Integration of ultrafine CuO nanoparticles with two-dimensional MOFs for enhanced electrochemical CO2 reduction to ethylene

doi:10.1016/S1872-2067(21)63947-5

Abstract

Abstract:

To facilitate the electrochemical CO₂ reduction (ECR) to fuels and valuable chemicals, the development of active, low cost, and selective catalysts is crucial. We report a novel ECR catalyst consisting of CuO nanoparticles with sizes ranging from 1.4 to 3.3 nm anchored on Cu metal-organic framework (Cu-MOF) nanosheets obtained through a one-step facile solvothermal method. The nanocomposites provide multiple sites for efficient ambient ECR, delivering an average C₂H₄ faradaic efficiency (FE) of ~50.0% at -1.1 V (referred to the reversible hydrogen electrode) in 0.1 mol/L aqueous KHCO₃ using a two-compartment cell, in stark contrast to a C₂H₄ FE of 25.5% and 37.6% over individual CuO and Cu-MOF respectively, also surpassing most newly reported Cu-based materials under similar cathodic voltages. The C₂H₄ FE remains at over 45.0% even after 10.0 h of successive polarization. Also, a ~7.0 mA cm^-2C₂H₄ partial geometric current density and 27.7% half-cell C₂H₄ power conversion efficiency are achieved. The good electrocatalytic performance can be attributed to the interface between CuO and Cu-MOF, with accessible metallic moieties and the unique two-dimensional structure of the Cu-MOF enhancing the adsorption and activation of CO₂ molecules. This finding offers a simple avenue to upgrading CO₂ to value-added hydrocarbons by rational design of MOF-based composites.

Key words: Carbon dioxide reduction, Electrocatalysis, Copper oxide, Metal-organic framework, Ethylene

Linlin Wang, Xin Li, Leiduan Hao, Song Hong, Alex W. Robertson, Zhenyu Sun. Integration of ultrafine CuO nanoparticles with two-dimensional MOFs for enhanced electrochemical CO₂ reduction to ethylene[J]. Chinese Journal of Catalysis, 2022, 43(4): 1049-1057.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63947-5

https://www.cjcatal.com/EN/Y2022/V43/I4/1049

Figures/Tables 5

Fig. 1. (a) Schematic of the synthesis of CuO/Cu-MOF composite; (b) XRD patterns of CuO/Cu-MOF and simulated Cu-BDC MOF; (c) FT-IR, (d) Cu 2p XPS, and (e) O 1s XPS spectra of CuO/Cu-MOF; (f) N2 adsorption-desorption profiles of CuO/Cu-MOF; (g) CO2 desorption curves of CuO/Cu-MOF and commercial CuO [CuO (coml)].

Fig. 2. Low-magnification (a) and high-magnification (b) HAADF-STEM images of CuO/Cu-MOF composite. EDS elemental maps of Cu (c), O (d), C (e), and N (f) over the region depicted in image (b), along with corresponding EDS spectrum (g). (h,i,k) High-resolution STEM images of CuO/Cu-MOF; The inset in (i) shows size distribution of CuO NPs; (j) Transformed STEM image of (k). (l,m) Enlarged STEM images of the areas enclosed in the dashed squares in (k). (n,o) Corresponding FFT patterns of the regions shown in (l and m).

Fig. 3. (a) LSV profiles of CuO/Cu-MOF in Ar- (black dotted line) or CO2- (red solid line) saturated 0.1 mol/L KHCO3 solution with a scan rate of 5.0 mV s?1; (b) ECR FE (bar) and overall current density (ball) against applied potential over CuO/Cu-MOF electrode in CO2-purged 0.1 mol/L KHCO3; (c) ECR FE (bar) and overall current density (ball) of CuO/Cu-MOF against mole ratio of 1,4-BDC and Cu(NO3)2·3H2O; (d) ECR FE (bar) and partial current density (ball) of CuO/Cu-MOF obtained with distinct copper precursor types together with Cu-MOF and CuO. Data in Fig. 3(b)?(d) are represented as mean ± SE.

