Ruthenium Nanoclusters and Single Atoms on α-MoC/N-Doped Carbon Achieves Low-input/Input-free Hydrogen Evolution via Decoupled/Coupled Hydrazine Oxidation

Yapeng Li; Shuwen Niu; Peigen Liu; Rongrong Pan; Huaikun Zhang; Nazir Ahmad; Yi Shi; Xiao Liang; Mingyu Cheng; Shenghua Chen; Junyi Du; Maolin Hu; Dingsheng Wang; Wei Chen; Yadong Li

doi:10.1002/anie.202316755

Ruthenium Nanoclusters and Single Atoms on α-MoC/N-Doped Carbon Achieves Low-input/Input-free Hydrogen Evolution via Decoupled/Coupled Hydrazine Oxidation

Angew Chem Int Ed Engl. 2024 May 13:e202316755. doi: 10.1002/anie.202316755. Online ahead of print.

Authors

Yapeng Li¹, Shuwen Niu¹, Peigen Liu², Rongrong Pan², Huaikun Zhang³, Nazir Ahmad⁴, Yi Shi², Xiao Liang⁵, Mingyu Cheng³, Shenghua Chen⁵, Junyi Du⁶, Maolin Hu¹, Dingsheng Wang⁷, Wei Chen⁸, Yadong Li⁵

Affiliations

¹ Wenzhou University, Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials Engineering, CHINA.
² University of Science and Technology of China, Center of Advanced Nanocatalysis (CAN), Department of Applied Chemistry, CHINA.
³ University of Science and Technology of China, CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, CHINA.
⁴ University of Science and Technology of China, Department of Materials Science and Engineering, CHINA.
⁵ Tsinghua University, Department of Chemistry, CHINA.
⁶ Suzhou Institute of Nano-tech and Nano-bionics, Division of Advanced Materials, CHINA.
⁷ Tsinghua University, Chemistry, CHINA.
⁸ Wenzhou University, College of Chemistry and Materials Engineering, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, 325027, Wenzhou, CHINA.

PMID: 38739420
DOI: 10.1002/anie.202316755

Abstract

The hydrazine oxidation-assisted H2 evolution method promises low-input and input-free hydrogen production. However, developing high-performance catalysts for hydrazine oxidation (HzOR) and hydrogen evolution (HER) is challenging. Here, we introduce a bifunctional electrocatalyst α-MoC/N-C/RuNSA, merging ruthenium (Ru) nanoclusters (NCs) and single atoms (SA) into cubic α-MoC nanoparticles-decorated N-doped carbon (α-MoC/N-C) nanowires, through electrodeposition. The composite showcases exceptional activity for both HzOR and HER, requiring -80 mV and -9 mV respectively to reach 10 mA cm-2. Theoretical and experimental insights confirm the importance of two Ru species for bifunctionality: NCs enhance the conductivity, and its coexistence with SA balances the H adsorption for HER and facilitates the initial dehydrogenation during the HzOR. In the overall hydrazine splitting (OHzS) system, α-MoC/N-C/RuNSA excels as both anode and cathode materials, achieving 10 mA cm-2 at just 64 mV. The zinc hydrazine (Zn-Hz) battery assembled with α-MoC/N-C/RuNSA cathode and Zn foil anode can exhibit 96% energy efficiency, as well as temporary separation of hydrogen gas during the discharge process. Therefore, integrating Zn-Hz with OHzS system enables self-powered H2 evolution, even in hydrazine sewage. Overall, the amalgamation of NCs with SA achieves diverse catalytic activities for yielding multifold hydrogen gas through advanced cell-integrated-electrolyzer system.

Keywords: Ru single atoms, Ru nanoclusters, Hydrogen Evolution Reaction, Hydrazine Oxidation Reaction, Bifunctionality.