Active Sites on ZnXZr1-XO2-X Solid Solution Catalysts for CO2-to-Methanol Hydrogenation
Active Sites on ZnXZr1-XO2-X Solid Solution Catalysts for CO2-to-Methanol Hydrogenation
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DOI：
10.1021/acscatal.2c01996
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发表时间：
2022-06-20
期刊：
影响因子：
12.9
通讯作者：
Iyoki, Kenta
中科院分区：
文献类型：
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作者：
Tada, Shohei;Ochiai, Nagomu;Iyoki, Kenta
最近，ZnxZr1-xO2-x催化剂引起了人们的关注。在这项研究中，我们研究了Zn含量对ZnxZr1-xO2-x催化剂上CO2加氢制甲醇的影响，并通过计算和实验确定了活性位点结构。当Zn含量较低时，ZnxZr1-xO2-x含有Zn簇（孤立的[ZnOa]簇和[ZnbOc]低聚物）。簇的存在表明 Zn-O-Zr 位点的形成。有趣的是，我们的计算表明，簇中的 Zn 物质很容易暴露在 ZnxZr1-xO2-x 表面上。这一结果与实验结果一致，表明Zn物种在ZnxZr1-xO2-x表面上分布不均匀，并沉积在表面附近。在 ZrO2 中添加过量的 Zn 导致了含 Zn 簇和 ZnO 纳米颗粒的形成。在反应过程中，来自簇的 Zn-O-Zr 位点表现出 CO2 转化为甲醇加氢的特定活性。了解活性位点结构将有助于 ZnxZr1-xO2-x 催化剂的未来发展。
Recently, ZnxZr1-xO2-x catalysts have attracted catalysts. In this study, we examined the effect of the Zn content on CO2-to-methanol hydrogenation over ZnxZr1-xO2-x catalysts and determined the active-site structure through both calculations and experiments. When the Zn content was low, ZnxZr1-xO2-x contained Zn clusters (isolated [ZnOa] clusters and [ZnbOc] oligomers). The presence of clusters indicates the formation of Zn-O-Zr sites. Interestingly, our calculations revealed that the Zn species in the clusters are easily exposed on the ZnxZr1-xO2-x surface. This result is in line with the experimental results, suggesting that Zn species were unevenly distributed on the ZnxZr1-xO2-x surface and deposited near the surface. The addition of excess Zn to ZrO2 led to the formation of both Zn-containing clusters and ZnO nanoparticles. During the reactions, the Zn-O- Zr sites derived from the clusters showed specific activity for CO2-to-methanol hydrogenation. Understanding the active-site structure will lead to the future development of ZnxZr1-xO2-x catalysts.