We devised ruthenium-based catalysts with hierarchical anatase TiO₂ nanospheres (HATNs) constructed by ultrathin nanosheets (NSs) exposed different degrees of {0 0 1} facets as the supports for semi-hydrogenation of benzene (SHB) and boosted the performances by manipulating the metal-support interfaces (MSIs). With the aid of systematic characterizations, it is identified that appropriately prolonging the solvothermal time gave rise to an enhancement in TiO₂ crystallinity and an increment in exposed degree of {0 0 1} facets. As a result, the amounts of acid sites and coordinatively unsaturated (cus) fivefold-coordinated Ti (Ti_5c) atoms on the Ru/HATNs catalysts were increased. The former aroused an enhancement in turnover frequency (TOF) of benzene by providing additional hydrogenation on the acid sites, and the latter boosted the cyclohexene selectivity. The initial selectivity and yield attained to 83% and 51%, respectively, on the Ru/HATNs-24 catalyst exposed the most {0 0 1} facets. Kinetics analysis and temperature-programmed desorption (TPD) of cyclohexene demonstrated that the cus Ti_5c atoms on the {0 0 1} facets can accelerate the rate of benzene hydrogenation more than that of cyclohexene hydrogenation, decrease the adsorption site and capacity of cyclohexene, and weaken the adsorption strength of cyclohexene, which are responsible for the selectivity enhancement.

我们设计了钌基催化剂，该催化剂具有通过暴露不同程度的{0 0 1}面的超薄纳米片（NSs）构成的分层锐钛矿型TiO ₂纳米球（HATNs）作为苯（SHB）半加氢的载体，并通过操作来提高性能金属支持接口（MSI）。借助于系统的表征，已确定适当延长溶剂热时间引起TiO ₂结晶度的提高和{0 0 1}面的暴露度的增加。结果，酸位点和配位不饱和（cus）五重配位的Ti（Ti _5c）Ru / HATNs催化剂上的原子增加了。前者通过在酸性位点上提供额外的氢化作用而提高了苯的周转频率（TOF），而后者则提高了环己烯的选择性。在Ru / HATNs-24催化剂上暴露最多{0 0 1}面的情况下，初始选择性和产率分别达到83％和51％。环己烯的动力学分析和程序升温脱附（TPD）证明CUS钛_5c中的{001}面的原子可以加速苯加氢超过该环己烯的氢化的速率，减少环己烯的吸附部位和容量，并削弱了环己烯的吸附强度，这是选择性提高的原因。