Enzymes feature the concerted operation of multiple components around an active site, leading to exquisite catalytic specificity. Realizing such configurations on synthetic catalyst surfaces remains elusive. Here, we report a nanoparticle/ordered-ligand interlayer that contains a multi-component catalytic pocket for high-specificity CO₂ electrocatalysis. The nanoparticle/ordered-ligand interlayer comprises a metal nanoparticle surface and a detached layer of ligands in its vicinity. This interlayer possesses unique pseudocapacitive characteristics where desolvated cations are intercalated, creating an active-site configuration that enhances catalytic turnover by two orders and one order of magnitude against a pristine metal surface and nanoparticle with tethered ligands, respectively. The nanoparticle/ordered-ligand interlayer is demonstrated across several metals with up to 99% CO selectivity at marginal overpotentials and onset overpotentials of as low as 27 mV, in aqueous conditions. Furthermore, in a gas-diffusion environment with neutral media, the nanoparticle/ordered-ligand interlayer achieves nearly unit CO selectivity at high current densities (98.1% at 400 mA cm⁻²).

酶具有活性位点周围多个成分的协同作用，从而导致精湛的催化特异性。在合成催化剂表面上实现这种构型仍然是遥不可及的。在此，我们报道了一种纳米颗粒/有序配体中间层，其中包含用于高特异性CO ₂的多组分催化口袋电催化。纳米粒子/有序配体中间层包括金属纳米粒子表面和在其附近的配体的分离层。该中间层具有独特的拟电容特性，其中插入了去溶剂化的阳离子，从而形成了活性位点构型，可将原始金属表面和带有束缚配体的纳米颗粒的催化转化率分别提高两个数量级和一个数量级。纳米粒子/有序配体中间层在几种金属上得到了证明，在水性条件下，在边缘超电势和起始超电势低至27 mV时，CO选择性高达99％。此外，在具有中性介质的气体扩散环境中，纳米颗粒/有序配体中间层在高电流密度下（400 mA时为98.1％）可实现几乎单位的CO选择性。^-2）。