Fig. 4. (a) ECR FE (bar) and C2H4 partial geometric current density (ball) of CuO/Cu-MOF obtained at varying conditions (solvothermal temperature, linker type), commercial Cu(OH)2, 1,4-BDC, CuO, Cu2O, and Cu powder; (b) ECR FE (bar) and C2H4 geometric current density (ball) of CuO/Cu-MOF in various electrolytes. The concentration of anions in various mixed electrolytes is 0.1 mol/L while the concentration of K+in all the cases is 0.2 mol/L. The cathodic potential applied is -1.1 V. Data are represented as mean ± SE.

Fig. 5. C2H4 FEs (a) and C2H4 EEs (b) of CuO/Cu-MOF and previously demonstrated Cu-based materials (summarized in Table S1) in an H-type cell; (c) Tafel plots for C2H4 production of CuO/Cu-MOF, neat Cu-MOF, and CuO; (d) Nyquist curves with corresponding fitting profiles for CuO/Cu-MOF, CuO, and Cu-MOF. The inset depicts the equivalent circuit used for fitting the data, where RS shows the combination of the resistance of electrodes and electrolyte, CPE and Rct represent the capacitance and charge transfer resistance of working electrode-electrolyte interface, respectively. (e) C2H4 FEs (bar) and corresponding partial current densities (ball) for CuO/Cu-MOF during cycles at -1.1 V with an interval of 1.0 h in CO2- and Ar-purged 0.1 mol/L KHCO3. Data are represented as mean ± SE. (f) Current density and C2H4 FE as function of time for electrolysis at a controlled cathodic voltage of -1.1 V. The mole ratio of 1,4-BDC and Cu(NO3)2·3H2O and solvothermal temperature used for the synthesis of CuO/Cu-MOF are 3:1 and 100.0 °C unless specified otherwise.

