Breaking the Thiophene-Removal Limit via Facet-Engineered Electronic Metal-Support Interaction on Cu/ZnO

Zinc oxide is a defect-tunable support that exhibits appreciable surface reducibility when promoted by metals. Previous studies have shown that tuning the metal–support interaction can improve desulfurization performance. However, in Cu/ZnO, the inherently weak Cu–ZnO metal-support interaction can limit ultradeep thiophene removal from coke oven gas. To address this limitation, the support morphology and surface-defect characteristics of ZnO were tuned to modify the Cu–Zn interfacial electronic environment in Cu/ZnO. At 200 °C, the plate-like Cu/ZnO achieved a breakthrough sulfur capacity of 34.1 mg/g which is approximately 26% higher than that of commercial ZnO, indicating improved performance for the removal of refractory organosulfur species during fine desulfurization. Combined structural characterization and structure-performance analysis indicate that ZnO morphology plays an important role in regulating the Cu–Zn interface. Controlling support morphology, defect-related surface properties, and synthesis conditions can strengthen the Cu–Zn electronic interaction and alter the local structure of Cu species. These changes are reflected in the Cu electronic state and coordination environment, and are closely linked to the desulfurization performance. These results show that coupling facet/morphology control with surface-defect regulation is an effective way to improve Cu–Zn interfacial properties for the removal of refractory organosulfur compounds from coal-derived gases.