Precise control over the dynamic transformations that electrocatalysts undergo under operating conditions offers a powerful strategy for tailoring catalytic selectivity. Herein, the electrochemical modification of Cu2-xS-derived catalysts to generate selective active sites for the electroreduction of CO2 to formate is investigated. Through a combination of in situ and ex situ characterization techniques, it is demonstrated that electrochemical cycling induces sulfur leaching, resulting in the formation of reduced, amorphous copper structures that exhibit enhanced selectivity toward formate production. Compared to the pristine material, the electrochemically modified catalyst achieves a twofold improvement in Faradaic efficiency, reaching values as high as 75% for CO2-to-formate conversion. These findings not only establish a cost-effective and scalable platform for catalyst fabrication and activation, but also open new avenues for advancing sustainable CO2 conversion technologies toward industrial implementation.

Centro de Física de Materiales and Material Physics Center CSIC UPV EHU University of the Basque Country UPV EHU Manuel Lardizabal 5 20018 San Sebastián Spain

Department of Chemical Biological Pharmaceutical and Environmental Sciences University of Messina ERIC aisbl and CASPE INSTM 5 Ferdinando Stagno d'Alcontres 31 98166 Messina Italy

Department of Chemistry Université de Montréal 1375 Ave Thérèse Lavoie Roux Montréal QC H2V 0B3 Canada

Department of Polymers and Advanced Materials Centro de Física de Materiales CSIC EHU University of the Basque Country EHU 20018 San Sebastián Spain

Department of Surface and Plasma Science Faculty of Mathematics and Physics Charles University 180 00 Prague 8 Czech Republic

Diamond Light Source Harwell Science and Innovation Campus Didcot OX11 0DE UK

Donostia International Physics Center DIPC 20018 San Sebastián Spain

IKERBASQUE Basque Foundation for Science 48009 Bilbao Spain

Institute of Advanced Materials Universitat Jaume 1 Av de Vicente Sos Baynat s n 12006 Castelló Spain

Institute of Inorganic Chemistry University of Bonn Gerhard Domagk Str 1 53121 Bonn Germany

Zobrazit více v PubMed

Lee M.‐Y., Park K. T., Lee W., Lim H., Kwon Y., Kang S., Crit. Rev. Environ. Sci. Technol. 2020, 50, 769.

Park S., Wijaya D. T., Na J., Lee C. W., Catalysts 2021, 11, 253.

Segets D., Andronescu C., Apfel U.‐P., Nat. Commun. 2023, 14, 7950. PubMed PMC

Wang M., Wang H., Gu Y., Zhu M., Kumar M., Liang J., Tie Z., Ma J., Jin Z., ACS Mater. Lett. 2023, 6, 100.

Lan C., Wang J., Guan S., Liu L., Zhang R., Yin P., Yang J., Liu H., Du X., Dong C., ChemSusChem 2025, 18, e2500386. PubMed

Jiang M., Zhu M., Wang H., Song X., Liang J., Lin D., Li C., Cui J., Li F., Zhang X. L., Nano Lett. 2022, 23, 291. PubMed

Yu F., Deng K., Du M., Wang W., Liu F., Liang D., Carbon Capture Sci. Technol. 2023, 6, 100081.

Jin S., Hao Z., Zhang K., Yan Z., Chen J., Angew. Chem. 2021, 133, 20795. PubMed

Ampelli C., Tavella F., Giusi D., Ronsisvalle A. M., Perathoner S., Centi G., Catal. Today 2023, 421, 114217.

Yang Z., Jin Y., Feng Z., Luo P., Feng C., Zhou Y., An X., Hao X., Abudula A., Guan G., ChemSusChem 2025, 18, e202401181. PubMed

Hori Y., Murata A., Takahashi R., Suzuki S., J. Am. Chem. Soc. 1987, 109, 5022.

Wang M., Li X., Ma X., Wang J., Jin X., Zhang L., Shi J., ChemSusChem 2023, 16, e202300879. PubMed

Yang S., Wang H., Xiong Y., Zhu M., Sun J., Jiang M., Zhang P., Wei J., Xing Y., Tie Z., Nano Lett. 2023, 23, 10140. PubMed

Lee S. H., Avilés Acosta J. E., Lee D., Larson D. M., Li H., Chen J., Lee J., Erdem E., Lee D. U., Blair S. J., J. Am. Chem. Soc. 2025, 147, 6536. PubMed PMC

Osowiecki W. T., Nussbaum J. J., Kamat G. A., Katsoukis G., Ledendecker M., Frei H., Bell A. T., Alivisatos A. P., ACS Appl. Energy Mater. 2019, 2, 7744.

Sebastián‐Pascual P., Escudero‐Escribano M., J. Electroanal. Chem. 2021, 896, 115446.

Vavra J., Ramona G. P. L., Dattila F., Kormányos A., Priamushko T., Albertini P. P., Loiudice A., Cherevko S., Lopéz N., Buonsanti R., Nat. Catal. 2024, 7, 89.

Lei Q., Huang L., Yin J., Davaasuren B., Yuan Y., Dong X., Wu Z.‐P., Wang X., Yao K. X., Lu X., Nat. Commun. 2022, 13, 4857. PubMed PMC

Wang J., Tan H., Zhu Y., Chu H., Chen H. M., Angew. Chem. 2021, 133, 17394.

