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Ru调控的电子结构CoNi-MOF纳米片提升了碱性和海水介质中的水电解动力学。

Ru-regulated electronic structure CoNi-MOF nanosheets advance water electrolysis kinetics in alkaline and seawater media.

作者信息

Li Wenqiang, Guo Bowen, Zhang Ka, Chen Xueyi, Zhang Heng, Chen Wanyu, Chen Haipeng, Li Huabo, Feng Xun

机构信息

College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471934, PR China.

College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471934, PR China; College of Chemistry and Pharmaceutical Engineering, Nanyang Normal University, Nanyang 473601, PR China.

出版信息

J Colloid Interface Sci. 2024 Aug 15;668:181-189. doi: 10.1016/j.jcis.2024.04.144. Epub 2024 Apr 21.

Abstract

Herein, an ion-exchange strategy is utilized to greatly improve the kinetics of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) by Ru-modified CoNi- 1,3,5-Benzenetricarboxylic acid (BTC)-metal organic framework nanosheets (Ru@CoNi-MOF). Due to the higher Ni active sites and lower electron transfer impedance, Ru@CoNi-MOF catalyst requires the overpotential as low as 47 and 279 mV, at a current density of 10 mA/cm toward HER and OER, respectively. Significantly, the mass activity of Ru@CoNi-MOF for HER and OER are 25.9 and 10.6 mA mg, nearly 15.2 and 8.8 times higher than that of Ni-MOF. In addition, the electrolyzer of Ru@CoNi-MOF demonstrates exceptional electrolytic performance in both KOH and seawater environment, surpasses the commercial Pt/C||IrO couple. Theoretical calculations prove that introducing Ru atoms in - CoNi-MOF modulates the electronic structure of Ni, optimizes adsorption energy for H* and reduces energy barrier of metal organic frameworks (MOFs). This modification significantly improves the kinetic rate of the Ru@CoNi-MOF during water splitting. Certainly, this study highlights the utilization of MOF nanosheets as advanced HER/OER electrocatalysts with immense potential, and will paves a way to develop more efficient MOFs for catalytic applications.

摘要

在此,通过钌修饰的钴镍-1,3,5-苯三甲酸(BTC)-金属有机框架纳米片(Ru@CoNi-MOF),采用离子交换策略极大地提高了析氢反应(HER)和析氧反应(OER)的动力学。由于具有更高的镍活性位点和更低的电子转移阻抗,Ru@CoNi-MOF催化剂在电流密度为10 mA/cm²时,HER和OER的过电位分别低至47和279 mV。值得注意的是,Ru@CoNi-MOF对于HER和OER的质量活性分别为25.9和10.6 mA mg⁻¹,分别比Ni-MOF高近15.2倍和8.8倍。此外,Ru@CoNi-MOF电解槽在KOH和海水环境中均表现出优异的电解性能,超过了商业Pt/C||IrO₂电极对。理论计算证明,在CoNi-MOF中引入Ru原子可调节Ni的电子结构,优化对H*的吸附能并降低金属有机框架(MOF)的能垒。这种修饰显著提高了Ru@CoNi-MOF在水分解过程中的动力学速率。当然,本研究突出了MOF纳米片作为具有巨大潜力的先进HER/OER电催化剂的应用,为开发更高效的用于催化应用的MOF铺平了道路。

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