Obtaining insights into the active-site structure of a catalyst during high-pressure and high-temperature catalytic reactions is extremely challenging. In this study, changes in the coordination structure of Zn species in Zn-doped ZrO₂ catalysts (Zn/(Zn + Zr) atomic ratio = 9%) during CO₂-to-methanol hydrogenation (cell temperature = 400 °C, pressure = 9 bars) was investigated using high-pressure in situ X-ray absorption fine structure measurements and density functional theory calculations. The formation of Zn–H species, which are considered the active sites for the reaction, was very limited, with most Zn species existing as [ZnO_a] isolated clusters. Additionally, the adsorption of CO₂ at the Zr⁴⁺ sites near the Zn species induced significant distortions in the coordination structure of the Zn species. This study provides new insights into the catalytic active-site structure.

中文翻译：

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Zn 掺杂 ZrO2 上 CO2 加氢制甲醇的高压原位 X 射线吸收精细结构测量


在高压和高温催化反应过程中深入了解催化剂的活性位点结构极具挑战性。在本研究中，Zn 掺杂 ZrO ₂催化剂（Zn/(Zn + Zr) 原子比 = 9%）中 Zn 配位结构在 CO ₂转化为甲醇加氢过程中（池温度 = 400 °C，压力= 9 巴）通过高压原位X 射线吸收精细结构测量和密度泛函理论计算进行了研究。被认为是反应活性位点的 Zn-H 物种的形成非常有限，大多数 Zn 物种以 [ZnO _a ] 孤立簇的形式存在。此外，CO ₂在Zn 物质附近的Zr ⁴⁺位点上的吸附引起了Zn 物质配位结构的显着扭曲。这项研究为催化活性位点结构提供了新的见解。