Yuan Enxian, Wang Changlong, Wu Chan, Shi Guojun, Jian Panming, Hou Xu
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, China.
School of Chemistry and Chemical Engineering, Southeast University, Nanjing, Jiangsu 211189, China.
ACS Appl Mater Interfaces. 2023 Sep 20;15(37):43845-43858. doi: 10.1021/acsami.3c09234. Epub 2023 Sep 10.
Cobalt is an alternative catalyst for furfural hydrogenation but suffers from the strong binding of H and furan ring on the surface, resulting in low catalytic activity and chemoselectivity. Herein, by constructing a Pd-Co interface in cobalt oxide-supported Pd catalysts to tailor the d-band center of Co, the concerted effort of Pd and Co boosts the catalytic performance for the hydroconversion of furfural to cyclopentanone and cyclopentanol. The increased dispersion of Pd on acid etching CoO promotes the reduction of Co to Co by enhancing hydrogen spillover, favoring the creation of the Pd-Co interface. Both experimental and theoretical calculations demonstrate that the electron transfer from Pd to Co at the interface results in the downshift of the d-band center of Co atoms, accompanied by the destabilization of H and furan ring adsorption on the Co surface, respectively. The former improves the furfural hydrogenation with TOF on Co elevating from 0.20 to 0.62 s, and the latter facilitates the desorption of formed furfuryl alcohol from the Co surface for subsequently hydrogenative rearrangement of the furan ring to cyclopentanone on acid sites. The resultant Pd/CoO-6 catalyst delivers superior activity with a 99% furfural conversion and 85% overall selectivity toward cyclopentanone/cyclopentanol. We anticipate that such a concept of tailoring the d-band center of Co via interface engineering provides novel insight and feasible approach for the design of highly efficient catalysts for furfural hydroconversion and beyond.
钴是糠醛加氢的一种替代催化剂，但由于氢和呋喃环在其表面的强吸附作用，导致催化活性和化学选择性较低。在此，通过在氧化钴负载的钯催化剂中构建钯-钴界面来调整钴的d带中心，钯和钴的协同作用提高了糠醛加氢转化为环戊酮和环戊醇的催化性能。钯在酸蚀氧化钴上的分散性增加，通过增强氢溢流促进了钴向钴的还原，有利于钯-钴界面的形成。实验和理论计算均表明，界面处从钯到钴的电子转移导致钴原子的d带中心下移，同时分别使氢和呋喃环在钴表面的吸附不稳定。前者提高了钴上糠醛加氢的转化频率，从0.20 s提升至0.62 s，后者促进了生成的糠醇从钴表面脱附，随后在酸性位点上呋喃环氢化重排为环戊酮。所得的Pd/CoO-6催化剂具有优异的活性，糠醛转化率达到99%，对环戊酮/环戊醇的总选择性为85%。我们预计，通过界面工程调整钴的d带中心这一概念，为糠醛加氢转化及其他反应的高效催化剂设计提供了新的见解和可行的方法。
