In Situ Generation of the Cu@3D-ZrOx Framework Catalyst for Selective Methanol Synthesis from CO2/H2,ACS Catalysis

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In Situ Generation of the Cu@3D-ZrOx Framework Catalyst for Selective Methanol Synthesis from CO2/H2
ACS Catalysis ( IF 11.3 ) Pub Date : 2019-12-02 00:00:00 , DOI: 10.1021/acscatal.9b03738
Tangkang Liu ₁ , Xinlin Hong ₁ , Guoliang Liu ₁

Affiliation

Cu-based catalysts have been widely studied for direct hydrogenation of CO₂ to methanol. Their activities quite depend on the amount of exposed active sites (e.g., Cu-oxide interfaces), which can be tuned by the particle size as well as porosity. Here, we report an active, selective, and stable Cu@ZrO_x catalyst with a three-dimensional (3D) porous framework structure via the in situ reconstruction of size-confined Cu@UiO-66. The optimized CU-0.5-300 catalyst shows a high methanol selectivity of 78.8% at a conversion of 13.1% at 260 °C, 4.5 MPa, giving a methanol space-time yield of 796 g·kg_cat^–1·h^–1. It also shows long-term stability for 105 h in a time-on-stream test. Such good performance benefits from abundant Cu–ZrO_x interfaces and a stable 3D ZrO_x framework. During the reaction, ZrO_x species in situ evolves from the unstable Zr-oxide cluster (the building unit of UiO-66) or amorphous ZrO₂ to a stable tetragonal ZrO₂ phase, but strong metal–support interaction (SMSI) at Cu–ZrO_x interfaces retains. The SMSI enables the formation of Cu⁺ at the ZrO₂ surface, which is strongly associated with the active sites for methanol synthesis. In situ diffuse-reflectance infrared Fourier transform spectroscopy studies reveal methanol synthesis which follows a HCOO-intermediated pathway. It is believed that this work provides an “in situ reconstruction” strategy to fabricate a practical Cu@ZrO_x framework catalyst for methanol production.

中文翻译：

原位生成Cu @ 3D-ZrOx骨架催化剂，用于由CO2 / H2选择性合成甲醇

铜基催化剂已被广泛研究用于将CO ₂直接加氢为甲醇。它们的活性完全取决于暴露的活性位点（例如，氧化铜界面）的数量，可以通过粒径和孔隙率对其进行调整。在这里，我们报告一个的活性，选择性，和稳定的Cu @的ZrO _X经由原位重建尺寸受限的Cu @ UIO-66催化剂与三维（3D）多孔骨架结构。优化的CU-0.5-300催化剂在260°C，4.5 MPa下的转化率为13.1％时显示出78.8％的高甲醇选择性，甲醇时空产率为796 g·kg _cat^–1 ·h ^–1。在运行时间测试中，它还显示了105小时的长期稳定性。如此出色的性能得益于丰富的Cu-ZrO_x接口和稳定的3D ZrO_x框架。在反应过程中，ZrO_x物种从不稳定的Zr氧化物簇（UiO-66的构造单元）或无定形ZrO₂演化为稳定的四方ZrO₂相，但在Cu– ZrO_x接口保留。SMSI使得能够在ZrO₂处形成Cu⁺表面，这与甲醇合成的活性位点密切相关。原位漫反射红外傅里叶变换光谱研究表明，甲醇合成遵循HCOO介导的途径。据信，这一工作提供了一个“原位重建”的策略来制造实用的Cu @的ZrO _X框架催化剂生产甲醇。

更新日期：2019-12-02

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