Carbonized metal-organic framework for carbon dioxide reduction to ethylene and ethanol

doi:10.11949/0438-1157.20220250

Abstract

Abstract:

Electrochemical catalytic reduction of carbon dioxide provides an efficient route for energy storage. Exploring efficient electrocatalysts with high ethylene selectivity and high yields is highly desirable but still challenging. Here, porous Cu-Cu₂O/C catalysts were prepared by simple carbonization of metal-organic framework (Cu-BTC) for efficient and selective electrocatalytic reduction of CO₂ to C₂₊ products. The carbonized MOF showed efficient performance for CO₂ reduction to C₂₊, with a maximum FE of 47.8% and a partial current density of 4.33 mA·cm^-2 at a potential of -1.3 V (vs RHE). The results show that the lower carbonization temperature is helpful to preserve the morphology of Cu-MOF, and the porous properties can also improve the electrochemical active area of Cu-MOF, and thus improve its performance for the electrochemical reduction of CO₂ to C₂₊ products.

Key words: Cu-BTC, carbonization, carbon dioxide reduction, electrocatalysis, ethylene

摘要：

电化学催化还原二氧化碳是一种有效的能源储存手段。探索具有高乙烯选择性和高产率的高效电催化剂是非常必要的，但仍然具有挑战性。通过对金属有机骨架（Cu-BTC）的简单碳化制备了多孔Cu-Cu₂O/C催化剂，用于高效且选择性地电催化CO₂还原为C₂₊产物。碳化的MOF表现出优异的还原CO₂为C₂₊的性能，在电位为-1.3 V（vs RHE）时，C₂₊的最大法拉第效率（FE）为47.8%，其部分电流密度为4.33 mA·cm^-2。研究表明，较低的碳化温度有助于保留Cu-MOF的形貌，抑制活性金属位点团聚，而多孔特性也能提升其电化学活性面积，进而提高其对CO₂电化学还原为C₂₊产物的性能。

关键词: Cu-BTC, 碳化, 二氧化碳还原, 电催化, 乙烯

CLC Number:

TQ 151.1

Lei WANG, Yong JIANG, Dazhong ZHONG, Jiayuan LI, Genyan HAO, Qiang ZHAO, Jinping LI. Carbonized metal-organic framework for carbon dioxide reduction to ethylene and ethanol[J]. CIESC Journal, 2022, 73(8): 3576-3585.

王磊, 蒋勇, 钟达忠, 李佳元, 郝根彦, 赵强, 李晋平. 碳化的MOF用于电催化还原二氧化碳制备乙烯和乙醇[J]. 化工学报, 2022, 73(8): 3576-3585.

Figures/Tables 9

Fig.1 Sample preparation flow chart and characterization of Cu-BTC

Fig.2 Thermogravimetric analysis (TGA) curves of pristine Cu-BTC in N2 atmosphere

Fig.3 Structural characterization and SEM images of Cu-BTC-X

Fig.4 TEM, HRTEM, and TEM EDX of Cu-BTC-300℃

Fig.5 Comparison of Faradic efficiency of Cu-BTC-X products and C2+ products

Fig.6 Total current density, partial current density of C2+ products and H2， and EIS spectra of Cu-BTC-X and stability test result of Cu-BTC-300℃

Fig.7 Time and current density of potentiostatic -1.1 V reduction; XRD patterns of Cu-BTC-300℃ before and after reduction; TEM of Cu-BTC-300℃ after reduction

Fig.8 CV curves collected in N2-saturated 0.1 mol·L-1 KHCO3 with different scan rates and the corresponding charging current density difference vs scan rate plots of Cu-BTC-X[Double-layer capacitance (Cdl) is equal to half of the linear slope]

Fig.9 XRD patterns, SEM, FE of Cu-BTC-300℃ after agitator treating of H2SO4, and comparison of current density before and after agitator treating of H2SO4

