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首页> 外文期刊>ACS catalysis >Monomeric MoS42--Derived Polymeric Chains with Active Molecular Units for Efficient Hydrogen Evolution Reaction
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Monomeric MoS42--Derived Polymeric Chains with Active Molecular Units for Efficient Hydrogen Evolution Reaction

机译：单体MOS42 - 衍生的聚合物链，具有活性分子单元，用于有效氢化反应

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摘要

Molybdenum sulfides have attracted widespread attention as promising nonprecious-metal catalysts for the hydrogen evolution reaction (HER). Since the MoS2 edge was proposed as a major active site, molecular and polymeric analogues to the MoS2 edge have been widely explored as the HER catalysts. In particular, amorphous MoSx coordination polymers have been considered as active HER catalysts because they are rich in unsaturated Mo-S coordination, which is the characteristic of the active MoS2 edge. Herein, we report that the simple monomeric thiomolybdate (MoS42-) could adopt a polymeric chain structure, which exhibited high HER activity; its turnover frequency surpassed those of dimeric [Mo2S12](2-)- and trimeric [Mo3S13](2-)-derived MoSx catalysts. This high HER activity of monomeric MoS42- is attributed to the polymerization of MoS42- anions, generating active molecular analogues that comprise monomeric S2- sites bridging Mo(V) and Mo(W). Density functional theory calculations of possible polymeric chain structures identified the Mo(IV)Mo(V)(2)(S-2(2-))(2)(S2-)(5) unit as the most plausible structure that best matched the experimentally deduced structure. The Gibbs free energy for hydrogen adsorption on the bridging S2- (p-S2-) site in Mo(IV)Mo(V)(2)(S-2(2-))(2)(S2-)(5) was found to be -0.05 eV, which is close to the thermoneutral state. Combined analyses by resonance Raman spectroscopy and extended X-ray absorption fine structure suggested the role of Mo-oxo (Mo=O-x) species to generate the active Mo(V)-(mu-S2-)-Mo(IV) center for effective hydrogen adsorption.
机译：硫化硫化物引起了广泛的关注，作为氢进化反应（她）的非普烈金属催化剂。由于MOS2边缘被提出为主要的活性位点，因此对MOS2边缘的分子和聚合物类似物被广泛探索为催化剂。特别地，无定形MOSX配位聚合物被认为是活性的催化剂，因为它们具有富含不饱和的MO-S配位，这是活性MOS2边缘的特征。在此，我们报告说简单的单体硫聚菌（MOS42-）可以采用聚合物链结构，其表现出高度的活性;其周转频率超过二聚体[Mo2S12]（2 - ） - 和三聚体[MO3S13]（2 - ） - 衍生的MOSX催化剂。这种高度的单体MOS42活性归因于MOS42-阴离子的聚合，产生包含桥接MO（V）和MO（W）的单体S2-位点的活性分子类似物。可能的聚合物链结构的密度官能理论计算鉴定了Mo（IV）Mo（V）（2）（2）（S-2（2 - ））（2）（S2 - ）（5）单位，作为最符合匹配的最合理的结构实验推导的结构。用于在Mo（IV）Mo（V）（2）（S-2）（2）（S-2）（2）（S2）（S2 - ）（5）中的桥接S2-（P-S2-）位点上的氢吸附的氢吸附能量被发现为-0.05eV，靠近热电因状态。通过共振拉曼光谱和延长X射线吸收细结构的组合分析表明Mo-Oxo（Mo = Ox）物种产生活性MO（V） - （Mu-S2 - ） - Mo（IV）的有效中心的作用氢吸附。

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