TY - JOUR
T1 - A Metal-Free Boron Carbon Nitride (BCN) Photocatalyst for Enhanced CO2-to-CH4 Conversion by Surface Electronic Tuning
AU - Zhang, Hansong
AU - Han, Xinyue
AU - Zhu, Jingming
AU - Lou, Siyu
AU - Song, Pengfei
AU - Dappe, Yannick J.
AU - Yang, Zhenhuai
AU - Wang, Yongjie
AU - Zhu, Jiaqi
N1 - Publisher Copyright:
© 2025 Wiley-VCH GmbH.
PY - 2025/4
Y1 - 2025/4
N2 - Graphitic carbon nitride (g-C3N4) has emerged as an attractive metal-free photocatalyst due to its numerous advantages like tunable surface chemistry, Earth abundance, and nontoxicity. Unfortunately, its photocatalytic efficiency has been seriously limited by charge carrier recombination and low reaction dynamics. Here, we report a metal-free BCN photocatalyst achieving highly selective CO2-to-CH4 conversion under visible light without requiring any metal cocatalyst. The exfoliated CN nanosheets can enrich the reaction interface with protons to accelerate the protonation of CO intermediate to further produce CH4. Moreover, B doping not only introduces more reactive defects but also tunes its electronic structure with a more negative conduction band for rapid electron extraction and enhance CO2-to-CH4 conversion. Photocatalytic measurements show that CH4 production rate and CH4/CO ratio are 24 and 13 times higher than those of bulk CN, respectively. The CH4 production rate can also reach 130 and 31 times higher than that of few-layer g-C3N4 (FL-CN) and Cu/FL-CN, respectively. The electron selectivity toward CH4 generation on BCN photocatalysts can reach ≈90%. Furthermore, sunlight driving CO2-to-CH4 conversion on such BCN photocatalysts has also been demonstrated. This work offers new insights for the design of customized multifunctional 2D materials for solar-driven CO2 conversion to CH4.
AB - Graphitic carbon nitride (g-C3N4) has emerged as an attractive metal-free photocatalyst due to its numerous advantages like tunable surface chemistry, Earth abundance, and nontoxicity. Unfortunately, its photocatalytic efficiency has been seriously limited by charge carrier recombination and low reaction dynamics. Here, we report a metal-free BCN photocatalyst achieving highly selective CO2-to-CH4 conversion under visible light without requiring any metal cocatalyst. The exfoliated CN nanosheets can enrich the reaction interface with protons to accelerate the protonation of CO intermediate to further produce CH4. Moreover, B doping not only introduces more reactive defects but also tunes its electronic structure with a more negative conduction band for rapid electron extraction and enhance CO2-to-CH4 conversion. Photocatalytic measurements show that CH4 production rate and CH4/CO ratio are 24 and 13 times higher than those of bulk CN, respectively. The CH4 production rate can also reach 130 and 31 times higher than that of few-layer g-C3N4 (FL-CN) and Cu/FL-CN, respectively. The electron selectivity toward CH4 generation on BCN photocatalysts can reach ≈90%. Furthermore, sunlight driving CO2-to-CH4 conversion on such BCN photocatalysts has also been demonstrated. This work offers new insights for the design of customized multifunctional 2D materials for solar-driven CO2 conversion to CH4.
KW - CH generation
KW - graphitic carbon nitride
KW - photocatalytic CO reduction
KW - proton-coupled electron transfer
KW - surface electronic tuning
UR - http://www.scopus.com/inward/record.url?scp=105000667840&partnerID=8YFLogxK
U2 - 10.1002/solr.202500037
DO - 10.1002/solr.202500037
M3 - Article
AN - SCOPUS:105000667840
SN - 2367-198X
VL - 9
JO - Solar RRL
JF - Solar RRL
IS - 8
M1 - 2500037
ER -