Surface-interface Control of CO2 Electroreduction on Gold-based Catalysts

doi:10.1007/s40242-026-6039-7

Abstract

Abstract: Electrochemical CO₂ reduction (CO₂RR) offers a compelling route for converting CO₂ into value-added chemicals using renewable electricity, yet its practical deployment is fundamentally constrained by sluggish kinetics, complex electrified interfaces, and limited control over product selectivity. Gold-based catalysts have long been regarded as benchmarks for CO-selective CO₂RR; however, growing evidence indicates that their catalytic behavior is not dictated by intrinsic adsorption energetics alone, but instead emerges from a tightly coupled interplay between surface structure, dynamic interface evolution, and the local reaction microenvironment. In this review, we critically examine recent advances in Au-based CO₂RR catalysts through the unifying lens of surface-interface control, encompassing morphology and defect engineering, alloy and cluster design, molecular surface modification, electrolyte cation regulation, and tandem or cascade catalytic architectures. Particular emphasis is placed on mechanistic insights derived from operando spectroscopy and kinetic analysis, which reveal dynamic phenomena, such as water-mediated proton transfer, CO-induced site blocking, surface reconstruction, and the breakdown of single-parameter activity descriptors. By integrating catalyst design with interfacial chemistry, mass transport, and solvation effects, this review establishes a unified mechanistic framework for understanding CO₂ electroreduction on gold-based catalysts and distills general principles for the rational design of efficient and selective electrochemical CO₂ conversion systems.

Key words: Gold-based catalyst, CO₂ electroreduction, Surface and interface control, Reaction microenvironment

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.

