Boosting the direct conversion of NH<sub>4</sub>HCO<sub>3</sub> electrolyte to syngas on Ag/Zn zeolitic imidazolate framework derived nitrogen-carbon skeleton

doi:10.1007/s11705-022-2289-1

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (9) : 1196-1207 https://doi.org/10.1007/s11705-022-2289-1

RESEARCH ARTICLE

Boosting the direct conversion of NH₄HCO₃ electrolyte to syngas on Ag/Zn zeolitic imidazolate framework derived nitrogen-carbon skeleton

Huiyi Li¹, Jianmin Gao¹(

), Jingjing Shan², Qian Du¹, Yu Zhang¹, Xin Guo³, Shaohua Wu⁴, Zhijiang Wang²

¹. Institute of Combustion Engineering, School of Energy Science and Engineering, Harbin Institute of Technology, Harbin 150001, China
². MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China
³. Harbin Bolier Co., Ltd., Harbin 150040, China
⁴. Department of Environmental Engineering, Shanxi University, Taiyuan 030006, China

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Abstract

The electrochemical reduction of NH₄HCO₃ to syngas can bypass the high energy consumption of high-purity CO₂ release and compression after the ammonia-based CO₂ capture process. This technology has broad prospects in industrial applications and carbon neutrality. A zeolitic imidazolate framework-8 precursor was introduced with different Ag contents via colloid chemical synthesis. This material was carbonized at 1000 °C to obtain AgZn zeolitic imidazolate framework derived nitrogen carbon catalysts, which were used for the first time for boosting the direct conversion of NH₄HCO₃ electrolyte to syngas. The AgZn zeolitic imidazolate framework derived nitrogen carbon catalyst with a Ag/Zn ratio of 0.5:1 achieved the highest CO Faradaic efficiency of 52.0% with a current density of 1.15 mA·cm^–2 at –0.5 V, a H₂/CO ratio of 1–2 (–0.5 to –0.7 V), and a stable catalytic activity of more than 6 h. Its activity is comparable to that of the CO₂-saturated NH₄HCO₃ electrolyte. The highly discrete Ag-N_x and Zn-N_x nodes may have combined catalytic effects in the catalysts synthesized by appropriate Ag doping and sufficient carbonization. These nodes could increase active sites of catalysts, which is conducive to the transport and adsorption of reactant CO₂ and the stability of *COOH intermediate, thus can improve the selectivity and catalytic activity of CO.

Keywords Ag catalyst zeolitic imidazolate framework CO₂ electroreduction ammonium bicarbonate electrolyte syngas

Corresponding Author(s): Jianmin Gao

About author:

^* These authors contributed equally to this work.

Just Accepted Date: 10 February 2023 Online First Date: 24 April 2023 Issue Date: 29 August 2023

Cite this article:

Huiyi Li,Jianmin Gao,Jingjing Shan, et al. Boosting the direct conversion of NH₄HCO₃ electrolyte to syngas on Ag/Zn zeolitic imidazolate framework derived nitrogen-carbon skeleton[J]. Front. Chem. Sci. Eng., 2023, 17(9): 1196-1207.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2289-1
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I9/1196

Fig.1 Schematic diagram of AgZn-NC-n preparation process.

Fig.2 SEM images of the (a) Zn-NC, (b) AgZn-NC-0.5, (c) AgZn-NC-0.5-800 °C, and (d) AgZn-NC-1 catalysts; particle diameter distributions of (e) Zn-NC, (f) AgZn-NC-0.5, (g) AgZn-NC-0.5-800 °C, and (h) AgZn-NC-1 catalysts.

Tab.1 Zn and Ag content on partial surface in various catalysts determined by EDX

Tab.2 Zn and Ag content in various catalysts determined by ICP

Fig.3 EDX mapping of the (a) Zn-NC, (b) AgZn-NC-0.5, (c) AgZn-NC-0.5-800 °C, and (d) AgZn-NC-1 catalysts (Red, green, purple, and light blue colors represent C, N, Zn, and Ag on the surface, respectively).

Fig.4 TEM, high-resolution TEM images and SAED pattern of the (a) Zn-NC, (b) AgZn-NC-0.5, (c) AgZn-NC-0.5-800 °C, and (d) AgZn-NC-1 catalysts.

Fig.5 (a) XRD patterns of the Zn-NC, AgZn-NC-0.5, AgZn-NC-0.5-800 °C, and AgZn-NC-1 catalysts; (b) N₂ adsorption/desorption plots of Zn-NC, AgZn-NC-0.5, AgZn-NC-0.5-800 °C, and AgZn-NC-1 catalysts.

