Selective CO2 electrocatalysis at the pseudocapacitive nanoparticle/ordered-ligand interlayer

Abstract

Enzymes distinctively feature concerted operation of multiple components around an active site, leading to exquisite specificity. Realizing such configurations on synthetic catalyst surfaces remains elusive. Here, we report the creation of a Nanoparticle/Ordered-Ligand Interlayer (NOLI) that contains a multi-component catalytic pocket for high-specificity CO 2 electrocatalysis. Through the collective behavior of ligands, the NOLI contains a detached ligand layer remaining within the metal surface vicinity. The interlayer possesses unique pseudocapacitive characteristics where desolvated cations are interposed and the resultant active site configuration enhances catalytic turnover by two orders of magnitude. The generality of the NOLI design is demonstrated across a number of transition metals, ultimately achieving up to 99% selectivity towards CO at marginal overpotentials, with onset overpotentials of as low as 27 mV.

Copper Sulfide as the Cation Exchange Template for Synthesis of Bimetallic Catalysts for CO2 Electroreduction

“…The change might be related to the surface ligands, which may affect electrochemical behavior and the stability of nanomaterials, yet more characterizations need to be done to confirm this. 41,50,51 Additionally, for C-nano-0, the Cu transformed into large clusters (500 nm, Figure S29), different from the filament structure of CAnano-2. This might come from the difference in the CO/CO 2 binding energy on Cu and Ag.…”

Copper sulfide as the cation exchange template for synthesis of bimetallic catalysts for CO2electroreduction

“…The change might be related to the surface ligands, which may affect electrochemical behavior and the stability of nanomaterials, yet more characterizations need to be done to conrm this. 42,53,54 Additionally, for C-nano-0, the Cu was transformed into large clusters ($500 nm, Fig. S30 †), different from the lament structure of CA-nano-2.…”

“…Previous research show such anionic ligands could be removed under negative potentials and may induce reconstruction of the nano-scale catalysts, which further inuence the performance. 42,43 Thus, for a consistent comparison, the electrodes were evaluated in the same potential sequence. All samples were tested for the same 1.5 h duration from the most positive potential (À0.2 V vs. RHE) to the most negative potential (À1.6 V vs. RHE), as shown in Fig.…”

Pocket the difference

“…Nature offers inspiration in the form of enzyme catalysts that have intricate nanoscale environments and allow high reaction efficiencies to be achieved, but realizing similar surroundings in synthetic catalysts has proved challenging. Now, writing in Nature Energy, Peidong Yang and colleagues at the University of California, Berkeley, Lawrence Berkeley National Laboratory and the Kavli Energy NanoScience Institute report a nanoparticle-ligand assembly that acts as a catalytic pocket to improve CO 2 to CO conversion efficiency 1 .…”

“…As a result, the CO 2 to CO conversion reached 97%. The researchers further tested their NOLI structure in a gas diffusion electrode in 1 M KHCO 3 , reaching 98.1% CO selectivity at 400 mA cm -2 and 2921 A g Ag - 1 . An interesting feature of the Ag-NOLI structure is that the Ag nanoparticles grew from 6 to 32 nm in the CO 2 reduction process, but this did not compromise the NOLI as the pocket for highly selective CO formation.…”