Copper-based hydrogen evolution electrocatalysts are promising materials to scale-up hydrogen production due to their reported high current densities; however, electrode durability remains a challenge. Here, we report a facile, cost-effective, and scalable synthetic route to produce Cu2-xS electrocatalysts, exhibiting hydrogen evolution rates that increase for ∼1 month of operation. Our Cu2-xS electrodes reach a state-of-the-art performance of ∼400 mA cm-2 at -1 V vs RHE under mild conditions (pH 8.6), with almost 100% Faradaic efficiency for hydrogen evolution. The rise in current density was found to scale with the electrode electrochemically active surface area. The increased performance of our Cu2-xS electrodes correlates with a decrease in the Tafel slope, while analyses by X-ray photoemission spectroscopy, operando X-ray diffraction, and in situ spectroelectrochemistry cooperatively revealed the Cu-centered nature of the catalytically active species. These results allowed us to increase fundamental understanding of heterogeneous electrocatalyst transformation and consequent structure-activity relationship. This facile synthesis of highly durable and efficient Cu2-xS electrocatalysts enables the development of competitive electrodes for hydrogen evolution under mild pH conditions.

Catalan Institute of Nanoscience and Nanotechnology and BIST Campus UAB Bellaterra 08193 Barcelona Catalonia Spain

Centro de Física de Materiales and Material Physics Center CSIC UPV EHU Manuel Lardizabal 5 20018 San Sebastián Spain

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 University of the Basque Country UPV EHU 20018 San Sebastián Spain

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

Donostia International Physics Center 20018 San Sebastián Spain

ICREA Pg Lluís Companys 23 08010 Barcelona Catalonia 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

Materials Chemistry Area Civil Engineering Department Corporación Universitaria Minuto de Dios Calle 80 Main Sede Bogotá Colombia Nanotechnology Applications Area Environmental Engineering Department Universidad Militar Nueva Granada Km 2 via Cajicá Zipaquirá 110311 Colombia

Photoactivated Processes Unit IMDEA Energy Institute Parque Tecnológico de Móstoles Avda Ramón de la Sagra 3 28935 Móstoles Madrid Spain

Research Cluster on Converging Sciences and Technologies Departamento de Ingeniería Electrónica Universidad Central Calle 5 No 21 38 Bogotá 110311 Colombia

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