Hydroxyl-functionalized SiO2-supported CuO Composite Catalysts Enabling Highly Selective CO2 Electroreduction to CH4 at Industrial Current Densities

doi:10.1007/s40242-026-6076-2

Chemical Research in Chinese Universities ›› 2026, Vol. 42 ›› Issue (3): 813-821.doi: 10.1007/s40242-026-6076-2

• Research Articles • Previous Articles Next Articles

Hydroxyl-functionalized SiO₂-supported CuO Composite Catalysts Enabling Highly Selective CO₂ Electroreduction to CH₄ at Industrial Current Densities

YANG Siheng¹, HU Qinyuan³, KONG Yuxuan¹, CAO Yuehan², HU Weiyao², RAN Lei², ZHENG Xueli¹, FU Haiyan¹, CHEN Hua¹, LI Ruixiang¹, CHENG Chong¹, LI Shuang¹, XUE Weichao¹, XU Jiaqi^1,2

1. Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, College of Polymer Science and Engineering, Sichuan University, Chengdu, Sichuan, 610064, P. R. China;
2. State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, School of New Energy and Materials, Southwest Petroleum University, Chengdu, 610500, P. R. China;
3. Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, 214122, P. R. China

Received:2026-03-24 Accepted:2026-05-01 Published:2026-06-02
Contact: XU Jiaqi,E-mail:jqxu@mail.ustc.edu.cn,jqxu@scu.edu.cn;XUE Weichao,E-mail:weichaoxue@scu.edu.cn E-mail:jqxu@mail.ustc.edu.cn,jqxu@scu.edu.cn;weichaoxue@scu.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (No. 22575158), the Sichuan Provincial Natural Science Foundation, China (Nos. 2024YFFK0016, 2026NSFSC0052), the Key Research Project of Sichuan Province, China (No. 2026YFHZ0251), the Chengdu Key Research Project, China (No. 2025-YF05-00618-SN), the Guangdong Province Natural Science Foundation, China (No. 2025A1515011976), and the Fundamental Research Funds for the Central Universities, China (No. 0082604151553).

Abstract

Abstract: Selective producing CH₄ by CO₂ electroreduction remains challenging, primarily hindered by the complexity of reduction products, sluggish protonation kinetics, and competitive hydrogen evolution reaction. Herein, we developed a silica-copper composite catalyst (CuO/SiO₂), where CuO nanoparticles are dispersed on the hydroxyl-functionalized SiO₂ nanosheet. The hydroxyl-functionalized SiO₂ support promotes the formation and transfer of interfacial reactive hydrogen species, lowers the energy barrier for the reduction of CO₂ to CH₄ by stabilizing *COOH, *CO, and *H intermediates. Meanwhile, it favors the hydrogenation of *CHO over C—C coupling between C1 intermediates, thereby shifting product selectivity from multi-carbon products towards CH₄. As a result, CuO/SiO₂ catalyst delivers high CH₄ selectivity over a broad current density range of 0.2–0.9 A/cm², with a peak Faradaic efficiency of 66.2% at 0.6 A/cm². This work demonstrates an effective interfacial engineering strategy for enhancing the selectivity of CO₂-to-CH₄ conversion.

Key words: CO₂ electroreduction, CO₂ methanation, Interfacial engineering, Silica

YANG Siheng, HU Qinyuan, KONG Yuxuan, CAO Yuehan, HU Weiyao, RAN Lei, ZHENG Xueli, FU Haiyan, CHEN Hua, LI Ruixiang, CHENG Chong, LI Shuang, XUE Weichao, XU Jiaqi. Hydroxyl-functionalized SiO₂-supported CuO Composite Catalysts Enabling Highly Selective CO₂ Electroreduction to CH₄ at Industrial Current Densities[J]. Chemical Research in Chinese Universities, 2026, 42(3): 813-821.

