Directed Electron Delivery from a Pb‐Free Halide Perovskite to a Co(II) Molecular Catalyst Boosts CO₂ Photoreduction Coupled with Water Oxidation

Abstract

The development of high‐performance photocatalytic systems for CO2 reduction is appealing to address energy and environmental issues, while it is challenging to avoid using toxic metals and organic sacrificial reagents. We here immobilize a family of cobalt phthalocyanine catalysts on Pb‐free halide perovskite Cs2AgBiBr6 nanosheets with delicate control on the anchors of the cobalt catalysts. Among them, the molecular hybrid photocatalyst assembled by carboxyl anchors achieves the optimal performance with an electron consumption rate of 300±13 μmol g−1 h−1 for visible‐light‐driven CO2‐to‐CO conversion coupled with water oxidation to O2, over 8 times of the unmodified Cs2AgBiBr6 (36±8 μmol g−1 h−1), also far surpassing the documented systems (< 150 μmol g−1 h−1). Besides the improved intrinsic activity, electrochemical, computational, ex‐/in‐situ X‐ray photoelectron and X‐ray absorption spectroscopic results indicate that the electrons photogenerated at the Bi atoms of Cs2AgBiBr6 can be directionally transferred to the cobalt catalyst via the carboxyl anchors which strongly bind to the Bi atoms, substantially facilitating the interfacial electron transfer kinetics and thereby the photocatalysis.

Designing atomic Ni/Cu pairs on a reactive BiOCl surface for efficient photo-chemical HCO3−-to-CO conversion

“…The photovoltaic peaks demonstrated by Ni 1 /Cu 1 -BOC surpassed that of BOC, further evidencing that Ni 1 /Cu 1 -BOC facilitated photoelectric conversion and charge carrier migration. 49–51…”

Highly Efficient, Noble-Metal-Free, Fully Aqueous CO2 Photoreduction Sensitized by a Robust Organic Dye

“…Ru­(bpy) 3 Cl 2 ·6H 2 O (bpy = 2,2′-bipyridine; RuBPY ) (98%, Aladdin), Eosin Y (99%, Aladdin), 4CzIPN (>99%, Sigma), 4DPAIPN (97%, Macklin), AscHNa (>99%, Aladdin), and other chemicals were commercially available and used without further purification. Co­(oTMPyP) , , CoQPY , and CoTCPc , were prepared as previously described.…”