Exploring the Reaction Mechanism of H2S Decomposition with MS3 (M = Mo, W) Clusters
Exploring the Reaction Mechanism of H2S Decomposition with MS3 (M = Mo, W) Clusters
复制标题
MS3(M=Mo,W)簇团簇探索H2S分解反应机理
DOI：
10.1021/acsomega.0c01430
复制
发表时间：
2020-05
期刊：
影响因子：
4.1
通讯作者：
Chen Wen-Jie
中科院分区：
文献类型：
--
作者：
Wang Bin;Zhang Si-Yuan;Ye Ling-Hong;Zhang Xiao-Fei;Zhang Yong-Fan;Chen Wen-Jie
H2S在自然界中大量存在，是工业中常见的副产品。硫化钼已被证明在催化分解硫化氢（H2S）以产生氢气中具有活性。本文采用密度泛函理论（DFT）方法研究了H2S与MS 3（M = Mo，W）团簇的反应机理. H2S与MoS 3的反应机理与与WS 3的反应机理大致相同，并且与MoS 3的反应的自由能分布略高于与WS 3的反应的自由能分布。总的驱动力（-ΔG）是正的，总的反应势垒（ΔGb）相当小，表明这样的H2生产是有利于产品的。MS_3（M = Mo，W）团簇具有爪形结构，具有亲电金属位点，可以接收接近的H_2S分子。经过多次氢原子转移（HAT）过程，最终形成MS 4·H2（IM-4）配合物，该配合物可在较低温度下脱附H2。单重态产物MS 4簇含有单重态S2部分，类似于硫化物催化剂表面上吸附的单重态S2。将理论计算结果与MoS 2催化剂多相催化分解H2S的实验结果进行了比较。我们的工作可能会提供一些见解的优化设计的相关催化剂。
H2S is abundantly available in nature, and it is a common byproduct in industries. Molybdenum sulfides have been proved to be active in the catalytic decomposition of hydrogen sulfide (H2S) to produce hydrogen. In this study, density functional theory (DFT) calculations are carried out to explore the reaction mechanisms of H2S with MS3 (M = Mo, W) clusters. The reaction mechanism of H2S with MoS3 is roughly the same as that of the reaction with WS3, and the free-energy profile of the reaction with MoS3 is slightly higher than that of the reaction with WS3. The overall driving forces (−ΔG) are positive, and the overall reaction barriers (ΔGb) are rather small, indicating that such H2 productions are product-favored. MS3 (M = Mo, W) clusters have clawlike structures, which have electrophilic metal sites to receive the approaching H2S molecule. After several hydrogen-atom transfer (HAT) processes, the final MS4·H2 (IM-4) complexes are formed, which could desorb H2 at a relatively low temperature. The singlet product MS4 clusters contain the singlet S2 moiety, similar to the adsorbed singlet S2 on the surface of sulfide catalysts. The theoretical results are compared with the experiments of heterogeneous catalytic decomposition of H2S by MoS2 catalysts. Our work may provide some insights into the optimal design of the relevant catalysts.
登录
查看更多内容
影响因子：
16.6
作者：
Liu JC;Ma XL;Li Y;Wang YG;Xiao H;Li J
通讯作者：
Li J
DOI：
10.1021/jp806166h
发表时间：
2008-10
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
Bin Wang;Hua‐Jin Zhai;Xin Huang;Lai‐Sheng Wang
通讯作者：
Bin Wang;Hua‐Jin Zhai;Xin Huang;Lai‐Sheng Wang
影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD
DOI：
10.1021/i160068a002
发表时间：
1978-01-01
期刊：
INDUSTRIAL & ENGINEERING CHEMISTRY FUNDAMENTALS
影响因子：
--
作者：
FUKUDA, K;DOKIYA, M;KOTERA, Y
通讯作者：
KOTERA, Y
影响因子：
2.8
作者：
Castleman, A. W., Jr.
通讯作者：
Castleman, A. W., Jr.