Promoting Photocatalytic CO<sub>2</sub> Methanation by the Construction of Cooperative Copper Dual-Active Sites

Zhang, Minghui; Mao, Yuyin; Bao, Xiaolei; Wang, Peng; Liu, Yuanyuan; Zheng, Zhaoke; Cheng, Hefeng; Dai, Ying; Wang, Zeyan; Huang, Baibiao

doi:10.1021/acscatal.4c00060

Cited by 18 publications

(1 citation statement)

References 59 publications

(86 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For CO 2 methanation with H 2 O reaction (CO 2 + 2H 2 O → CH 4 + 2O 2 ) without adding sacrificial agents, the protons are only original from the released protons in H 2 O oxidation. This means that for effective CO 2 methanation to be achieved, CO 2 reduction and H 2 O oxidation must be favorable. − Moreover, when the H 2 O oxidation occurs directly adjacent to CO 2 reduction, a significantly shorter proton migration facilitates the protonation of the reduced CO 2 . The accumulated electrons focused on a single reaction site will produce an intensive electrostatic repulsive force.…”

Section: Introductionmentioning

confidence: 99%

Cooperation of Strong Electric Field and H₂O Dissociation on Co₃O₄-Decorated SiC Rods for Photodriven CO₂ Methanation with 100% Selectivity

Lin,

Cai,

Xiao

et al. 2024

Inorg. Chem.

View full text Add to dashboard Cite

Solar-driven methanation of carbon dioxide (CO 2 ) with water (H 2 O) has emerged as an important strategy for achieving both carbon neutrality and fuel production. The selective methanation of CO 2 was often hindered by the sluggish kinetics and the multiple competition of other C 1 byproducts. To overcome this bottleneck, we utilized a biomass synthesis method to synthesize SiC rods and then constructed a direct Z-scheme heterojunction Co 3 O 4 /SiC catalyst. The substantial difference in work functions between SiC and Co 3 O 4 served as a significant source of the charge driving force, facilitating the conversion of CO 2 to CH 4 . The high-valent cobalt Co(IV) in Co 3 O 4 acts as an active species to promote efficient dissociation of water. This favorable condition greatly enhanced the likelihood of a high concentration of electrons and protons around a single site on the catalyst surface for CO 2 methanation. DFT calculation showed that the energy barrier of CO 2 hydrogenation was significantly reduced at the Co 3 O 4 /SiC heterojunction interface, which changed the reaction pathway and completely converted the product from CO to CH 4 . The optimum CH 4 evolution rate of Co 3 O 4 /SiC samples was 21.3 μmol g −1 h −1 with 100% selectivity. This study has an important guiding significance for the selective regulation of CO 2 to CH 4 products in photocatalysis applications.

show abstract

Section: Introductionmentioning

confidence: 99%

Cooperation of Strong Electric Field and H₂O Dissociation on Co₃O₄-Decorated SiC Rods for Photodriven CO₂ Methanation with 100% Selectivity

Lin,

Cai,

Xiao

et al. 2024

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

Rapid Charge Transfer Endowed by Hollow‐structured Z‐Scheme Heterojunction for Coupling Benzylamine Oxidation With CO₂ Reduction

Tang,

Bao,

et al. 2024

Adv Funct Materials

View full text Add to dashboard Cite

In the field of photocatalysis, ultrafast electron transfer at the interface is the key factor affecting photocatalytic activity. Herein, ultrafast carrier transport is achieved through constructing a Z‐scheme heterojunction of CoSe@Zn0.5Cd0.5S (CoSe@ZCS), which is prepared by in situ growth of ZCS on the ZIF‐67‐derived hollow CoSe. The ultrafast charge transfer at the Z‐scheme heterojunction interface is verified by advanced fs‐transient absorption, which provides vital evidence for the specific mechanism of photocatalytic charge transfer. In addition, the presence of key intermediates (*COOH and C═N) is detected by in‐situ FTIR spectroscopy, which further clarified the mechanism of coupling benzylamine oxidation with CO2 photoconversion. DFT calculations also confirm that the Z‐scheme heterojunction effectively reduces the energy barrier of the rate‐limiting step of *COOH formation, facilitating the photocatalytic CO2 reduction process of ZCS. Benefiting from the ultrafast electron transfer at the interface of the Z‐scheme heterojunction, CoSe@ZCS exhibits excellent bifunctional photocatalytic performance. This work lays the foundation for further exploration of the charge transfer mode at the heterojunction interface to facilitate solar‐driven energy conversion.