References 33

1	Goeppert A, Czaun M, Jones J P, et al. Recycling of carbon dioxide to methanol and derived products — closing the loop[J]. Chemical Society Reviews, 2014, 43(23): 7995-8048.
2	Kagawa S, Suh S, Hubacek K, et al. CO₂ emission clusters within global supply chain networks: implications for climate change mitigation[J]. Global Environmental Change, 2015, 35: 486-496.
3	Markewitz P, Kuckshinrichs W, Leitner W, et al. Worldwide innovations in the development of carbon capture technologies and the utilization of CO₂ [J]. Energy & Environmental Science, 2012, 5(6): 7281.
4	Atsonios K, Panopoulos K D, Kakaras E. Thermocatalytic CO₂ hydrogenation for methanol and ethanol production: process improvements[J]. International Journal of Hydrogen Energy, 2016, 41(2): 792-806.
5	Fu Y H, Sun D R, Chen Y J, et al. An amine-functionalized titanium metal-organic framework photocatalyst with visible-light-induced activity for CO₂ reduction[J]. Angewandte Chemie International Edition, 2012, 51(14): 3364-3367.
6	Habisreutinger S N, Schmidt-Mende L, Stolarczyk J K. Photocatalytic reduction of CO₂ on TiO₂ and other semiconductors[J]. Angewandte Chemie International Edition, 2013, 52(29): 7372-7408.
7	Costentin C, Robert M, Savéant J M. Catalysis of the electrochemical reduction of carbon dioxide[J]. Chemical Society Reviews, 2013, 42(6): 2423-2436.
8	Qiao J L, Liu Y Y, Hong F, et al. A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels[J]. Chemical Society Reviews, 2014, 43(2): 631-675.
9	Gu Z X, Shen H, Shang L M, et al. Nanostructured copper-based electrocatalysts for CO₂ reduction[J]. Small Methods, 2018, 2(11): 1800121.
10	Nitopi S, Bertheussen E, Scott S B, et al. Progress and perspectives of electrochemical CO₂ reduction on copper in aqueous electrolyte[J]. Chemical Reviews, 2019, 119(12): 7610-7672.
11	El-Zahab B, Donnelly D, Wang P. Particle-tethered NADH for production of methanol from CO₂ catalyzed by coimmobilized enzymes[J]. Biotechnology and Bioengineering, 2008, 99(3): 508-514.
12	Bhatia S K, Bhatia R K, Jeon J M, et al. Carbon dioxide capture and bioenergy production using biological system — a review[J]. Renewable and Sustainable Energy Reviews, 2019, 110: 143-158.
13	Lu Q, Rosen J, Zhou Y, et al. A selective and efficient electrocatalyst for carbon dioxide reduction[J]. Nature Communications, 2014, 5: 3242.
14	Mistry H, Varela A S, Bonifacio C S, et al. Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene[J]. Nature Communications, 2016, 7: 12123.
15	Luc W, Collins C, Wang S W, et al. Ag-Sn bimetallic catalyst with a core-shell structure for CO₂ reduction[J]. Journal of the American Chemical Society, 2017, 139(5): 1885-1893.
16	Lv W X, Zhou J, Bei J J, et al. Electrodeposition of nano-sized bismuth on copper foil as electrocatalyst for reduction of CO₂ to formate[J]. Applied Surface Science, 2017, 393: 191-196.
17	Jouny M, Luc W, Jiao F. High-rate electroreduction of carbon monoxide to multi-carbon products[J]. Nature Catalysis, 2018, 1(10): 748-755.