Tab.3 Elemental quantification determined by XPS for the AgZn-NC-n catalysts (at %)

Tab.4 Proportion of each type N content in AgZn-NC-n (%)

Fig.6 XPS spectra of the Zn-NC, AgZn-NC-0.5, AgZn-NC-0.5-800 °C, and AgZn-NC-1 catalysts: (a) survey, (b) Zn 2p, (c) C 1s, and (d) N 1s spectrum.

Fig.7 (a) LSVs; (b) FEs for CO and H₂; (c)

j H 2

and j_CO; (d) molar ratio of H₂/CO for the Zn-NC, AgZn-NC-0.5, AgZn-NC-0.5-800 °C, and AgZn-NC-1 catalysts in the saturated NH₄HCO₃ electrolyte.

Fig.8 Catalytic stability at –0.5 V for 6 h on the AgZn-NC-0.5 catalyst in the saturated NH₄HCO₃ electrolyte without CO₂ bubbling.

Fig.9 Tafel plots for the Zn-NC, AgZn-NC-0.5, AgZn-NC-0.5-800 °C, and AgZn-NC-1 catalysts in the saturated NH₄HCO₃ electrolyte without CO₂ bubbling.

Fig.10 (a) j_H2 and j_CO at different applied potentials; (b) FEs for Zn-NC with Ar and Zn-NC with CO₂ in the saturated NH₄HCO₃ electrolyte.

