Sulfur Moiety as a Double-Edged Sword for Realizing Ultrafine Supported Metal Nanoclusters with a Cationic Nature.
Sulfur Moiety as a Double-Edged Sword for Realizing Ultrafine Supported Metal Nanoclusters with a Cationic Nature.
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DOI：
10.1021/acsami.8b18952
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发表时间：
2019-03
影响因子：
9.5
通讯作者：
Xinping Duan;Liao Ning;Yan Yin;Yanting Huang;Jian Gao;Haiqiang Lin;K. Tan;Huihuang Fang;Linmin Ye;Xin Lu;Youzhu Yuan
中科院分区：
文献类型：
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作者：
Xinping Duan;Liao Ning;Yan Yin;Yanting Huang;Jian Gao;Haiqiang Lin;K. Tan;Huihuang Fang;Linmin Ye;Xin Lu;Youzhu Yuan
非均匀分散的金属纳米团簇具有高的热稳定性和稳定的非金属性质，显示出优异的催化性能。在这项工作中，我们报告的作用，硫部分在氢氯化催化碳载金（Au/C）。实验和理论分析的结合表明，在≥180 °C时，Au/-SO 3 H界面上的-SO 3 H及其衍生的-SO2 H硫物种具有较高的热稳定性和催化活性。相比之下，接枝的硫醇基团（-SH）和衍生的低价硫物种的碳显着不稳定的Au纳米簇，促进其快速烧结成大的Au纳米粒子，并导致其阳离子性质的损失。理论计算表明，-SO 3 H有利于吸附和稳定阳离子Au物种。与Auα+/Au 0原子比分别为1.02和0.24（α = 1或3）的Au/C和Au-SH/C相比，-SO 3 H基团与阳离子Au物种之间的相互作用使Au的高氧化态得以有效保留（Auα+/Au 0 = 3.82），从而显著提高了乙炔氢氯化反应的活性和耐久性。这些结果清楚地表明了乙炔氢氯化反应中硫部分对催化Au组分的双刃剑效应。硫物质在金属纳米团簇的稳定化/去稳定化中的双刃剑效应也适用于其他金属，例如Ru、Pd、Pt和Cu。总体而言，这项研究丰富了一般的金属簇的稳定性的理解，并提供了一个湿化学策略稳定支持的无配体纳米簇的洞察力。
Heterogeneously and uniformly dispersed metal nanoclusters with high thermal stability and stable nonmetallic nature show outstanding catalytic performance. In this work, we report on the role of sulfur moieties in hydrochlorination catalysis over carbon-supported gold (Au/C). A combination of experimental and theoretical analyses shows that the -SO3H and derived -SO2H sulfur species in high oxidation states at the interface between Au and -SO3H at ≥180 °C give rise to high thermal stability and catalytic activity. By contrast, the grafted thiol group (-SH) and the derived low-valence sulfur species on carbon markedly destabilize the Au nanoclusters, promoting their rapid sintering into large Au nanoparticles and leading to the loss of their cationic nature. Theoretical calculations suggest that -SO3H favorably adsorbs and stabilizes cationic Au species. Compared to Au/C and Au-SH/C with the Auα+/Au0 atomic ratios of 1.02 and 0.24, respectively (α = 1 or 3), the activity and durability of acetylene hydrochlorination are remarkably enhanced by the interaction between the -SO3H moieties and cationic Au species that enables the high oxidation state of Au to be effectively retained (Auα+/Au0 = 3.82). These results clearly demonstrate the double-edged sword effect of sulfur moieties on the catalytic Au component in acetylene hydrochlorination. The double-edged sword effect of sulfur species in the stabilization/destabilization of metal nanoclusters is also applicable to other metals such as Ru, Pd, Pt, and Cu. Overall, this study enriches the general understanding of the stabilization of metal clusters and provides insight into a wet chemistry strategy for stabilizing supported ligand-free nanoclusters.