References

[1] Heinecke C. L., Ni T. W., Malola S., Mäkinen V., Wong O. A., Häkkinen H., Ackerson C. J., J. Am. Chem. Soc., 2012, 134, 13316.
[2] Häkkinen H., Nat. Chem., 2012, 4, 443.
[3] Zeng C., Liu C., Pei Y., Jin R., ACS Nano, 2013, 7, 6138.
[4] Zhu M., Aikens C. M., Hollander F. J., Schatz G. C., Jin R., J. Am. Chem. Soc., 2008, 130, 5883.
[5] Zhang S., Fan Q., Xia R., Meyer T., J. Acc. Chem. Res., 2020, 53, 255.
[6] Zhang L., Zhao Z. J., Gong J., Angew. Chem. Int. Ed., 2017, 56, 11326.
[7] Li S., Nagarajan A. V., Du X., Li Y., Liu Z., Kauffman D. R., Mpourmpakis G., Jin R., Angew. Chem. Int. Ed., 2022, 61, e202211771.
[8] Nam D. H., Luna P. D., Rosas-Hernández A., Thevenon A., Li F., Nat. Mater., 2020, 19, 266.
[9] Overa S., Ko B. H., Zhao Y., Jiao F., Acc. Chem. Res., 2022, 55, 638.
[10] Zheng T., Jiang K., Wang H., Adv. Mater., 2018, 30, 1802066.
[11] Yang D., Wang J., Wang Q., Yuan Z., Dai Y., Zhou C., Wan X., Zhang Q., Yang Y., ACS Nano, 2022, 16, 15681.
[12] Kauffman D. R., Alfonso D., Matranga C., Qian H., Jin R., J. Am. Chem. Soc., 2012, 134, 10237.
[13] Zhuang S., Chen D., Ng W. P., Liu L. J., Sun M.-Y., Liu D., Nawaz T., Xia Q., Wu X., Huang Y. L., Lee S., Yang J., Yang J., He J., Angew. Chem. Int. Ed., 2023, 62, e202306696.
[14] Seong H., Efremov V., Park G., Kim H., Yoo J. S., Lee D., Angew. Chem. Int. Ed., 2021, 60, 14563.
[15] Kulkarni V. K., Khiarak B. N., Takano S., Malola S., Albright E. L., Levchenko T. I., Aloisio M. D., Dinh C. T., Tsukuda T., Häkkinen H., Crudden C. M., J. Am. Chem. Soc., 2022, 144, 9000.
[16] Chen Y., Zhu H., Li J., Liu M., Zhang Y., Liu Y.-N., Wang Q., Adv. Funct. Mater., 2026, 36, e15847.
[17] Wang H., Kang X., Han B., Chem. Soc. Rev., 2025, 54, 10156.
[18] Liu Z., Chen J., Li B., Jiang D., Wang L., Yao Q., Xie J., J. Am. Chem. Soc., 2024, 146, 11773.
[19] Wang J., Xu F., Wang Z. Y., Zang S. Q., Mak T. C. W., Angew. Chem. Int. Ed., 2022, 61, e202207492.
[20] Sun Y., Liu X., Xiao K., Zhu Y., Chen M., ACS Catal., 2021, 11, 11551.
[21] Narouz M. R., Osten K. M., Unsworth P. J., Man R. W. Y., Salorinne K., Takano S., Tomihara R., Kaappa S., Malola S., Dinh C. T., Padmos J. D., Ayoo K., Garrett P. J., Nambo M., Horton J. H., Sargent E. H., Häkkinen H., Tsukuda T., Crudden C. M., Nat. Chem., 2019, 11, 419.
[22] Levchenko T. I., Yi H., Aloisio M. D., Dang N. K., Gao G., Sharma S., Dinh C. T., Crudden C. M., ACS Catal., 2024, 14, 4155.
[23] Zhao S., Austin N., Li M., Song Y., House S. D., Bernhard S., Yang J. C., Mpourmpakis G., Jin R., ACS Catal., 2018, 8, 4996.
[24] Shi P., Yan Y., Yang S., Hao J., Wang M., Lu T., Chem. Sci., 2025, 16, 11711.
[25] Tan Y., Sun G., Jiang T., Liu D., Li Q., Yang S., Chai J., Gao S., Yu H., Zhu M., Angew. Chem. Int. Ed., 2024, 63, e202317471.
[26] Liu X., Wang E., Zhou M., Wan Y., Zhang Y., Liu H., Zhao Y., Li J., Gao Y., Zhu Y., Angew. Chem. Int. Ed., 2022, 61, e202207685.
[27] Li S., Nagarajan A. V., Alfonso D. R., Sun M., Kauffman D. R., Mpourmpakis G., Jin R., Angew. Chem. Int. Ed., 2021, 60, 6351.
[28] Zhuang S., Chen D., Liao L., Zhao Y., Xia N., Zhang W., Wang C., Yang J., Wu Z., Angew. Chem. Int. Ed., 2020, 59, 3073.
[29] Li S., Alfonso D., Nagarajan A. V., House S. D., Yang J. C., Kauffman D. R., Mpourmpakis G., Jin R., ACS Catal., 2020, 10, 12011.
