a surrogate for 2,6dicyanopyridine (Scheme S2). As determined by the XPS study (Figure 1), a much lower N containing of 6.8 at.% was achieved for porous TTF-2 (SBET = 2522 m2 g-1, Figure S11). Additionally, the zinc content in TTF-2 was measured to be 2.3 wt%. As a result, the maximum FECO thus obtained is only ca. 22 % at -0.43 V (Figure 3b), significantly lower than that of TTF1. FECO decreases with more negative potential applied, which could be due to the increase in the competitive hydrogen evolution reaction from the electrocatalytic water splitting (Figure S12). The resulting CO partial current density is also much lower than that of TTF-1 (Figure 2c).


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Based on the Zn XPS result, the remaining Zn may not play a significant role in determining the CO2RR performance since no catalytic activity was obtained for pyridine-linked CTF and huge CO2 reduction difference was achieved for TTF-1 and TTF-2. We reasoned that the sacrificial pyridine linkers may play a crucial role in achieving such a high-performance catalytic activity. In addition to the high electrocatalytic activity of TTF-1, we further examined its durability, as the stability is another important indicator for the development of new catalysts for electrochemical CO2 reduction. The changes in current density and FECO was summarized and shown in Figure 4. Its chronoamperometric (i~t) responses under a bias potential of -0.54 V (η = 420 mV) was continuously recorded for 12 h. To our delight, no significant loss of the current density was observed throughout the whole test. The catalytic activity (FECO) maintains very well, around ca. 75%. We reasoned that the robust nanoporous architecture could help maintaining the electrocatalytic activity of pyridinic N-doped sites, resulting a high-performance durability.

Figure 4. Stability test of CO2RR on TTF-1.


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CONCLUSIONS In summary, we present a sacrificial synthesis of a pyrolyzed porous triazine-based framework for electrochemical CO2 reduction in water. The resulting framework exhibits a highly selective reduction of CO2 into CO in water, with a high Faradaic efficiency of ca. 82 % under a low applied overpotential of 560 mV. The in situ conversion of pyridine-based backbones inside the architecture of the conjugated triazine framework to pyridinic N-doped sites under the high-temperature ZnCl2-promoted polymerization process plays a crucial role in achieving this success. Given the fact that a wide variety of conjugated triazine frameworks have been built based on various aromatic nitriles,30 we anticipated this new study can open up new possibilities for the rational design and synthesis of porous triazine-based frameworks for electrocatalytic reduction of CO2, evidently advancing the development of porous organic polymers and CO2RR electrocatalysts.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website. Experimental details, Scheme S1, Figure S1-11 and Table S1 can be found. AUTHOR INFORMATION Corresponding Author X.Z., Email: [email protected] ([email protected]). H.L., Email: [email protected]. S.D., Email: [email protected].


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Author Contributions ‡ X.Z.

and C.T. contributed equally.

ACKNOWLEDGMENT This research was supported financially by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, US Department of Energy. Financial supports from National Program for Thousand Young Talents of China, Foundation research project of Jiangsu Province (BK20171242), National Natural Science Foundation of China (21633013) and Key Research Program of Frontier Sciences of CAS (QYZDJ-SSW-SLH051) were much appreciated.

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