18	Zhong D Z, Zhao Z J, Zhao Q, et al. Coupling of Cu(100) and (110) facets promotes carbon dioxide conversion to hydrocarbons and alcohols[J]. Angewandte Chemie International Edition, 2021, 60(9): 4879-4885.
19	Zhao K, Quan X. Carbon-based materials for electrochemical reduction of CO₂ to C₂₊ oxygenates: recent progress and remaining challenges[J]. ACS Catalysis, 2021, 11(4): 2076-2097.
20	Peterson A A, Nørskov J K. Activity descriptors for CO₂ electroreduction to methane on transition-metal catalysts[J]. The Journal of Physical Chemistry Letters, 2012, 3(2): 251-258.
21	Zhou Y S, Che F L, Liu M, et al. Dopant-induced electron localization drives CO₂ reduction to C₂ hydrocarbons[J]. Nature Chemistry, 2018, 10(9): 974-980.
22	Liang Z Q, Zhuang T T, Seifitokaldani A, et al. Copper-on-nitride enhances the stable electrosynthesis of multi-carbon products from CO₂ [J]. Nature Communications, 2018, 9: 3828.
23	Zhang H G, Li J Z, Tan Q, et al. Metal-organic frameworks and their derived materials as electrocatalysts and photocatalysts for CO₂ reduction: progress, challenges, and perspectives[J]. Chemistry - A European Journal, 2018, 24(69): 18137-18157.
24	Li X F, Zhu Q L. MOF-based materials for photo- and electrocatalytic CO₂ reduction[J]. EnergyChem, 2020, 2(3): 100033.
25	Hu H, Han L, Yu M Z, et al. Metal-organic-framework-engaged formation of Co nanoparticle-embedded carbon@Co₉S₈ double-shelled nanocages for efficient oxygen reduction[J]. Energy & Environmental Science, 2016, 9(1): 107-111.
26	Yang L, Gao M G, Dai B, et al. An efficient NiS@N/S-C hybrid oxygen evolution electrocatalyst derived from metal-organic framework[J]. Electrochimica Acta, 2016, 191: 813-820.
27	Zheng Y L, Cheng P, Xu J S, et al. MOF-derived nitrogen-doped nanoporous carbon for electroreduction of CO₂ to CO: the calcining temperature effect and the mechanism[J]. Nanoscale, 2019, 11(11): 4911-4917.
28	Yao K L, Xia Y J, Li J, et al. Metal-organic framework derived copper catalysts for CO₂ to ethylene conversion[J]. Journal of Materials Chemistry A, 2020, 8(22): 11117-11123.
29	Majidi L, Ahmadiparidari A, Shan N N, et al. 2D copper tetrahydroxyquinone conductive metal-organic framework for selective CO₂ electrocatalysis at low overpotentials[J]. Advanced Materials, 2021, 33(10): 2004393.
30	Zhang R R, Hu L, Bao S X, et al. Surface polarization enhancement: high catalytic performance of Cu/CuO _x /C nanocomposites derived from Cu-BTC for CO oxidation[J]. Journal of Materials Chemistry A, 2016, 4(21): 8412-8420.
31	Kar A K, Srivastava R. Selective synthesis of Cu-Cu₂O/C and CuO-Cu₂O/C catalysts for Pd-free C-C, C-N coupling and oxidation reactions[J]. Inorganic Chemistry Frontiers, 2019, 6(2): 576-589.
32	Yang F, Deng P L, Wang Q Y, et al. Metal-organic framework-derived cupric oxide polycrystalline nanowires for selective carbon dioxide electroreduction to C₂ valuables[J]. Journal of Materials Chemistry A, 2020, 8(25): 12418-12423.
33	Zheng Y, Vasileff A, Zhou X L, et al. Understanding the roadmap for electrochemical reduction of CO₂ to multi-carbon oxygenates and hydrocarbons on copper-based catalysts[J]. Journal of the American Chemical Society, 2019, 141(19): 7646-7659.