[30] Li F., Qin H., Gu J., EnergyChem, 2025, 7, 100156.
[31] Zhao J., Ziarati A., Rosspeintner A., Bürgi T., Angew. Chem. Int. Ed., 2024, 63, e202316649.
[32] Cai X., Li G., Hu W., Zhu Y., ACS Catal., 2022, 12, 10638.
[33] Ziarati A., Gotfredsen H., Rosspeintner A., Zhao J., Anderson H. L., Bürgi T., Angew. Chem. Int. Ed., 2025, 64, e202414908.
[34] Chen L., Guo Z., Huang H., Tian W., Chang X., Hu Q., Liu D., Sun C., Gao M., Han S., Lv S., Zhou H., Hu L., Mou H., Gao X., Hao Y., Yang W., Li Q., Wang B., Song J., Nat. Commun., 2026, 17, 1734.
[35] Chen L., Hao Y., Li J., Hu L., Guo Y., Li S., Liu D., Zhu Z., Wu S., Huang H., Yin A. X., Wang B., Zhang Y. W., Sci. China Chem., 2022, 65, 2188.
[36] Chen L., Hao Y., Li J., Hu L., Zuo X., Dai C., Yu Z. L., Huang H., Tian W., Liu D., Chang X., Li P., Shao R., Wang B., Yin A. X., Small, 2023. 19, 2301639.
[37] Xu C., Han S., Zhang K., Feng Q., Bao L., Gao M., Gao W. Y., Pak Y. L., Mou H., Chen L., Gao X., Hao Y., Chinese Chem, Lett., 2026, 37, 112179.
[38] Zhu Z., Yu Z. L., Gao W. Y., Su X., Chen L. W., Hao Y. C., Wu S. Q., Liu D., Jing X., Huang H. Z., Yin A. X., ChemSusChem, 2022, 15, e202200211.
[39] Liu M., Liu M., Wang X., Kozlov S. M., Cao Z., Luna P. D., Li H., Qiu X., Liu K., Hu J., Jia C., Wang P., Joule, 2019, 3, 1703.
[40] Liu Q., Yang X., Li L., Miao S., Li Y., Li Y., Wang X., Huang Y., Zhang T., Nat. Commun., 2017, 8, 1407.
[41] Ke X., Xu W., Liu C., Wang Y., Huang X., Xiao R., Xu X., Li T., Shao Z., Energy Environ. Sci., 2025, 18, 7792.
[42] Kuhl K. P., Hatsukade T., Cave E. R., Abram D. N., Kibsgaard J., Jaramillo T. F., J. Am. Chem. Soc., 2014, 136, 14107.
[43] Jung Y., Abbas H. G., Kim S., Kim B., Cho J., Han S., Song H., Takaoka Y., Song J. T., Ishihara T., Choi C. H., Ringe S., Oh J., J. Am. Chem. Soc., 2025, 147, 39796.
[44] Liang L., Feng Q., Wang X., Hübner J., Gernert U., Heggen M., Wu L., Hellmann T., Hofmann J. P., Strasser P., Angew. Chem. Int. Edit., 2022, 62, e202218039.
[45] Xue T., Xu G., Liu C., Li R., Wu Y., Guo Y., Gong S., Shao Z., Cai X., Zou H., Cui L., Zhao J., Gao Z., Yang S., Li J., Han B., Peng L., Angew. Chem. Int. Ed., 2025, 64, e202500092
[46] Ma A., Li Y., Zuo Y., Zhang S., Wang Y., Ren Y., Hussain E., Ma X., Wang S., Rare Met., 2025, 44, 4691.
[47] Tang Y. F., Liu L. B., Yu M., Liu S., Sui P. F., Sun W., Fu X. Z., Luo J. L., Liu S., Chem. Soc. Rev., 2024, 53, 9344.
[48] Gao F., Yue M. F., Wun D., Cheung F., Yang W., He Z. F., Gu Y., Zheng S., Zhong X., Ma S., Chen W. P., Tian J. H., Dong J. C., Li J. F., J. Am. Chem. Soc., 2025, 147, 19859.
[49] Marcandalli G., Villalba M., Koper M. T. M., Langmuir, 2021, 37, 5707.
[50] Zhu Z. H., Liang Z. L., Jiao Z. H., Jiang X. L., Xie Y., Xu H., Zhao B., Angew. Chem. Int. Ed., 2022, 61, e202214243.
[51] Mariano R. G., McKelvey K., White H. S., Kanan M. W., Science, 2017, 358, 1187.
[52] Feng X., Jiang K., Fan S., Kanan M. W., J. Am. Chem. Soc., 2015, 137, 4606.
[53] Liu M., Pang Y., Zhang B., Luna P. D., Voznyy O., Xu J., Zheng X., Dinh C. T., Fan F., Cao C., Nature, 2016, 537, 382.
[54] Zhu W., Michalsky R., Metin O., Lv H., Guo S., Wright C. J., Sun X., Peterson A. A., Sun S., J. Am. Chem. Soc., 2013, 135, 16833.
[55] Lu X., Yu T., Wang H., Qian L., Lei P., ACS Catal., 2020, 10, 15, 8860.
