TY - JOUR
T1 - Cobalt-Embedded Metal-Covalent Organic Frameworks for CO2 Photoreduction
AU - Lu, Wanpeng
AU - Tait, Claudia E.
AU - Avci, Gokay
AU - Li, Xian’e
AU - Crumpton, Agamemnon E.
AU - Shao, Paul
AU - Aitchison, Catherine M.
AU - Ceugniet, Fabien
AU - Yao, Yuyun
AU - Frogley, Mark D.
AU - Decarolis, Donato
AU - Yao, Nan
AU - Jelfs, Kim E.
AU - McCulloch, Iain
N1 - Publisher Copyright:
© 2025 The Authors. Published by American Chemical Society.
PY - 2025/3/19
Y1 - 2025/3/19
N2 - With the pressing urgency to reduce carbon footprint, photocatalytic carbon dioxide reduction has attracted growing attention as a sustainable mitigating option. Considering the important role of catalytic active sites (CASs) in the catalytic processes, control and design of the density and environment of CASs could enhance the catalyst performance. Herein, we report a novel metal-covalent organic framework (MCOF), MCOF-Co-315, featuring earth-abundant Co cocatalysts and conjugation through a covalently bonded backbone. MCOF-Co-315 showed a CO production rate of 1616 μmol g-1 h-1 utilizing Ru(bpy)3Cl2 as photosensitizer and triethanolamine (TEOA) as sacrificial electron donor with a 1.5 AM filter, vis mirror module (390-740 nm), and irradiation intensity adjusted to 1 sun and an especially outstanding apparent quantum yield (AQY) of 9.13% at 450 nm. The photocatalytic reaction was studied with electron paramagnetic resonance (EPR) spectroscopy, X-ray absorption near-edge structure (XANES), and in situ synchrotron Fourier Transform Infrared (FT-IR) spectroscopy, and an underlying mechanism is proposed.
AB - With the pressing urgency to reduce carbon footprint, photocatalytic carbon dioxide reduction has attracted growing attention as a sustainable mitigating option. Considering the important role of catalytic active sites (CASs) in the catalytic processes, control and design of the density and environment of CASs could enhance the catalyst performance. Herein, we report a novel metal-covalent organic framework (MCOF), MCOF-Co-315, featuring earth-abundant Co cocatalysts and conjugation through a covalently bonded backbone. MCOF-Co-315 showed a CO production rate of 1616 μmol g-1 h-1 utilizing Ru(bpy)3Cl2 as photosensitizer and triethanolamine (TEOA) as sacrificial electron donor with a 1.5 AM filter, vis mirror module (390-740 nm), and irradiation intensity adjusted to 1 sun and an especially outstanding apparent quantum yield (AQY) of 9.13% at 450 nm. The photocatalytic reaction was studied with electron paramagnetic resonance (EPR) spectroscopy, X-ray absorption near-edge structure (XANES), and in situ synchrotron Fourier Transform Infrared (FT-IR) spectroscopy, and an underlying mechanism is proposed.
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U2 - 10.1021/jacs.4c18450
DO - 10.1021/jacs.4c18450
M3 - Article
C2 - 40053392
AN - SCOPUS:86000521071
SN - 0002-7863
VL - 147
SP - 9056
EP - 9061
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 11
ER -