References

[1] Wang G., Chen J., Ding Y., Cai P., Yi L., Li Y., Tu C., Hou Y., Wen Z., Dai L., Chem. Soc. Rev., 2021, 50, 4993.
[2] Sheng X., Ge W., Jiang H., Li C., Adv. Mater., 2022, 34, 2201295.
[3] Fang W., Guo W., Lu R., Yan Y., Liu X., Wu D., Li F. M., Zhou Y., He C., Xia C., Niu H., Wang S., Liu Y., Mao Y., Zhang C., You B., Pang Y., Duan L., Yang X., Song F., Zhai T., Wang G., Guo X., Tan B., Yao T., Wang Z., Xia B. Y., Nature, 2024, 626, 86.
[4] Zhang H., Liu S., Zhang C., Liu W., Dong H., Shi Z., Xu H., Liu J., Wang D., Jiao J., Gao M., Lu T., Angew. Chem. Int. Ed., 2025, 65, e18519.
[5] Xiong L., Fu X., Chin. J. Catal., 2025, 73, 39.
[6] Li J. K., Ma J. J., Chen Y., Zhao S. N., Song S., Zang S. Q., ACS Nano, 2025, 19, 32858.
[7] Zhang Z., Guo H., Li S., Gao S., Wang X., Li M., Yan W., Xu H., Nat. Commun., 2025, 16, 7559.
[8] Gao G., Khiarak B. N., Liu H., Tran-Phú T., Obasanjo C. A., Crane J., Lai H. D. T., da Silva G. T. S. T., Golovanova V., Li J., Ze H., Weiss J., Zhang Z., Lee S., Hocking R. K., Garcia de Arquer F. P., Sargent E. H., Dinh C.-T., Nat. Energy, 2025, 10, 1360.
[9] Xiong L., Zhang X., Chen L., Deng Z., Han S., Chen Y., Zhong J., Sun H., Lian Y., Yang B., Yuan X., Yu H., Liu Y., Yang X., Guo J., Rümmeli M. H., Jiao Y., Peng Y., Adv. Mater., 2021, 33, 2101741.
[10] Ling P., Liu Y., Wang Z., Li L., Hu J., Zhu J., Yan W., Jiang H., Hou Z., Sun Y., Xie Y., Nano Lett., 2022, 22, 2988.
[11] Zhang H., Chang X., Chen J. G., Goddard W. A., Xu B., Cheng M.-J., Lu Q., Nat. Commun., 2019, 10, 3340.
[12] Zhu J., Lv L., Zaman S., Chen X., Dai Y., Chen S., He G., Wang D., Mai L., Energy Environ. Sci., 2023, 16, 4812.
[13] Li J., Wei M., Ji B., Hu S., Xue J., Zhao D., Wang H., Liu C., Ye Y., Xu J., Zeng J., Ye R., Zheng Y., Zheng T., Xia C., Angew. Chem. Int. Ed., 2025, 64, e202417008.
[14] Zhao P., Ai J., Jiang H., Yang S., Shen H., Zhang J., Guo Y., Zhang Q., Zhang H., Angew. Chem. Int. Ed., 2025, 64, e202516184.
[15] Wang M., Xie Y., Fang M., Zhang Y., Wang Y., Zhang Z., Jia S., Chen C., Wu H., He M., Han B., J. Am. Chem. Soc., 2025, 147, 44781.
[16] Yang Z., Zhang J., Tan X., Zhu H., Xu L., Wu X., Xu Z., Guo J., Jia D., Chen C., J. Am. Chem. Soc., 2025, 147, 35985.
[17] Xiong L., Zhan S., Ciano L. D., Li S., Liu R., Lu S., Yao P., Fu X., Yue Q., Adv. Mater., 2026, 38, e12478.
[18] Xu Q., Xu Z., Li A., Chang M., Li Y.-F., Jia K., Zhang L., ACS Catal., 2026, 16, 1456.