References

[1]	Q. Fan, M. L. Zhang, M. W. Jia, S. Z. Liu, J. S. Qiu, Z. Y. Sun, Mater. Today Energy, 2018, 10, 280-301.
[2]	H. C. Tao, Q. Fan, T. Ma, S. Z. Liu, H. Gysling, J. Texter, Z. Y. Sun, Prog. Mater. Sci., 2020, 111, 100637.
[3]	Y. Zhou, N. Han, Y. Li, Acta Phys.-Chim. Sin., 2020, 36, 2001041.
[4]	C. Yan, L. Lin, G. X. Wang, X. H. Bao, Chin. J. Catal., 2019, 40, 23-27.
[5]	J. Shao, Y. Wang, D. Gao, K. Ye, Q. Wang, G. Wang, Chin. J. Catal., 2020, 41, 1393-1400.
[6]	G. Li, Y. Qin, Y. Wu, L. Pei, Q. Hu, H. Yang, Q. Zhang, J. Liu, C. He, Chin. J. Catal., 2020, 41, 830-838.
[7]	H. Bao, Y. Qiu, X. Peng, J.-A. Wang, Y. Mi, S. Zhao, X. Liu, Y. Liu, R. Cao, L. Zhuo, J. Ren, J. Sun, J. Luo, X. Sun, Nat. Commun., 2021, 12, 238.
[8]	Y. Mi, Y. Qiu, Y. Liu, X. Peng, M. Hu, S. Zhao, H. Cao, L. Zhuo, H. Li, J. Ren, X. Liu, J. Luo, Adv. Funct. Mater., 2020, 30, 2003438.
[9]	F. Lv, N. Han, Y. Qiu, X. Liu, J. Luo, Y. Li, Coord. Chem. Rev., 2020, 422, 213435.
[10]	J. Xu, S. Lai, M. Hu, S. Ge, R. Xie, F. Li, D. Hua, H. Xu, H. Zhou, R. Wu, J. Fu, Y. Qiu, J. He, C. Li, H. Liu, Y. Liu, J. Sun, X. Liu, J. Luo, Small Methods, 2020, 4, 2000567.
[11]	S. Gao, Y. Liu, Z. Xie, Y. Qiu, L. Zhuo, Y. Qin, J. Ren, S. Zhang, G. Hu, J. Luo, X. Liu, Small Methods, 2021, 5, 2001039.
[12]	T. Ma. Q. Fan, X. Li, J. S. Qiu, T. B. Mu, Z. Y. Sun, J. CO₂ Utiliz., 2019, 30, 168-182.
[13]	Z. Liu, Acta Phys.-Chim. Sin., 2020, 36, 1912045.
[14]	Z. Y. Sun, T. Ma, H. C. Tao, Q. Fan, B. X. Han, Chem, 2017, 3, 560-587.
[15]	Y. Zhou, F. Che, M. Liu, C. Zou, Z. Liang, P. De Luna, H. Yuan, J. Li, Z. Wang, H. Xie, H. Li, P. Chen, E. Bladt, R. Quintero-Bermudez, T.-K. Sham, S. Bals, J. Hofkens, D. Sinton, G. Chen, E. H. Sargent, Nat. Chem., 2018, 10, 974-980.
[16]	A. Vasileff, C. C. Xu, Y. Jiao, Y. Zheng, S. Z. Qiao, Chem, 2018, 4, 1809-1831.
[17]	Y. A. Wu, I. McNulty, C. Liu, K. C. Lau, Q. Liu, A. P. Paulikas, C. J. Sun, Z. H. Cai, J. R. Guest, Y. Ren, V. Stamenkovic, L. A. Curtiss, Y. Z. Liu, T. Rajh, Nat. Energy, 2019, 4, 957-968.
[18]	S. L. Chu, X. P. Yan, C. Choi, S. Hong, A. W. Robertson, J. Masa, B. X. Han, Y. S. Jung, Z. Y. Sun, Green Chem., 2020, 22, 6540-6546.
[19]	W. Luc, X. B. Fu, J. J. Shi, J. J. Lv, M. Jouny, B. H. Ko, Y. B. Xu, Q. Tu, X. B. Hu, J. S. Wu, Q. Yue, Y. Y. Liu, F. Jiao, Y. J. Kang, Nat. Catal., 2019, 2, 423-430.
[20]	L. D. Hao, Q. N. Xia, Q. Zhang, J. Masa, Z. Y. Sun, Chin. J. Catal., 2021, 42, 1903-1920.