[56] Zhu W., Zhang Y. J., Zhang H., Lv H., Li Q., Michalsky R., Peterson A. A., Sun S., J. Am. Chem. Soc., 2014, 136, 16132.
[57] Wang Y., Cao L., Libretto N. J., Li X., Li C., Wan Y., He C., Lee J., Gregg J., Zong H., Su D., Miller J. T., Mueller T., Wang C., J. Am. Chem. Soc., 2019, 141, 16635.
[58] Yuan X., Zhang L., Li L., Dong H., Chen S., Zhu W., Hu C., Deng W., Zhao Z. J., Gong J., J. Am. Chem. Soc., 2019, 141, 4791.
[59] Deng G., Yun H., Bootharaju M. S., Sun F., Lee K., Liu X., Yoo S., Tang Q., Hwang Y. J., Hyeon T., J. Am. Chem. Soc., 2023, 145, 27407.
[60] Ma A., Wang J., Wang Y., Zuo Y., Ren Y., Ma X., Wang S., Polyoxometalates, 2024, 3, 9140054.
[61] Sun K., Cheng T., Wu L., Hu Y., Zhou J., Maclennan A., Jiang Z., Gao Y., J. Am. Chem. Soc., 2017, 139, 15608.
[62] Dai S., Huang T. H., Liu W. I., Hsu C. W., Lee S. W., Chen T. Y., Wang Y. C., Wang J. H., Wang K. W., Nano Lett., 2021, 21, 9293.
[63] Ismail A. M., Samu G. F., Nguyën H. C., Csapó E., López N., Janáky C., ACS Catal., 2020, 10, 5681.
[64] Jin Z., Liu K., Pan Z., Shan X., Cai F., Yang D., Li P., Yu G., Zhou M., J. Am. Chem. Soc., 2026, 148, 622.
[65] Sun K., Shi Y., Li H., Shan J., Sun C., Wu Z., ChemSusChem, 2021, 14, 4929.
[66] Gao D., Zhang Y., Zhou Z., Cai F., Zhao X., Huang W., Li Y., Zhu J., Liu P., Yang F., Wang G., Bao X., J. Am. Chem. Soc., 2017, 139, 5652.
[67] Zhao Z., Tan C., Sun P., Li F., Wang X., J. Mater. Chem. A, 2024, 12, 21716.
[68] Song X., Wang M., Zhang Z., Yao Q., Mao S., Wang W., Yang S., Ding X., Zhang G., Wang Z., Wang C., Kong Z., Wu J., Zhang L., Huang Y., Song H., Nano Res., 2025, 18, 94907704.
[69] Sun F., Zhou X., Qin L., Tang Z., Wang L., Tang Q., ACS Catal., 2025, 15, 4605.
[70] Wang J., Yu J., Sun M., Liao L., Zhang Q., Zhai L., Zhou X., Li L., Wang G., Meng F., Shen D., Li Z., Bao H., Wang Y., Zhou J., Chen Y., Niu W., Huang B., Gu L., Lee C. S., Fan Z., Small, 2022, 18, 2106766.
[71] Cao Z., Kim D., Hong D., Yu Y., Xu J., Lin S., Wen X., Nichols E. M., Jeong K., Reimer J. A., Yang P., J. Am. Chem. Soc., 2016, 138, 8120.
[72] Chen Y., Wei K., Duan H., Sun H., Yu Z., Zohaib A., Zhu P., He J., Sun S., J. Am. Chem. Soc., 2025, 147, 14845.
[73] Wang H., Fu Y., Chen Z. N., Zhuang W., Cao M., Cao R., Nano Res., 2023, 16, 4723.
[74] Souza M. L., Lima F. H. B., ACS Catal., 2021, 11, 12208.
[75] Xu Y., Qiu Y., Chang X., Xiao H., Xu B., Nat. Chem., 2026, 18, 544.
[76] Gorthy S., Verma S., Sinha N., Shetty S., Nguyen H., Neurock M., ACS Catal., 2023, 13, 12924.
[77] Ovalle V. J., Hsu Y., Agrawal N., Janik M. J., Waegele M. M., Nat. Catal., 2022, 5, 624.
[78] Wang Y., Fu J., Feng Y., Zhao K., Wang L., Cai J., Wang X., Chen T., Yang F., Hu J., Xu B., Wang D., Wan L., J. Am. Chem. Soc., 2024, 146, 27713.
[79] Shi K., Janisch J., Ren Z., Meng Z., Israel D., Le D., Kaden W. E., Rahman T. S., Feng X., J. Am. Chem. Soc., 2025, 147, 23277.
[80] Cui Z., Wong A. J., Janik M. J., Co A. C., Sci. Adv., 2025. 11, 6465.
[81] Guan Y., Zhou X., Yan Q., Wang Z., Yang J., Tang Q., Wang L., Xia N., Angew. Chem. Int. Ed., 2025, 64, e202508459.
[82] Zhu M., Yao Y., Liu Z., Chen D., Yang J., Yao Q., Hu W., Jiang Z., Xie J., Angew. Chem. Novit, 2025, 1, e70001.
[83] Su S., Zhou Y., Xiong L., Jin S., Du Y., Zhu M., Angew. Chem. Int. Ed., 2024, 63, e202404629.
