High Loading of Transition Metal Single Atoms on Chalcogenide Catalysts.
High Loading of Transition Metal Single Atoms on Chalcogenide Catalysts.
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DOI：
10.1021/jacs.1c01097
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发表时间：
2021-05
影响因子：
15
通讯作者：
Jianwei Zheng;K. Lebedev;Simson Wu;C. Huang;Tuğçe Ayvalı;Tai‐Sing Wu;Yiyang Li;P. Ho;Y. Soo-Y.-S
中科院分区：
文献类型：
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作者：
Jianwei Zheng;K. Lebedev;Simson Wu;C. Huang;Tuğçe Ayvalı;Tai‐Sing Wu;Yiyang Li;P. Ho;Y. Soo-Y.-S
过渡金属掺杂硫系化合物是一类重要的催化剂，由于其独特的物理化学性质，在石油化工和能源相关的化学转化方面受到了越来越多的关注。对于实际应用来说，通过金属在硫化物表面的均匀分散来实现最大的原子利用率是必不可少的。在这里，我们报告了一种使用硫脲配位的过渡金属络合物的沉积方法的详细研究。这种方法可以制备包括贵金属和非贵金属过渡金属(Fe，Co，Ni，Cu，Pt，Pd，Ru)在内的各种单原子库，其金属负载量高达10wt%，用于各种超薄2D硫化物(MoS2，MoSe2，WS2和WSe2)。最新的表征表明，掺杂的单一过渡金属原子与剥离的2D材料中的表面阴离子和阴离子空位发生强烈的相互作用，导致金属在没有团聚的情况下高度分散。以MoS_2上的Fe为基准，发现Fe原子分散到10wt%，超过这一负载量，明显形成共面Fe团簇。Fe原子在导带具有较高的电子密度，与相应的表面Fe团簇和其他已报道的用于逆水煤气变换反应的Fe催化剂相比，在CO2加氢合成CO Per Fe反应中表现出更好的本征活性和稳定性。
Transition metal doped chalcogenides are one of the most important classes of catalysts that have been attracting increasing attention for petrochemical and energy related chemical transformations due to their unique physiochemical properties. For practical applications, achieving maximum atom utilization by homogeneous dispersion of metals on the surface of chalcogenides is essential. Herein, we report a detailed study of a deposition method using thiourea coordinated transition metal complexes. This method allows the preparation of a library of a wide range of single atoms including both noble and non-noble transition metals (Fe, Co, Ni, Cu, Pt, Pd, Ru) with a metal loading as high as 10 wt % on various ultrathin 2D chalcogenides (MoS2, MoSe2, WS2 and WSe2). As demonstrated by the state-of-the-art characterization, the doped single transition metal atoms interact strongly with surface anions and anion vacancies in the exfoliated 2D materials, leading to high metal dispersion in the absence of agglomeration. Taking Fe on MoS2 as a benchmark, it has been found that Fe is atomically dispersed until 10 wt %, and beyond this loading, formation of coplanar Fe clusters is evident. Atomic Fe, with a high electron density at its conduction band, exhibits a superior intrinsic activity and stability in CO2 hydrogenation to CO per Fe compared to corresponding surface Fe clusters and other Fe catalysts reported for reverse water-gas-shift reactions.