[21]	H. B. Aiyappa, J. Masa, C. Andronescu, M. Muhler, R. A. Fischer, W. Schuhmann, Small Methods, 2019, 3, 1800415.
[22]	C. S. Diercks, Y. Z. Liu, K. E. Cordova, O. M. Yaghi, Nat. Mater., 2018, 17, 301-307.
[23]	Z. Weng, Y. Wu, M. Wang, J. Jiang, K. Yang, S. Huo, X.-F. Wang, Q. Ma, G. W. Brudvig, V. S. Batista, Y. Liang, Z. Feng, H. Wang, Nat. Commun., 2018, 9, 415.
[24]	R. Senthil Kumar, S. Senthil Kumar, M. Aabu Kulandainathan, Electrochem. Commun., 2012, 25, 70-73.
[25]	J.-X. Wu, S.-Z. Hou, X.-D. Zhang, M. Xu, H.-F. Yang, P.-S. Cao, Z.-Y. Gu, Chem. Sci., 2019, 10, 2199-2205.
[26]	J. Albo, D. Vallejo, G. Beobide, O. Castillo, P. Castano, A. Irabien, ChemSusChem, 2017, 10, 1100-1109.
[27]	F. Yang, A. Chen, P. Deng, Y. Zhou, Z. Shahid, H. Liu, B. Y. Xia, Chem. Sci., 2019, 10, 7975-7981.
[28]	K. Huang, S. Guo, R. Wang, S. Lin, N. Hussain, H. Wei, B. Deng, Y. Long, M. Lei, H. Tang, H. Wu, Chin. J. Catal., 2020, 41, 1754-1760.
[29]	J.-D. Yi, D.-H. Si, R. Xie, Q. Yin, M.-D. Zhang, Q. Wu, G.-L. Chai, Y.-B. Huang, R. Cao, Angew. Chem. Int. Ed., 2021, 60, 17108-17114.
[30]	L. Majidi, A. Ahmadiparidari, N. Shan, S. N. Misal, K. Kumar, Z. Huang, S. Rastegar, Z. Hemmat, X. Zou, P. Zapol, J. Cabana, L. A. Curtiss, A. Salehi-Khojin, Adv. Mater., 2021, 33, 2004393.
[31]	Z. Meng, J. Luo, W. Li, K. A. Mirica, J. Am. Chem. Soc., 2020, 142, 21656-21669.
[32]	X.-F. Qiu, H.-L. Zhu, J.-R. Huang, P.-Q. Liao, X.-M. Chen, J. Am. Chem. Soc., 2021, 143, 7242-7246.
[33]	F. Y. Zhang, J. L. Zhang, B. X. Zhang, L. R. Zheng, X. Y. Cheng, Q. Wan, B. X. Han, J. Zhang, Nat. Commun., 2020, 11, 1431.
[34]	H. M. T. Galvis, J. H. Bitter, C. B. Khare, M. Ruitenbeek, A. Dugulan, K. P. de Jong, Science, 2012, 335, 835-838
[35]	Z. Tavakoli, J. CO₂ UtiliZ., 2020, 41, 101288.
[36]	G. Kliche, Z. V. Popovic, Phys. Rev. B, 1990, 42, 10060-10066.
[37]	Y. Q. Jiang, C. Choi, S. Hong, S. L. Chu, T. S. Wu, Y. L. Soo, L. Hao, Y. S. Jung, Z. Y. Sun, Cell Rep. Phys. Sci., 2021, 2, 100356.
[38]	M. W. Jia, S. Hong, T. S. Wu, X. Li, Y. L. Soo, Z. Y. Sun, Chem. Commun., 2019, 55, 12024-12027.
[39]	S. Dieckhöfer, D. Öhl, J. R. C. Junqueira, T. Quast, T. Turek, W. Schuhmann, Chem. Eur. J., 2021, 27, 5906-5912.
[40]	X. Zhang, J. C. Li, Y. Y. Li, Y. Jung, Y. Kuang, G. Z. Zhu, Y. Y. Liang, H. G. Dai, J. Am. Chem. Soc., 2021, 143, 3245-3255.
[41]	N. Altaf, S. Y. Liang, L. Huang, Q. Wang, J. Energy Chem., 2020, 48, 169-180.
[42]	Y. Yang, Y. Zhang, J.-S. Hu, L.-J. Wan, Acta Phys.-Chim. Sin., 2020, 36, 1906085.