[84] Bian G., Chen D., Chen Y., Zhang W., Fang L., You Q., Wang R., Gu W., Zhou Y., Yan N., Zhuang S., Ji S., Zhou M., Wang C., Liao L., Tang Q., Yang J., Wu Z., Sci. Adv., 2025, 11, 15.
[85] Gao Z., Wei K., Wu T., Dong J., Jiang D., Sun S., Wang L., J. Am. Chem. Soc., 2022, 144, 5258.
[86] Han S. M., Park M., Kim J., Leex D., Angew. Chem. Int. Ed., 2024, 63, e202404387.
[87] Cai H., Yang H., Li D., He S., Zhang X., Hu Q., He C., Angew. Chem. Int. Ed., 2024, 64, e202425325.
[88] Jeong S., Huang C., Levell Z., Skalla R. X., Hong W., Escorcia N. J., Losovyj Y., Zhu B., Butrum-Grifth A. N., Liu Y., Li C. W., J. Am. Chem. Soc., 2024, 146, 7, 4508.
[89] Wang S., Jung H. D., Choi H., Kim J., Back S., Oh J., Nano Energy, 2024, 130, 110176.
[90] Kuang S., Su Y., Li M., Liu H., Chuai H., Chen X., Hensen E. J. M., Meyer T. J., Zhang S., Ma X., P. Natl. Acad. Sci., 2023, 120, e2214175120.
[91] Jia H., Yang Y., Chow T. H., Zhang H., Liu X., Wang J., Zhang C., Adv. Funct. Mater., 2021, 31, 2101255.
[92] Zhang Z., Ma X., Song Y., Yang X., Fang Q., Yamauchi Y., Tang J., Angew. Chem. Int. Ed., 2025, 64, e202511704.
[93] Bhoumik N. C., Padovan Q. A., Akter T., Stem D. K., Barile C. J., Angew. Chem. Int. Ed., 2024, 64, e202423882.
[94] Yao Y., Delmo E. P., Shao M., Angew. Chem. Int. Ed., 2024, e202415894.
[95] Tao Z., Pearce A. J., Mayer J. M., Wang H., J. Am. Chem. Soc., 2022, 144, 8641.
[96] Cui Z., Wong A. J., Janik M. J., Co A. C., J. Am. Chem. Soc., 2024, 146, 23872.
[97] Wang H., Fisher H., Huang-Fu Z., Brown J. B., Zhang T., Song F., Qian Y., Rao Y. J. Am. Chem. Soc., 2025, 147, 19101.
[98] Shi R., Guo J., Zhang X., Waterhouse G. I. N., Han Z., Zhao Y., Shang L., Zhou C., Jiang L., Zhang T. Nat. Commun., 2020, 11, 3028.
[99] Cui Z., Aztergo K. D., Hwang J., Co A. C. Nat. Catal., 2025, 8, 1117.
[100] Li D., Chem. Res. Chinese Universities, 2025, 41, 472.
[101] Zhou Y., Ibáñez-Alé E., López N., Cuenya B., Kley C. S, Nat. Chem., 2026, 18, 473.
[102] Zeng M., Zou S., Huang L., Zhang J., Wang J., Feng X., J. Am. Chem. Soc., 2026, 148, 4475.
[103] Dong J., Liu Y., Pei J., Li H., Ji S., Shi L., Zhang Y., Li C., Tang C., Liao J., Xu S., Zhang H., Li Q., Zhao S., Nat. Commun., 2023, 14, 6849.
[104] Lu W., Zhao X., Chem. Res. Chinese Universities, 2025, 41, 432.
[105] Shi X., Shi L., Wang J., Zhou Y., Zhao S., Matter, 2024, 7, 4233.
[106] S R., Battineni G., J. Comput. Cogn. Eng., 2025, 4, 56.
[107] Vaiyapuri T., Elashmawi W. H., S S., Asiedu W., J. Comput. Cogn. Eng., 2025, 4, 332.
[108] Mohsen B. M., Mohsen M., J. Comput. Cogn. Eng., 2025, 5, 169.

Surface-interface Control of CO₂ Electroreduction on Gold-based Catalysts

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 4

Recommended Articles

Metrics

Comments

[1]	Shiyu Yao, Junkuo Gao. Structure-Activity Relationships in Metal-Organic Framework-based Catalysts for Electrochemical CO₂ Reduction [J]. Chemical Research in Chinese Universities, 2026, 42(3): 711-737.
[2]	Siheng Yang, Qinyuan Hu, Yuxuan Kong, Yuehan Cao, Weiyao Hu, Lei Ran, Xueli Zheng, Haiyan Fu, Hua Chen, Ruixiang Li, Chong Cheng, Shuang Li, Weichao Xue, Jiaqi Xu. 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.
[3]	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.
[4]	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.