The electroreduction of CO₂, driven by renewable electricity, can be used to sustainably generate synthetic fuels. So far, only copper-based materials have been used to catalyse the formation of multicarbon products, albeit limited to C₂ or C₃ molecules. Herein, we disclose that inorganic nickel oxygenate-derived electrocatalysts can generate linear and branched C₃ to C₆ hydrocarbons with sustained Faradaic efficiencies of up to 6.5%, contrasting with metallic nickel, which is practically inactive. Operando X-ray absorption spectroscopy, electrochemical CO stripping and density functional theory pinpoint the presence of stable, polarized Ni^δ+ active sites associated with Ni–O bonds, which bind CO moderately. The reduction of selected C₁ molecules and density functional theory simulations suggest that the Ni^δ+ sites promote a mechanism reminiscent of the Fischer–Tropsch synthesis: COOH + CH_x coupling followed by successive CH_x insertions. Our results disclose atom polarization to be the key that prevents the CO poisoning of nickel and enables CO₂ reduction to a wider pool of valuable products.

由可再生电力驱动的 CO ₂电还原可用于可持续地生产合成燃料。到目前为止，只有铜基材料被用于催化多碳产物的形成，尽管仅限于 C ₂或 C ₃分子。在此，我们公开了无机氧化镍衍生的电催化剂可以生成直链和支链 C ₃至 C ₆烃，其持续法拉第效率高达 6.5%，而金属镍实际上是不活泼的。操作 X 射线吸收光谱、电化学 CO 溶出和密度泛函理论确定了稳定的极化 Ni ^{δ +}与 Ni-O 键相关的活性位点，适度结合 CO。选择的 C ₁分子的减少和密度泛函理论模拟表明，Ni ^{δ +}位点促进了一种类似于 Fischer-Tropsch 合成的机制：COOH + CH _x耦合，然后是连续的 CH _x插入。我们的结果表明，原子极化是防止镍的 CO 中毒并使 CO ₂还原为更广泛的有价值产品的关键。