Integration of ultrafine CuO nanoparticles with two-dimensional MOFs for enhanced electrochemical CO₂ reduction to ethylene

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 5

References

Related Articles 15

Recommended Articles

Metrics

[1]	Xiaolong Tang, Feng Li, Fang Li, Yanbin Jiang, Changlin Yu. Single-atom catalysts for the photocatalytic and electrocatalytic synthesis of hydrogen peroxide [J]. Chinese Journal of Catalysis, 2023, 52(9): 79-98.
[2]	Ji Zhang, Aimin Yu, Chenghua Sun. Theoretical insights into heteronuclear dual metals on non-metal doped graphene for nitrogen reduction reaction [J]. Chinese Journal of Catalysis, 2023, 52(9): 263-270.
[3]	Jin-Nian Hu, Ling-Chan Tian, Haiyan Wang, Yang Meng, Jin-Xia Liang, Chun Zhu, Jun Li. Theoretical screening of single-atom electrocatalysts of MXene-supported 3d-metals for efficient nitrogen reduction [J]. Chinese Journal of Catalysis, 2023, 52(9): 252-262.
[4]	Yan Hong, Qi Wang, Ziwang Kan, Yushuo Zhang, Jing Guo, Siqi Li, Song Liu, Bin Li. Recent progress in advanced catalysts for electrochemical nitrogen reduction reaction to ammonia [J]. Chinese Journal of Catalysis, 2023, 52(9): 50-78.
[5]	Hui Gao, Gong Zhang, Dongfang Cheng, Yongtao Wang, Jing Zhao, Xiaozhi Li, Xiaowei Du, Zhi-Jian Zhao, Tuo Wang, Peng Zhang, Jinlong Gong. Steering electrochemical carbon dioxide reduction to alcohol production on Cu step sites [J]. Chinese Journal of Catalysis, 2023, 52(9): 187-195.
[6]	Xinyi Zou, Jun Gu. Strategies for efficient CO₂ electroreduction in acidic conditions [J]. Chinese Journal of Catalysis, 2023, 52(9): 14-31.
[7]	Shijie Li, Chunchun Wang, Kexin Dong, Peng Zhang, Xiaobo Chen, Xin Li. MIL-101(Fe)/BiOBr S-scheme photocatalyst for promoting photocatalytic abatement of Cr(VI) and enrofloxacin antibiotic: Performance and mechanism [J]. Chinese Journal of Catalysis, 2023, 51(8): 101-112.
[8]	Fei Yan, Youzi Zhang, Sibi Liu, Ruiqing Zou, Jahan B Ghasemi, Xuanhua Li. Efficient charge separation by a donor-acceptor system integrating dibenzothiophene into a porphyrin-based metal-organic framework for enhanced photocatalytic hydrogen evolution [J]. Chinese Journal of Catalysis, 2023, 51(8): 124-134.
[9]	Bo Zhou, Jianqiao Shi, Yimin Jiang, Lei Xiao, Yuxuan Lu, Fan Dong, Chen Chen, Tehua Wang, Shuangyin Wang, Yuqin Zou. Enhanced dehydrogenation kinetics for ascorbic acid electrooxidation with ultra-low cell voltage and large current density [J]. Chinese Journal of Catalysis, 2023, 50(7): 372-380.
[10]	Huijie Li, Manzhou Chi, Xing Xin, Ruijie Wang, Tianfu Liu, Hongjin Lv, Guo-Yu Yang. Highly selective photoreduction of CO₂ catalyzed by the encapsulated heterometallic-substituted polyoxometalate into a photo-responsive metal-organic framework [J]. Chinese Journal of Catalysis, 2023, 50(7): 343-351.
[11]	Yuannan Wang, Lina Wang, Kexin Zhang, Jingyao Xu, Qiannan Wu, Zhoubing Xie, Wei An, Xiao Liang, Xiaoxin Zou. Electrocatalytic water splitting over perovskite oxide catalysts [J]. Chinese Journal of Catalysis, 2023, 50(7): 109-125.
[12]	Na Zhou, Jiazhi Wang, Ning Zhang, Zhi Wang, Hengguo Wang, Gang Huang, Di Bao, Haixia Zhong, Xinbo Zhang. Defect-rich Cu@CuTCNQ composites for enhanced electrocatalytic nitrate reduction to ammonia [J]. Chinese Journal of Catalysis, 2023, 50(7): 324-333.
[13]	Sang Eon Jun, Sungkyun Choi, Jaehyun Kim, Ki Chang Kwon, Sun Hwa Park, Ho Won Jang. Non-noble metal single atom catalysts for electrochemical energy conversion reactions [J]. Chinese Journal of Catalysis, 2023, 50(7): 195-214.
[14]	Qing Niu, Linhua Mi, Wei Chen, Qiujun Li, Shenghong Zhong, Yan Yu, Liuyi Li. Review of covalent organic frameworks for single-site photocatalysis and electrocatalysis [J]. Chinese Journal of Catalysis, 2023, 50(7): 45-82.
[15]	Shuaiqi Meng, Zhongyu Li, Peng Zhang, Francisca Contreras, Yu Ji, Ulrich Schwaneberg. Deep learning guided enzyme engineering of Thermobifida fusca cutinase for increased PET depolymerization [J]. Chinese Journal of Catalysis, 2023, 50(7): 229-238.