The development of integrated multi-catalyst processes has become of high interest to transform abundant feedstocks or environmental pollutants to commodity chemicals in a one pot, one pass fashion. Specifically, CO₂ poses a large environmental burden and would thus be a desirable, relatively abundant C1 source in multi-step synthetic chemistry. Herein we disclose the synthesis of aldehydes from CO₂ via the integration of electrochemical CO₂ reduction (CO₂RR) and hydroformylation, taking advantage of the typically unwanted concomitant hydrogen evolution (HER) to generate the necessary CO and H₂ needed for hydroformylation. Though typical hydroformylation catalysts based on Rh would be deactivated under CO₂RR conditions, we circumvent this limitation by spatially segregating our CO₂RR and hydroformylation systems in a vial-in-vial reactor, while allowing CO and H₂ transport between catalyst sites. In this manner, 97% aldehyde yield from CO₂RR and styrene was achieved selectively using a classic homogeneous hydroformylation catalyst in HRh(CO)(PPh₃)₃, and 43% aldehyde yield was obtained using a heterogenized version of this Rh catalyst onto mesoporous silica. This work not only repurposes undesired HER in CO₂RR and prepares aldehydes from CO₂ without added H₂, but expands the scope of processes that transform feedstocks all the way to commodity chemicals in a one pass manner.

中文翻译：

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集成电化学 CO2 还原和加氢甲酰化

集成多催化剂工艺的开发已引起人们的高度关注，以一锅、一次的方式将丰富的原料或环境污染物转化为商品化学品。具体而言，CO ₂造成很大的环境负担，因此是多步合成化学中理想的、相对丰富的C1源。在本文中，我们公开了通过电化学CO 2 还原(CO 2 RR)和加氢甲酰化的_集成 ，由CO _2合成醛，利用通常不需要的伴随析氢(HER)来产生加氢甲酰化所需的必要的CO和H ₂。虽然基于Rh的典型加氢甲酰化催化剂在CO ₂ RR条件下会失活，但我们通过在瓶中瓶反应器中空间隔离我们的CO ₂ RR和加氢甲酰化系统来规避这一限制，同时允许CO和H ₂在催化剂位点之间传输。以这种方式，使用 HRh(CO)(PPh ₃ ) ₃中的经典均相加氢甲酰化催化剂选择性地从 CO ₂ RR 和苯乙烯获得了 97% 的醛收率，并且使用该 Rh 催化剂的多相化版本获得了 43% 的醛收率。介孔二氧化硅。这项工作不仅在CO ₂ RR中重新利用不需要的HER并在不添加H _{2的情况下从CO 2}制备醛，而且扩大了以一次性方式将原料一直转化为商品化学品的工艺范围。