钌基电催化剂的设计合成及其析氢性能研究

  发展氢气作为可再生能源的能源载体，已经被认为是实现全球“碳中和”目标的重要战略。电解水制氢具有高能效、零污染的优势。析氢反应（Hydrogen Evolution Reaction，HER）是电解水制氢的阴极反应，多采用铂基催化剂驱动反应。然而铂的成本昂贵和储备稀缺限制了其大规模的应用，因此开发高活性、低成本和高寿命的析氢反应催化剂尤为重要。本文通过对催化剂微观形貌的设计、活性组分电子结构的调控等方式致力于开发Ru基析氢电催化剂。本文研究两种策略：

  采用模板法制备多级结构大孔-介孔的P掺杂碳载体负载原子级分散的Ru-Mo纳米团簇和Ru单原子催化剂，第二种金属Mo的引入既可以提高催化剂的析氢性能，又可以有效地抑制Ru纳米团簇结晶化，趋于形成无定形的超小Ru-Mo纳米团簇，提高金属原子的利用率。Ru-Mo/PC催化剂为析氢反应提供高密度、多样化的活性位点，有利于提升析氢性能。电化学析氢反应测试结果表明，RuMo_1.5/PC在碱性介质中表现出优异的析氢性能，10 mA cm⁻²电流密度时仅需过电位17.9 mV。

  过渡金属磷化物（Transition-metal Phosphides, TMPs）因经济和易获取的特点备受关注。采用商业碳载体EC制备磷化钌催化剂，通过退火温度的调控得到碳负载不同化学组成的磷化钌催化剂。在酸性和碱性介质中RuP@EC催化剂的析氢活性优于Ru₂P@EC，归因于RuP@EC催化剂中P含量较高，带负电荷的P原子可以作为氢离子的受体，并使氢离子在活性位点Ru中心原子上还原生成H₂。采用介孔碳制备磷化钌催化剂，随着退火温度升高，RuP纳米颗粒易团聚成大颗粒尺寸，其具有较低的表面能，可以使P稳定不易被氧化，从而提升电化学析氢性能。

    Developing hydrogen as an energy carrier for renewable energy has been considered an important strategy for achieving global carbon neutrality. Hydrogen production from water electrolysis has advantages of high energy efficiency and zero pollution. Hydrogen evolution reaction (HER) is the cathode reaction of hydrogen production from water electrolysis, and platinum-based catalysts are often used to drive the reaction. However, the high cost and scarce reserves of platinum limit its large-scale application, so it is particularly important to develop HER catalysts with high activity, low cost and high life. In this paper, Ru-based electrocatalysts were developed for HER through the design of catalyst microstructure and the regulation of active component electronic structure. Two strategies were explored in this work.

    Hierarchical macroporous-mesoporous P-doped carbon supports were prepared by template method to support atomically dispersed Ru-Mo nanoclusters and Ru monoatomic catalysts. The introduction of the second metal Mo can not only improve the hydrogen evolution performance of the catalyst, but also effectively inhibit the crystallization of Ru nanoclusters, tending to form amorphous ultra-small Ru-Mo nanoclusters and improve the utilization rate of metal atoms. Ru-Mo/PC catalyst provides high-density and diversified active sites for hydrogen evolution reaction, which is conducive to improving hydrogen evolution performance. Electrochemical hydrogen evolution test results showed that RuMo_1.5 /PC exhibited excellent HER performance in alkaline medium, and only 17.9 mV of overpotential was required at a current density of 10 mA cm⁻².

    Transition-metal phosphides (TMPs) have attracted much attention due to their economic and accessible characteristics. Ruthenium phosphide catalysts were prepared by commercial carbon support EC, and carbon supported ruthenium phosphide catalysts with different chemical compositions were obtained by adjusting the annealing temperature. In acidic and alkaline media, the HER activity of RuP@EC catalyst is better than that of Ru₂P@EC, which is attributed to the high P content in RuP@EC catalyst. The negatively charged P atom can be used as the receptor of H⁺, and the H⁺ can be reduced to H₂ on the active site Ru center atom. Mesoporous carbon was used to prepare ruthenium phosphate catalyst. With the increase of annealing temperature, RuP nanoparticles are easy to agglomerate into large particle size, which has low surface energy and can make P stable and difficult to be oxidized, thus improving the electrochemical hydrogen evolution performance.

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