[1]	Hao WANG, Zhenlei WANG. Model simplification strategy of cracking furnace coking based on adaptive spectroscopy method [J]. CIESC Journal, 2023, 74(9): 3855-3864.
[2]	Lingding MENG, Ruqing CHONG, Feixue SUN, Zihui MENG, Wenfang LIU. Immobilization of carbonic anhydrase on modified polyethylene membrane and silica [J]. CIESC Journal, 2023, 74(8): 3472-3484.
[3]	Chengying ZHU, Zhenlei WANG. Operation optimization of ethylene cracking furnace based on improved deep reinforcement learning algorithm [J]. CIESC Journal, 2023, 74(8): 3429-3437.
[4]	Mengmeng ZHANG, Dong YAN, Yongfeng SHEN, Wencui LI. Effect of electrolyte types on the storage behaviors of anions and cations for dual-ion batteries [J]. CIESC Journal, 2023, 74(7): 3116-3126.
[5]	Zhen LI, Bo ZHANG, Liwei WANG. Development and properties of PEG-EG solid-solid phase change materials [J]. CIESC Journal, 2023, 74(6): 2680-2688.
[6]	Zizong WANG, Hansheng SUO, Xueliang ZHAO. Research and construction of digital twin intelligent ethylene plant [J]. CIESC Journal, 2023, 74(3): 1175-1186.
[7]	Qian LIU, Yu CAO, Qi ZHOU, Jingshan MU, Wei LI. Design of Ziegler-Natta catalyst modified with pore structure and preparation of UHMWPE with high impact resistance and low entanglement [J]. CIESC Journal, 2023, 74(3): 1092-1101.
[8]	Huihuang FANG, Jinxing CHENG, Yu LUO, Chongqi CHEN, Chen ZHOU, Lilong JIANG. Recent progress on ammonia oxidation catalysts at anode and their performances in low-temperature direct ammonia alkaline exchange membrane fuel cells [J]. CIESC Journal, 2022, 73(9): 3802-3814.
[9]	Xiaoqiang FAN, Zhengliang HUANG, Jingyuan SUN, Jingdai WANG, Xiaofei WANG, Xiaobo HU, Guodong HAN, Yongrong YANG, Wenqing WU. Development of cloudy gas-liquid fluidized bed ethylene polymerization process and high performance products [J]. CIESC Journal, 2022, 73(6): 2742-2747.
[10]	Hang GUO, Wenli HAN, Xiaoling DONG, Wencui LI. Adjusting carbonization process to optimize sodium storage performance of coal-based hard carbon anode [J]. CIESC Journal, 2022, 73(4): 1794-1806.
[11]	Shiyi GE, Yao YANG, Zhengliang HUANG, Jingyuan SUN, Jingdai WANG, Yongrong YANG. Analyzing particle growth and morphology evolution of polyethylene based on electrostatic separation [J]. CIESC Journal, 2022, 73(4): 1585-1596.
[12]	Lixia WANG, Zhaojie BI, Miaolei SHI, Chen WANG, Dongfang WANG, Qian LI. Effect of blending mode and ratio of UHMWPE/PEG on the entanglement behavior and properties of UHMWPE [J]. CIESC Journal, 2022, 73(2): 933-940.
[13]	Xiaoyang YANG, Baofeng WANG, Xutao SONG, Fengling YANG, Fangqin CHENG. Migration of sulfur and nitrogen during co-hydrothermal carbonization process of sewage sludge and high-sulfur coal [J]. CIESC Journal, 2022, 73(11): 5211-5219.
[14]	Bo ZHANG, Xiaofei CHEN, Siyao ZHAO, Xin ZHOU. Progress of ethane-selective adsorbents for efficient purification of ethylene [J]. CIESC Journal, 2022, 73(10): 4255-4267.
[15]	GAO Shuaitao, LIU Xueke, ZHANG Li, LIU Fen, YU Jiang, SHANG Jianfeng, OU Tianxiong, ZHOU Zheng, CHEN Pingwen. Aspen Plus simulation on selective separation of high concentration acid gas of H₂S and CO₂ [J]. CIESC Journal, 2021, 72(S1): 413-420.