Integrated CO₂ capture and hydrogenation to methanol may replace fossil resources for production of clean fuels, chemicals, and materials. As opposed to the classic concept of lowering the transition state barriers in the rate determination step, here we demonstrate that suppression of a resting state species can also be a viable approach to accomplish catalytic improvement. As a promising NH/M bifunctional molecular catalyst for integrated CO₂ capture and conversion to methanol, Ru-MACHO-BH in the presence of amine additives was evaluated in the presence of a second catalyst, preferably ZnO. The latter is capable of suppressing the Ru-formate resting state intermediate by accelerating formate to formamide formation. This strategy is capable of advancing methanol formation and CO₂ conversion, adding up to 100 and 294 turnover numbers, respectively, under mild operational conditions. Operando high-pressure ATR-IR spectroscopy evidenced the existence of such Ru-formate resting state species in the presence of amine additives and its disappearance upon addition of ZnO under catalytic conditions. Given that metal oxide enhances the amide bond formation rate, but has insignificant activity in catalytic hydrogenation of CO₂ and the formamide intermediate, its promoting effect can be fully ascribed to an increased availability of the active Ru-dihydride species upon suppressing the dormant Ru-formate catalyst intermediate.

中文翻译：

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在常规金属氧化物存在下抑制休眠的 Ru 状态促进了 Ru-MACHO-BH 催化的 CO2 捕获和加氢合成甲醇

集成的 CO ₂捕获和加氢制甲醇可能会取代化石资源用于生产清洁燃料、化学品和材料。与在速率确定步骤中降低过渡态势垒的经典概念相反，在这里我们证明抑制静止状态物种也可以是实现催化改进的可行方法。作为用于集成 CO ₂捕获和转化为甲醇的有前途的 NH/M 双功能分子催化剂，在第二催化剂（优选 ZnO）存在下评估了在胺添加剂存在下的 Ru-MACHO-BH。后者能够通过加速甲酸盐到甲酰胺的形成来抑制 Ru-甲酸盐静止状态中间体。该策略能够促进甲醇的形成和 CO₂转换，在温和的操作条件下，分别加起来为 100 和 294 转换数。Operando高压 ATR-IR 光谱证明了在存在胺添加剂的情况下存在这种甲酸钌静止状态物种，并且在催化条件下添加 ZnO 后其消失。鉴于金属氧化物提高了酰胺键的形成速率，但对 CO ₂和甲酰胺中间体的催化加氢活性不显着，其促进作用可以完全归因于在抑制休眠的 Ru-甲酸催化剂中间体。