Coupling atom ensemble and electron transfer in PdCu for superior catalytic kinetics in hydrogen generation

• Published in: Nano research Vol. 16; no. 7; pp. 9012 - 9021
• Main Authors: Zhao, Xinru, Liu, Yanyan, Yuan, Huiyu, Wen, Hao, Zhang, Huanhuan, Ashraf, Saima, Guan, Shuyan, Liu, Tao, Mehdi, Sehrish, Shen, Ruofan, Guo, Xianji, Fan, Yanping, Liu, Baozhong, Li, Baojun
• Format: Journal Article
• Language: English
• Published: Beijing Tsinghua University Press 01.07.2023; Springer Nature B.V
• Subjects: Activation energy; Alloys; Ammonia; Atomic/Molecular Structure and Spectra; Biomedicine; Biotechnology; Carbon; Catalysts; Chemistry and Materials Science; Condensed Matter Physics; Electron density; Electron transfer; Energy; Experimental research; Hydrogen; Hydrogen bonds; Hydrogen production; Hydrolysis; Kinetics; Materials Science; Nanoalloys; Nanocomposites; Nanoparticles; Nanotechnology; Palladium; Reaction kinetics; Research Article; Titanium dioxide; ensemble effect; borohydride hydrolysis; d-band holes; PdCu nanoalloy; dual-active sites
• ISSN: 1998-0124; 1998-0000
• DOI: 10.1007/s12274-023-5667-1

The design of high-performance catalysts is the key to the efficient utilization of hydrogen energy. In this work, a PdCu nanoalloy was successfully anchored on TiO 2 encapsulated with carbon to construct a catalyst. Outstanding kinetics of the hydrolysis of ammonia borane (turnover frequency of 279 mol H 2 ⋅ min − 1 ⋅ mol Pd − 1 ) ranking the third place among Pd-based catalysts was achieved in the absence of alkali. Both experimental research and theoretical calculations reveal a lower activation energy of the B-H bond on the PdCu nanoalloy catalyst than that on pristine Pd and a lower activation energy of the O-H bond than that on pristine Cu. The redistribution of d electron and the shift of the d-band center play a critical role in increasing the electron density of Pd and improving the catalytic performances of Pd 0.1 Cu 0.9 /TiO 2 -porous carbon (Pd 0.1 Cu 0.9 /T-PC). This work provides novel insights into highly dual-active alloys and sheds light on the mechanism of dual-active sites in promoting borohydride hydrolysis.