Grosse P., Yoon A., Rettenmaier C., Herzog A., Chee S. W., Roldan Cuenya B., Nat. Commun. 2021, 12, 6736. PubMed PMC

Arán‐Ais R. M., Rizo R., Grosse P., Algara‐Siller G., Dembélé K., Plodinec M., Lunkenbein T., Chee S. W., Cuenya B. R., Nat. Commun. 2020, 11, 3489. PubMed PMC

Grosse P., Gao D., Scholten F., Sinev I., Mistry H., Roldan Cuenya B., Angew. Chem. 2018, 130, 6300. PubMed

Möller T., Scholten F., Thanh T. N., Sinev I., Timoshenko J., Wang X., Jovanov Z., Gliech M., Roldan Cuenya B., Varela A. S., Angew. Chem. 2020, 132, 18130. PubMed PMC

Gianolio D., Higham M. D., Quesne M. G., Aramini M., Xu R., Large A. I., Held G., ACS Catal. 2023, 13, 5876. PubMed PMC

Zhang J., Xia S., Wang Y., Wu J., Wu Y., Iscience 2024, 27, 110005. PubMed PMC

Xi W., Zhou H., Yang P., Huang H., Tian J., Ratova M., Wu D., ACS Catal. 2024, 14, 13697.

Zheng X., De Luna P., de Arquer F. P. G., Zhang B., Becknell N., Ross M. B., Li Y., Banis M. N., Li Y., Liu M., Joule 2017, 1, 794.

Liang S., Xiao J., Zhang T., Zheng Y., Wang Q., Liu B., Angew. Chem. 2023, 135, e202310740. PubMed

Philips M. F., Gruter G.‐J. M., Koper M. T. M., Schouten K. J. P., ACS Sustain. Chem. Eng. 2020, 8, 15430.

Ampelli C., Giusi D., Miceli M., Merdzhanova T., Smirnov V., Chime U., Astakhov O., Martín A. J., Veenstra F. L. P., Pineda F. A. G., Energy Environ. Sci. 2023, 16, 1644.

Xiang H., Miller H. A., Bellini M., Christensen H., Scott K., Rasul S., Yu E. H., Sustain. Energy Fuels 2020, 4, 277.

Deng Y., Huang Y., Ren D., Handoko A. D., Seh Z. W., Hirunsit P., Yeo B. S., ACS Appl. Mater. Interfaces 2018, 10, 28572. PubMed

García‐Muelas R., Dattila F., Shinagawa T., Martín A. J., Pérez‐Ra, mírez J., López N., J. Phys. Chem. Lett. 2018, 9, 7153. PubMed PMC

Shinagawa T., Larrazábal G. O., Martín A. J., Krumeich F., Pérez‐Ramírez J., ACS Catal. 2018, 8, 837.

Lim J. W., Dong W. J., Park J. Y., Hong D. M., Lee J.‐L., ACS Appl. Mater. Interfaces 2020, 12, 22891. PubMed

Fernández‐Climent R., Redondo J., García‐Tecedor M., Spadaro M. C., Li J., Chartrand D., Schiller F., Pazos J., Hurtado M. F., de la Peña O’Shea V., ACS Catal. 2023, 13, 10457. PubMed PMC

Li T., Yang C., Luo J.‐L., Zheng G., ACS Catal. 2019, 9, 10440.

Zhang Q., Ren Q., Cui R., Zhang L., Luo L., ACS Catal. 2025, 15, 6702.

Herzog A., Bergmann A., Jeon H. S., Timoshenko J., Kühl S., Rettenmaier C., Lopez Luna M., Haase F. T., Roldan Cuenya B., Angew. Chem., Int. Ed. 2021, 60, 7426. PubMed PMC

Rossi K., Buonsanti R., Acc. Chem. Res. 2022, 55, 629. PubMed

Zhao J., Zhao Y., Yue W.‐C., Zheng S.‐M., Li X., Gao N., Zhu T., Zhang Y.‐J., Xia G.‐M., Wang B., CrystEngComm 2021, 23, 6107.

Suresh S., Karthikeyan S., Jayamoorthy K., J. Sci. Adv. Mater. Devices 2016, 1, 343. PubMed

Shi H., Luo L., Li C., Li Y., Zhang T., Liu Z., Cui J., Gu L., Zhang L., Hu Y., Adv. Funct. Mater. 2024, 34, 2310913.

Klysubun W., Thongkam Y., Pongkrapan S., Won‐in K., T‐Thienprasert J., Anal. Bioanal. Chem. 2011, 399, 3033. PubMed

Gaur A., Shrivastava B. D., Joshi S. K., J. Phys.: Conf. Ser. 2009, 190, 12084.

Stojkovikj S., El‐Nagar G. A., Gupta S., Najdoski M., Koleva V., Tzanoudakis T., Firschke F., Bogdanoff P., Mayer M. T., Adv. Funct. Mater. 2025, 35, 2415405.

Kim Y.‐G., Baricuatro J. H., Javier A., Gregoire J. M., Soriaga M. P., Langmuir 2014, 30, 15053. PubMed

Scholten F., Nguyen K. C., Bruce J. P., Heyde M., Roldan Cuenya B., Angew. Chemie Int. Ed. 2021, 60, 19169. PubMed PMC

Lazanas A. C., Prodromidis M. I., ACS Meas. Sci. au 2023, 3, 162. PubMed PMC

Heidary N., Ly K. H., Kornienko N., Nano Lett. 2019, 19, 4817. PubMed

Du Z.‐Y., Wang K., Li S.‐B., Xie Y.‐M., Tian J.‐H., Zheng Q.‐N., Ip W. F., Zhang H., Li J.‐F., Tian Z.‐Q., J. Phys. Chem. C 2024, 128, 11741.

Li H., Wei P., Gao D., Wang G., Curr. Opin. Green Sustain. Chem. 2022, 34, 100589.