Raju Karimadom Basil, Varshney Shalaka, Zidki Tomer, Meyerstein Dan, Kornweitz Haya
Chemical Science Department and The Radical Research Centre, Ariel University P.O.B. 3 Ariel, 40700, Ariel, Israel.
Chemistry Department, Ben-Gurion University, Beer-Sheva, Israel.
Chemphyschem. 2022 Jul 5;23(13):e202200069. doi: 10.1002/cphc.202200069. Epub 2022 May 17.
The mechanism of the catalytic hydrolysis of BH on Au(111) as studied by DFT is reported. The results are compared to the analogous process on Ag(111) that was recently reported. It is found that the borohydride species are adsorbed stronger on the Au -NP surface than on the Ag -NP surface. The electron affinity of the Au is larger than that of Ag. The results indicate that only two steps of hydrolysis are happening on the Au(111) surface and the reaction mechanism differs significantly from that on the Ag(111) surface. These remarkable results were experimentally verified. Upon hydrolysis, only three hydrogens of BH are transferred to the Au surface, not all four, and H generation is enhanced in the presence of surface H atoms. Thus, it is proposed that the BH hydrolysis and reduction mechanisms catalyzed by M -NPs depend considerably on the nature of the metal.
报道了通过密度泛函理论（DFT）研究的BH在Au(111)上催化水解的机理。将结果与最近报道的Ag(111)上的类似过程进行了比较。发现硼氢化物物种在金纳米颗粒（Au-NP）表面的吸附比在银纳米颗粒（Ag-NP）表面更强。金的电子亲和力大于银。结果表明，在Au(111)表面仅发生两步水解，且反应机理与Ag(111)表面有显著差异。这些显著结果得到了实验验证。水解时，BH中只有三个氢转移到金表面，而非全部四个氢，并且在表面氢原子存在下氢的生成会增强。因此，有人提出M-NPs催化的BH水解和还原机理在很大程度上取决于金属的性质。
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