[19] Zhou M., Wang Y., Liu S., Yin Y., Peng Y., Jiao J., Yang J., Zhao W., Wang H., Duan R., Zhu Q., Sun X., Xu Y., Zhang J., Kang X., Han B., Angew. Chem. Int. Ed., 2026, 65, e20997.
[20] Gong J., Li J., Liu C., Wei F., Yin J., Li W., Xiao L., Wang G., Lu J., Zhuang L., Chin. J. Catal., 2022, 43, 3101.
[21] Ji D., Yang Z., Yao Y., Hou Y., He Z., Da P., Shen W., An L., Sun Y., Xi P., Yan C.-H., Small, 2025, 21, 2503169.
[22] Wen X., Min Q., Liu X., Zhao G., Wang J., Xu Q., Shi G., Zhang L., Zhang W., Su Y., ACS Catal., 2025, 15, 14215.
[23] Jiang X., Ge W., Fan Y., Sheng X., Jiang H., Li C., AIChE J., 2025, 71, e18663.
[24] Li M., Yu Y., Chen L., Cao K., Zhang J.-N., Appl. Catal. B, 2026, 394, 126820.
[25] Flanigen E. M., Bennett J. M., Grose R. W., Cohen J. P., Patton R. L., Kirchner R. M., Smith J. V., Nature, 1978, 271, 512.
[26] Mirfendereski S. M., Mazaheri T., Energy Fuels, 2025, 39, 19526.
[27] Yuan S., Wang R., Xue R., Wu L., Zhang G., Li H., Wang Q., Yin J., Luo L., Shen S., An L., Yan X., Zhang J., ACS Energy Lett., 2024, 9, 5945.
[28] Subramanian S., Kok J., Gholkar P., Kumar A. S., van Montfort H.-P. I., Kortlever R., Urakawa A., Dam B., Burdyny T., Energy Environ. Sci., 2024, 17, 6728.
[29] Bai Q., Xiong L., Zhang Y., Ma M., Jiao Z., Lyu F., Deng Z., Peng Y., EES Catal., 2024, 2, 1228.
[30] Tang Z., Dong Z., Yuan L., Li B., Zhu Y., EES Catal., 2025, 3, 943.
[31] Gu J., Liu S., Ni W., Ren W., Haussener S., Hu X., Nat. Catal., 2022, 5, 268.
[32] Qu Y., Yang K., Li W., Wang G., Xiao L., Wang G., Zhuang L., ACS Energy Lett., 2024, 9, 3042.
[33] Wei X., Wang Z., Xie Q., Mu X., Chu H., Li Y., Liu H., Wang H., Liu W., Song S., Zhang H., Wang X., Angew. Chem. Int. Ed., 2026, 138, e18437.
[34] Zhang L., Ma H., Sun Y., Zhao Y., Deng H., Wang Y., Wang F., Wen X.-D., Luo M., Nat. Commun., 2025, 16, 5039.
[35] Xu J., Zhang L., Zhao M., Sun L., Xie Q., Wang Y., Song S., Zhang H., Wang X., Angew. Chem. Int. Ed., 2026, 138, e19311.
[36] Zhang T., Jin Y., Lou S. N., Yan T., Xiao T., Liu Z., Lin J., Kuang S., Zhang S., Ma X., Appl. Catal. B, 2024, 353, 124065.
[37] Xu J., Wang K., Zhao M., Zhang R., Cui W., Liu L., Wang X., Wang J., Song S., Zhang H., Angew. Chem. Int. Ed., 2025, 64, e202423438.
[38] Zhu C., Wang D., Zeng L., Feng G., Liang Y., Zheng W., Lin W., Peng X., Liu Z., Sang X., Yang B., Li Z., Zhang Q., Lei L., Hou Y., J. Am. Chem. Soc., 2025, 147, 26185.