1	K Jiang, P Ashworth, S Zhang, X Liang, Y Sun, D Angus. China’s carbon capture, utilization and storage (CCUS) policy: a critical review. Renewable & Sustainable Energy Reviews, 2020, 119: 109601 https://doi.org/10.1016/j.rser.2019.109601
2	L I Eide, M Batum, T Dixon, Z Elamin, A Graue, S Hagen, S Hovorka, B Nazarian, P H Nøkleby, G I Olsen, P Ringrose, R A M Vieira. Enabling large-scale carbon capture, utilisation, and storage (CCUS) using offshore carbon dioxide (CO2) infrastructure developments—a review. Energies, 2019, 12(10): 1945 https://doi.org/10.3390/en12101945
3	D Feng, D Guo, Y Zhang, S Sun, Y Zhao, G Chang, Q Guo, Y Qin. Adsorption-enrichment characterization of CO2 and dynamic retention of free NH3 in functionalized biochar with H2O/NH3·H2O activation for promotion of new ammonia-based carbon capture. Chemical Engineering Journal, 2021, 409: 128193 https://doi.org/10.1016/j.cej.2020.128193
4	W Deng, L Zhang, H Dong, X Chang, T Wang, J Gong. Achieving convenient CO2 electroreduction and photovoltage in tandem using potential-insensitive disordered Ag nanoparticles. Chemical Science, 2018, 9(32): 6599–6604 https://doi.org/10.1039/C8SC02576B
5	Y Zhang, S Wang, D Feng, J Gao, L Dong, Y Zhao, S Sun, Y Huang, Y Qin. Functional biochar synergistic solid/liquid-phase CO2 capture: a review. Energy & Fuels, 2022, 36(6): 2945–2970 https://doi.org/10.1021/acs.energyfuels.1c04372
6	C T Molina, C Bouallou. Assessment of different methods of CO2 capture in post-combustion using ammonia as solvent. Journal of Cleaner Production, 2015, 103: 463–468 https://doi.org/10.1016/j.jclepro.2014.03.024
7	Y Zhang, J Gao, D Feng, Q Du, S Wu, Y Zhao. Optimization of the process of antisolvent crystallization of carbonized ammonia with a low carbon-to-nitrogen ratio. Fuel Processing Technology, 2017, 155: 59–67 https://doi.org/10.1016/j.fuproc.2016.03.012
8	Y Zhang, J Gao, M He, D Feng, Q Du, S Wu. Simulation optimization of a new ammonia-based carbon capture process coupled with low-temperature waste heat utilization. Energy & Fuels, 2017, 31(4): 4219–4225 https://doi.org/10.1021/acs.energyfuels.6b03361
9	Y Zhang, J Gao, D Feng, Q Du, S Wu, Y Zhao. Study on regenerative process of the new carbon capture technique based on antisolvent crystallization to strengthen crystallization. Canadian Journal of Chemical Engineering, 2017, 95(10): 1979–1984 https://doi.org/10.1002/cjce.22827
10	A Sreedhar, I N Reddy, J S Noh. Photocatalytic and electrocatalytic reduction of CO2 and N2 by Ti3C2 MXene supported composites for a cleaner environment: a review. Journal of Cleaner Production, 2021, 328: 129647 https://doi.org/10.1016/j.jclepro.2021.129647
11	Z W Seh, J Kibsgaard, C F Dickens, I Chorkendorff, J K Nørskov, T F Jaramillo. Combining theory and experiment in electrocatalysis: insights into materials design. Science, 2017, 355(6321): eaad4998 https://doi.org/10.1126/science.aad4998
12	J Resasco, L D Chen, E Clark, C Tsai, C Hahn, T F Jaramillo, K Chan, A T Bell. Promoter effects of alkali metal cations on the electrochemical reduction of carbon dioxide. Journal of the American Chemical Society, 2017, 139(32): 11277–11287 https://doi.org/10.1021/jacs.7b06765
13	S Shakeel, A H Anwer, M Z Khan. Nitric acid treated graphite granular cathode for microbial electro reduction of carbon dioxide to acetate. Journal of Cleaner Production, 2020, 269: 122391 https://doi.org/10.1016/j.jclepro.2020.122391
14	Z Ming, Z Kun, D Jun. Overall review of China’s wind power industry: status quo, existing problems and perspective for future development. Renewable & Sustainable Energy Reviews, 2013, 24: 379–386 https://doi.org/10.1016/j.rser.2013.03.029
15	J Liu, J Yang, J Wang, M Yang, C Tian, X He. The research of utilization hours of coal-fired power generation units based on electric energy balance. IOP Conference Series. Earth and Environmental Science, 2018, 108: 052097 https://doi.org/10.1088/1755-1315/108/5/052097
16	H Li, J Gao, Q Du, J Shan, Y Zhang, S Wu, Z Wang. Direct CO2 electroreduction from NH4HCO3 electrolyte to syngas on bromine-modified Ag catalyst. Energy, 2021, 216: 119250 https://doi.org/10.1016/j.energy.2020.119250
17	H Li, J Gao, J Shan, Q Du, Y Zhang, X Guo, M Xie, S Wu, Z Wang. Effect of halogen-modification on Ag catalyst for CO2 electrochemical reduction to syngas from NH4HCO3 electrolyte. Journal of Environmental Chemical Engineering, 2021, 9(6): 106415 https://doi.org/10.1016/j.jece.2021.106415
18	Y Wang, J Zhang. Structural engineering of transition metal-based nanostructured electrocatalysts for efficient water splitting. Frontiers of Chemical Science and Engineering, 2018, 12(4): 838–854 https://doi.org/10.1007/s11705-018-1746-3
19	Z Lei, Y Tan, Z Zhang, W Wu, N Cheng, R Chen, S Mu, X Sun. Defects enriched hollow porous Co-N-doped carbons embedded with ultrafine CoFe/Co nanoparticles as bifunctional oxygen electrocatalyst for rechargeable flexible solid zinc-air batteries. Nano Research, 2020, 14(3): 868–878 https://doi.org/10.1007/s12274-020-3127-8
