Aluminum-incorporation activates vanadium carbide with electron-rich carbon sites for efficient pH-universal hydrogen evolution reaction.
Aluminum-incorporation activates vanadium carbide with electron-rich carbon sites for efficient pH-universal hydrogen evolution reaction.
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DOI：
10.1016/j.jcis.2023.11.106
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发表时间：
2023-11
影响因子：
9.9
通讯作者：
Yanan Zheng;Yiwei Mou;Yanwei Wang;Jin Wan;Guangxu Yao;Chuanzhen Feng;Yue Sun;Longhua Dai
中科院分区：
文献类型：
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作者：
Yanan Zheng;Yiwei Mou;Yanwei Wang;Jin Wan;Guangxu Yao;Chuanzhen Feng;Yue Sun;Longhua Dai
碳化钒（VC）因其类似铂的性质和丰富的地球储量而成为最具潜力的析氢反应催化剂。然而，由于反应中间体与催化剂的不利相互作用，其表现出不足的催化性能。本文以NH 4VO 3为主要原料，通过精确控制CH 4/Ar流量比，采用化学气相碳化法首次制备了非过渡金属Al掺杂VC（1 0 0）纳米花碳杂化泡沫镍（Al-VC@C/NF）高效HER催化剂。Al-VC@C/NF催化剂在0.5 M H2SO 4和1 M KOH中的过电位在10 mA cm− 2的电流密度下分别仅为58 mV和97 mV，这是非贵金属碳化钒基催化剂中最好的HER性能。同时，Al-VC@C/NF具有较小的Tafel斜率（45 mV dec-1和73 mV dec-1），在酸性和碱性介质中具有优异的稳定性。理论计算表明，掺杂Al原子可以诱导电子在碳化钒表面重新分布，形成富电子碳位，从而显著降低HER过程中的能垒。这项工作提供了一种新的策略，通过非过渡金属掺杂调制钒基碳作为有效的HER催化剂。
Vanadium carbide (VC) is the greatest potential hydrogen evolution reaction (HER) catalyst because of its platinum-like property and abundant earth reserves. However, it exhibits insufficient catalytic performance due to the unfavorable interaction of reaction intermediates with catalysts. In this work, using NH4VO3as the main raw material, the flow ratio of CH4to Ar was accurately controlled, and a non-transition metal Al-doped into VC (1 0 0) nano-flowers with carbon hybrids on nickel foams (Al-VC@C/NF) was prepared for the first time as a high-efficiency HER catalyst by chemical vapor carbonization. The overpotential of Al-VC@C/NF catalysts in 0.5 M H2SO4and 1 M KOH at a current density of 10 mA cm−2are only 58 mV and 97 mV, respectively, which are the best HER performance among non-noble metal vanadium carbide based catalysts. Simultaneously, Al-VC@C/NF exhibits small Tafel slope (45 mV dec-1and 73 mV dec-1) and excellent stability in acidic and alkaline media. Theoretical calculations demonstrate that doped Al atoms can induce electron redistribution on the vanadium carbide surface to form electron-rich carbon sites, which significantly reduces the energy barrier during the HER process. This work provides a new tactic to modulate vanadium-based carbons as efficient HER catalysts through non-transition metal doping.