Hydroxyl-functionalized SiO₂-supported CuO Composite Catalysts Enabling Highly Selective CO₂ Electroreduction to CH₄ at Industrial Current Densities

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	ZHENG Dahai, ZHANG Kaiyang, ZHANG Kerun, GAO Wenyan, BAO Lan, GAO Mingming, LIU Di, PAK Yen Leng, MOU Hongyu, GAO Xing, CHEN Liwei, HAN Suqin, GUO Zhenbin. Surface-interface Control of CO₂ Electroreduction on Gold-based Catalysts [J]. Chemical Research in Chinese Universities, 2026, 42(3): 689-710.
[2]	YAO Shiyu, GAO Junkuo. Structure-Activity Relationships in Metal-Organic Framework-based Catalysts for Electrochemical CO₂ Reduction [J]. Chemical Research in Chinese Universities, 2026, 42(3): 711-737.
[3]	LI Junze, WANG Yongxiang, BAO Han, ZENG Shuangqin, GAO Xiuzhi, HE Xiaowu, ZHENG Mingji, FENG Ningdong, WANG Qiang, XU Jun, DENG Feng. Probing Framework Boron Speciation and Spatial Distribution in MFI Zeolites by Solid-state NMR [J]. Chemical Research in Chinese Universities, 2026, 42(1): 134-142.
[4]	CHEN Yaxin, LI Lin, WANG Jiaze, LI Yi. Impact of Al Distribution on Ethylene/Ethane Selective Separation over Aluminosilicate Zeolites: A High-throughput Theoretical Study [J]. Chemical Research in Chinese Universities, 2026, 42(1): 167-175.
[5]	LIU Chuang, GAO Tengyuan, WANG Guohong, CHENG Qiang, WANG Kai. Efficient CO₂ Photoreduction into Solar Fuels over MoO_3-x/COF S-Scheme Photocatalyst [J]. Chemical Research in Chinese Universities, 2025, 41(4): 726-733.
[6]	CHEN Long, WANG Yunzheng, LV Jiangang, YANG Weimin. Impact of Various Silicon Sources on the Synthesis of Mordenite and Differences in the Carbonylation Reaction of Dimethyl Ether [J]. Chemical Research in Chinese Universities, 2025, 41(1): 59-65.
[7]	LI Baoyan, MENG Jingjing, LI Yingding, JIANG Lingxia, CHENG Tanyu, LIU Guohua. Protonated Mesoporous Aluminosilica Nanospheres Boosting Aza-Michael Cyclization and Diels-Alder Reaction [J]. Chemical Research in Chinese Universities, 2024, 40(6): 1127-1133.
[8]	HUANG Yitong, WANG Yaquan, LIU Wenrong, BU Lingzhen, QU Liping, CHU Kailiang, GUO Niandong, ZHANG Xian, SU Xuemei, LI Yaoning, SANG Juncai. Synthesis of LSX Using Seed-iteration Approach with High N₂ Adsorption Capacity for Air Separation [J]. Chemical Research in Chinese Universities, 2024, 40(6): 1192-1200.
[9]	WEI Lili, FAN Yuanqing, LIN Haifeng, CHE Shunai. Synthesis of Anisotropic Silica Nanoparticles [J]. Chemical Research in Chinese Universities, 2024, 40(6): 1220-1226.
[10]	JIA Xiaohao, SUN Panpan, LIU Aoqun, CHEN Jinxiu, WANG Jingyi, ZHANG Heng, ZHU Wancheng. One-pot Mild Hydrothermal Synthesis of the Nanosheets Constructed Cobalt Silicate Hydroxide Hierarchical Porous Hollow Submicron Spheres as Efficient Adsorbents for Organic Dyes Removal [J]. Chemical Research in Chinese Universities, 2023, 39(4): 680-689.
[11]	MENG Chenchen, HUANG Min, LI Yunchao. Optimized Preparation of CuS@SiO₂ Core-Shell Nanoparticles with Strong LSPR Absorption and Excellent Photostability for Highly Efficient Solar-driven Interfacial Water Evaporation [J]. Chemical Research in Chinese Universities, 2023, 39(4): 697-704.
[12]	GONG Yu, PAN Jing, ZHANG Lingling, WANG Xiao, SONG Shuyan, ZHANG Hongjie. Metal-Organic Frameworks-derived Indium Clusters/Carbon Nanocomposites for Efficient CO₂ Electroreduction [J]. Chemical Research in Chinese Universities, 2022, 38(5): 1287-1291.
[13]	WU Liting, XIN Yujia, GUO Zhaoyang, GAO Wei, ZHU Yanpeng, br, WANG Yinsong, RAN Ruixue, YANG Xiaoying. Cell Membrane-camouflaged Multi-functional Dendritic Large Pore Mesoporous Silica Nanoparticles for Combined Photothermal Therapy and Radiotherapy of Cancer [J]. Chemical Research in Chinese Universities, 2022, 38(2): 562-571.
[14]	MI Zhenrui, LU Tingting, ZHANG Jia-Nan, XU Ruren, YAN Wenfu. Synthesis of Pure Silica Zeolites [J]. Chemical Research in Chinese Universities, 2022, 38(1): 9-17.
[15]	YI Jundong, LI Qiuxia, CHI Shaoyi, HUANG Yuanbiao, CAO Rong. Boron-doped Covalent Triazine Framework for Efficient CO₂ Electroreduction [J]. Chemical Research in Chinese Universities, 2022, 38(1): 141-146.