[JACS] 我室汪骋教授发表论文:Cooperative Stabilization of the [Pyridinium-CO2-Co] Adduct on a Metal–Organic Layer Enhances Electrocatalytic CO2 Reduction

2019年10月22日

我室汪骋教授在 JACS 上发表论文:Cooperative Stabilization of the [Pyridinium-CO2-Co] Adduct on a Metal–Organic Layer Enhances Electrocatalytic CO2 Reduction

文章链接:https://pubs.acs.org/doi/10.1021/jacs.9b09227

摘要:

Pyridinium has been shown as a co-catalyst for electrochemical reduction of CO2 on metal and semiconductor electrodes but its exact role has been difficult to elucidate. In this work, we create cooperative cobalt-protoporphyrin (CoPP) and pyridinium (pyH+) catalytic sites on metal-organic layers (MOLs) for electrocatalytic CO2 reduction reaction (CO2RR). Constructed from [Hf63-O)43-OH)4(HCO2)6] secondary building units (SBUs) and terpyridine-based tricarboxylate ligands, the MOL was post-synthetically functionalized with CoPP via carboxylate exchange with formate capping groups. The CoPP group and the pyridinium (pyH+) moiety on the MOL coactivate CO2 by forming the [pyH+--O2C-CoPP] adduct, which enhances CO2RR and suppresses hydrogen evolution to afford a high CO/H2 selectivity of 11.8. Cooperative stabilization of the [pyH+--O2C-CoPP] intermediate led to a catalytic current density of 1314 mA/mgCo for CO production at -0.86 VRHE, which corresponds to a turnover frequency of 0.4 s-1.