Abstract
The metal–anion interaction (MAI) widely exists over supported metal catalysts, which has a significant effect on tuning metal sites and reaction performance. However, the effect of MAI on NH3 synthesis and the reaction mechanism is still elusive. Here, we report that the strength of Ru–anion interaction gradually increases from Ru–N to Ru–H and Ru–O when the anion of the support is changed from H (ZrH2) to N (ZrN) and O (ZrO2). Moreover, the Ru–anion interaction induced by different support compositions can affect the hydrogen spillover and N2 activation route. Due to the weak Ru–N interaction, the aggregation of Ru particles is observed over Ru/ZrN. Although Ru particles are highly dispersed over ZrO2 owing to the strong Ru–O interaction, hydrogen poisoning is inevitable over Ru/ZrO2. Comparatively, hydrogen poisoning can be alleviated over Ru/ZrH2 via hydrogen spillover to its support. The results of NEXAFS, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and isotope-labeling experiments show that N2 can be activated via both dissociative and associative routes over Ru/ZrH2. Consequently, the developed Ba-promoted Ru/ZrH2 catalyst displays a high NH3 synthesis rate of 27.5 mmol g–1 h–1 and robust stability during 300 h time-on-stream at 400 °C and 1 MPa.
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