Chen Min, Liu Longgang, Chen Xueyan, Qin Xiaoxiao, Zhang Jianghao, Xie Shaohua, Liu Fudong, He Hong, Zhang Changbin
State Key Joint Laboratory of Environment Simulation and Pollution Control, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, China.
School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, China.
Nat Commun. 2024 Nov 2;15(1):9478. doi: 10.1038/s41467-024-53909-8.
Efficient heterogeneous catalyst design primarily focuses on engineering the active sites or supports, often neglecting the impact of trace impurities on catalytic performance. Herein, we demonstrate that even trace amounts of sulfate (SO) residuals on Ru/TiO can totally change the CO reduction from methanation to reverse-water gas shift (RWGS) reaction under atmospheric pressure. We reveal that air annealing causes the trace amount of SO to migrate from TiO to Ru/TiO interface, leading to the significant changes in product selectivity from CH to CO. Detailed characterizations and DFT calculations show that the sulfate at Ru/TiO interface notably enhances the H transfer from Ru particles to the TiO support, weakening the CO intermediate activation on Ru particles and inhibiting the further hydrogenation of CO to CH. This discovery highlights the vital role of trace impurities in CO hydrogenation reaction, and also provides broad implications for the design and development of more efficient and selective heterogeneous catalysts.
高效多相催化剂的设计主要集中在对活性位点或载体进行工程设计，常常忽略痕量杂质对催化性能的影响。在此，我们证明，即使是Ru/TiO上痕量的硫酸盐（SO）残留也能在常压下使CO还原反应从甲烷化完全转变为逆水煤气变换（RWGS）反应。我们发现空气退火会使痕量的SO从TiO迁移至Ru/TiO界面，导致产物选择性从CH显著变为CO。详细的表征和密度泛函理论（DFT）计算表明，Ru/TiO界面处的硫酸盐显著增强了氢从Ru颗粒向TiO载体的转移，削弱了Ru颗粒上CO中间体的活化，并抑制了CO进一步氢化为CH。这一发现突出了痕量杂质在CO加氢反应中的关键作用，也为设计和开发更高效、更具选择性的多相催化剂提供了广泛的启示。
