Meng Chao, Zhao Guofeng, Shi Xue-Rong, Chen Pengjing, Liu Ye, Lu Yong
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China.
Department of Materials Engineering, Shanghai University of Engineering Science, Shanghai 201620, China.
Sci Adv. 2021 Aug 4;7(32). doi: 10.1126/sciadv.abi6012. Print 2021 Aug.
Direct CO hydrogenation to methanol using renewable energy-generated hydrogen is attracting intensive attention, but qualifying catalysts represents a grand challenge. Pure-/multi-metallic systems used for this task usually have low catalytic activity. Here, we tailored a highly active and selective InNiC/ZrO catalyst by tuning the performance-relevant electronic metal-support interaction (EMSI), which is tightly linked with the ZrO type-dependent oxygen deficiency. Highly oxygen-deficient monoclinic-ZrO support imparts high electron density to InNiC because of the considerably enhanced EMSI, thereby enabling InNiC/monoclinic-ZrO with an intrinsic activity three or two times as high as that of InNiC/amorphous-ZrO or InNiC/tetragonal-ZrO The EMSI-governed catalysis observed in the InNiC/ZrO system is extendable to other oxygen-deficient metal oxides, in particular InNiC/FeO, achieving 25.7% CO conversion with 90.2% methanol selectivity at 325°C, 6.0 MPa, 36,000 ml g hour, and H/CO = 10:1. This affordable catalyst is stable for at least 500 hours and is also highly resistant to sulfur poisoning.
利用可再生能源产生的氢气将一氧化碳直接加氢制甲醇正引起广泛关注，但制备合格的催化剂是一项巨大挑战。用于此任务的纯金属/多金属体系通常催化活性较低。在此，我们通过调节与性能相关的电子金属-载体相互作用（EMSI）来定制一种高活性和选择性的InNiC/ZrO催化剂，该相互作用与ZrO类型相关的氧缺陷紧密相连。高度缺氧的单斜ZrO载体由于EMSI显著增强，赋予InNiC高电子密度，从而使InNiC/单斜ZrO的本征活性比InNiC/非晶ZrO或InNiC/四方ZrO高三倍或两倍。在InNiC/ZrO体系中观察到的由EMSI控制的催化作用可扩展到其他缺氧金属氧化物，特别是InNiC/FeO，在325°C、6.0 MPa、36,000 ml g-1小时-1以及H2/CO = 10:1的条件下，实现了25.7%的CO转化率和90.2%的甲醇选择性。这种经济实惠的催化剂至少稳定500小时，并且对硫中毒也具有高度抗性。