20	R Wang, X Sun, S Ould-Chikh, D Osadchii, F Bai, F Kapteijn, J Gascon. Metal-organic-framework-mediated nitrogen-doped carbon for CO2 electrochemical reduction. ACS Applied Materials & Interfaces, 2018, 10(17): 14751–14758 https://doi.org/10.1021/acsami.8b02226
21	X Wang, Z Chen, X Zhao, T Yao, W Chen, R You, C Zhao, G Wu, J Wang, W Huang, J Yang, X Hong, S Wei, Y Wu, Y Li. Regulation of coordination number over single Co sites: triggering the efficient electroreduction of CO2. Angewandte Chemie International Edition, 2018, 57(7): 1944–1948 https://doi.org/10.1002/anie.201712451
22	Q Huo, J Li, X Qi, G Liu, X Zhang, B Zhang, Y Ning, Y Fu, J Liu, S Liu. Cu, Zn-embedded MOF-derived bimetallic porous carbon for adsorption desulfurization. Chemical Engineering Journal, 2019, 378: 122106 https://doi.org/10.1016/j.cej.2019.122106
23	R Li, X Ren, X Feng, X Li, C Hu, B Wang. A highly stable metal- and nitrogen-doped nanocomposite derived from Zn/Ni-ZIF-8 capable of CO2 capture and separation. Chemical Communications, 2014, 50(52): 6894–6897 https://doi.org/10.1039/c4cc01087f
24	Z Zhang, S Xian, Q Xia, H Wang, Z Li, J Li. Enhancement of CO2 adsorption and CO2/N2 selectivity on ZIF-8 via postsynthetic modification. AIChE Journal, 2013, 59(6): 2195–2206 https://doi.org/10.1002/aic.13970
25	W Zhang, Y Hu, L Ma, G Zhu, Y Wang, X Xue, R Chen, S Yang, Z Jin. Progress and perspective of electrocatalytic CO2 reduction for renewable carbonaceous fuels and chemicals. Advancement of Science, 2018, 5(1): 1700275
26	Z Wang, H Jin, T Meng, K Liao, W Meng, J Yang, D He, Y Xiong, S Mu. Fe, Cu-coordinated ZIF-derived carbon framework for efficient oxygen reduction reaction and zinc-air batteries. Advanced Functional Materials, 2018, 28(39): 1802596 https://doi.org/10.1002/adfm.201802596
27	V Nallathambi, J W Lee, S P Kumaraguru, G Wu, B N Popov. Development of high performance carbon composite catalyst for oxygen reduction reaction in PEM proton exchange membrane fuel cells. Journal of Power Sources, 2008, 183(1): 34–42 https://doi.org/10.1016/j.jpowsour.2008.05.020
28	I Herrmann, U I Kramm, S Fiechter, P Bogdanoff. Oxalate supported pyrolysis of CoTMPP as electrocatalysts for the oxygen reduction reaction. Electrochimica Acta, 2009, 54(18): 4275–4287 https://doi.org/10.1016/j.electacta.2009.02.056
29	K Sun, L Wu, W Qin, J Zhou, Y Hu, Z Jiang, B Shen, Z Wang. Enhanced electrochemical reduction of CO2 to CO on Ag electrocatalysts with increased unoccupied density of states. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2016, 4(32): 12616–12623 https://doi.org/10.1039/C6TA04325A
30	Y S Ham, S Choe, M J Kim, T Lim, S K Kim, J J Kim. Electrodeposited Ag catalysts for the electrochemical reduction of CO2 to CO. Applied Catalysis B: Environmental, 2017, 208: 35–43 https://doi.org/10.1016/j.apcatb.2017.02.040
31	M N Hossain, Z Liu, J Wen, A Chen. Enhanced catalytic activity of nanoporous Au for the efficient electrochemical reduction of carbon dioxide. Applied Catalysis B: Environmental, 2018, 236: 483–489 https://doi.org/10.1016/j.apcatb.2018.05.053
32	S Lee, G Park, J Lee. Importance of Ag–Cu biphasic boundaries for selective electrochemical reduction of CO2 to ethanol. ACS Catalysis, 2017, 7(12): 8594–8604 https://doi.org/10.1021/acscatal.7b02822
33	J Gao, S Zhao, S Guo, H Wang, Y Sun, B Yao, Y Liu, H Huang, Z Kang. Carbon quantum dot-covered porous Ag with enhanced activity for selective electroreduction of CO2 to CO. Inorganic Chemistry Frontiers, 2019, 6(6): 1453–1460 https://doi.org/10.1039/C9QI00217K
34	J Rosen, G S Hutchings, Q Lu, S Rivera, Y Zhou, D G Vlachos, F Jiao. Mechanistic insights into the electrochemical reduction of CO2 to CO on nanostructured Ag surfaces. ACS Catalysis, 2015, 5(7): 4293–4299 https://doi.org/10.1021/acscatal.5b00840
35	T Li, E W Lees, M Goldman, D A Salvatore, D M Weekes, C P Berlinguette. Electrolytic conversion of bicarbonate into CO in a flow cell. Joule, 2019, 3(6): 1487–1497 https://doi.org/10.1016/j.joule.2019.05.021
36	R Sui, J Pei, J Fang, X Zhang, Y Zhang, F Wei, W Chen, Z Hu, S Hu, W Zhu, Z Zhuang. Engineering Ag-Nx single-atom sites on porous concave N-doped carbon for boosting CO2 electroreduction. ACS Applied Materials & Interfaces, 2021, 13(15): 17736–17744 https://doi.org/10.1021/acsami.1c03638
37	C Y Lee, Y Zhao, C Wang, D R G Mitchell, G G Wallace. Rapid formation of self-organised Ag nanosheets with high efficiency and selectivity in CO2 electroreduction to CO. Sustainable Energy & Fuels, 2017, 1(5): 1023–1027 https://doi.org/10.1039/C7SE00069C

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[4]	Joseph LEE, Bo FENG. A thermodynamic study of the removal of HCl and H₂S from syngas[J]. Front Chem Sci Eng, 2012, 6(1): 67-83.
[5]	Bowu CHENG, Zhaofei CAO, Yong BAI, Dexiang ZHANG. Preparation and selection of Fe-Cu sorbent for COS removal in syngas[J]. Front Chem Eng Chin, 2010, 4(4): 441-444.
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