Bao Chaosheng, Li Yan-Ting, Zhang Qiang, Hu Tong-Liang
School of Materials Science and Engineering, National Institute for Advanced Materials, Nankai University, Tianjin 300350 China.
School of Materials Science and Engineering, National Institute for Advanced Materials, Nankai University, Tianjin 300350 China.
J Colloid Interface Sci. 2025 May 15;686:1147-1156. doi: 10.1016/j.jcis.2025.02.019. Epub 2025 Feb 4.
The catalytic hydrogenation of CO to methanol represents a promising strategy to reduce CO emissions and mitigate the energy crisis. For this conversion, reoUiO-66 with topological defects was synthesized through acid etching, and a novel Cu-based catalyst (Cu@reoUiO-66) was prepared by incorporating active Cu onto reoUiO-66. The introduction of topological defects enhanced the specific surface area (892.2 m g) and CO capture capacity (35.1 cm g) of reoUiO-66, surpassing those of UiO-66 (718.3 m g, 30.9 cm g), thereby facilitating mass transfer during the reaction. Regarding CO hydrogenation, Cu@reoUiO-66 achieved a CO conversion rate of 6.1 % and a methanol selectivity of 53.1 %. Moreover, the methanol space-time yield of the Cu@reoUiO-66 reached 336.1 mg gh and almost no decreased after continuous reaction for 70 h, which is nearly ten times that of traditional Cu/ZrO catalysts and better than many reported metal-organic framework (MOF)-based catalysts. The characterization results showed that the abundant exposed active sites induced by topological defects facilitated the fixation of active metals and reactants, thereby accelerating the activation of reactants. This study demonstrated that structural defects in the support significantly influence catalyst behavior and catalytic activity. Furthermore, it highlighted that MOFs with tunable structures serve as an ideal platform for catalyst design and structure-activity relationship studies.
将一氧化碳催化加氢制甲醇是一种减少一氧化碳排放和缓解能源危机的有前景的策略。对于这种转化反应，通过酸蚀刻合成了具有拓扑缺陷的reoUiO-66，并通过将活性铜负载到reoUiO-66上制备了一种新型铜基催化剂（Cu@reoUiO-66）。拓扑缺陷的引入提高了reoUiO-66的比表面积（892.2 m²/g）和一氧化碳捕获能力（35.1 cm³/g），超过了UiO-66（718.3 m²/g，30.9 cm³/g），从而促进了反应过程中的传质。关于一氧化碳加氢反应，Cu@reoUiO-66实现了6.1%的一氧化碳转化率和53.1%的甲醇选择性。此外，Cu@reoUiO-66的甲醇时空产率达到336.1 mg g⁻¹ h⁻¹，连续反应70小时后几乎没有下降，这几乎是传统Cu/ZrO催化剂的十倍，且优于许多已报道的基于金属有机框架（MOF）的催化剂。表征结果表明，拓扑缺陷诱导的大量暴露活性位点促进了活性金属和反应物的固定，从而加速了反应物的活化。这项研究表明载体中的结构缺陷对催化剂性能和催化活性有显著影响。此外，它强调了具有可调结构的MOF作为催化剂设计和构效关系研究的理想平台。