show abstract

Achieving Almost 100% Selectivity in Photocatalytic CO₂ Reduction to Methane via In‐Situ Atmosphere Regulation Strategy

Zhang,

Deng,

Wang

et al. 2024

Advanced Materials

View full text Add to dashboard Cite

Artificial photosynthesis, harnessing solar energy to convert CO2 into hydrocarbons, presents a promising solution for climate change and energy scarcity. However, photocatalytic CO2 reduction often terminates at the CO stage due to limited electron transfer capacity, hindering the formation of higher‐energy hydrocarbons such as CH4. This study introduces, for the first time, an in‐situ atmosphere regulation strategy, refined from molecular imprinting methodologies, using dynamically reacting molecules to precisely engineer photocatalytic surface sites for selective *CO adsorption and hydrogenation in CO2‐to‐CH4 conversion. Specifically, the single‐atom Cu catalyst (Cu‐SA‐CO) is prepared by anchoring single‐atom Cu onto defective TiO2 substrates (Cu‐SA‐CO) under a CO reduction atmosphere. Under illumination, the catalyst exhibited outstanding CH4 selectivity (almost 100%) and productivity (58.5 µmol g−1 h−1). Mechanistic investigations reveal that the coordination environment of the Cu single atoms is significantly affected by dynamically reacting molecules (CO and *CHxO) during synthesis, leading to a Ti‐Cu‐O structure. The structure, with the synergistic interaction between Cu single atoms and oxygen defects, significantly enhances *CO adsorption and hydrogenation, thereby promoting the formation of methane. This work pioneers the use of dynamically reactive molecules as imprinted templates to tune photocatalytic CO2 reduction selectivity, providing a novel avenue for designing efficient photocatalysts.

show abstract

Promoting Photocatalytic CO₂ Methanation by the Construction of Cooperative Copper Dual-Active Sites

Cited by 18 publications

References 59 publications

Cooperation of Strong Electric Field and H₂O Dissociation on Co₃O₄-Decorated SiC Rods for Photodriven CO₂ Methanation with 100% Selectivity

Cooperation of Strong Electric Field and H₂O Dissociation on Co₃O₄-Decorated SiC Rods for Photodriven CO₂ Methanation with 100% Selectivity

Rapid Charge Transfer Endowed by Hollow‐structured Z‐Scheme Heterojunction for Coupling Benzylamine Oxidation With CO₂ Reduction

Achieving Almost 100% Selectivity in Photocatalytic CO₂ Reduction to Methane via In‐Situ Atmosphere Regulation Strategy

Contact Info

Product

Resources

About

Promoting Photocatalytic CO2 Methanation by the Construction of Cooperative Copper Dual-Active Sites

Cited by 18 publications

References 59 publications

Cooperation of Strong Electric Field and H2O Dissociation on Co3O4-Decorated SiC Rods for Photodriven CO2 Methanation with 100% Selectivity

Cooperation of Strong Electric Field and H2O Dissociation on Co3O4-Decorated SiC Rods for Photodriven CO2 Methanation with 100% Selectivity

Rapid Charge Transfer Endowed by Hollow‐structured Z‐Scheme Heterojunction for Coupling Benzylamine Oxidation With CO2 Reduction

Achieving Almost 100% Selectivity in Photocatalytic CO2 Reduction to Methane via In‐Situ Atmosphere Regulation Strategy

Contact Info

Product

Resources

About

Promoting Photocatalytic CO₂ Methanation by the Construction of Cooperative Copper Dual-Active Sites

Cooperation of Strong Electric Field and H₂O Dissociation on Co₃O₄-Decorated SiC Rods for Photodriven CO₂ Methanation with 100% Selectivity

Cooperation of Strong Electric Field and H₂O Dissociation on Co₃O₄-Decorated SiC Rods for Photodriven CO₂ Methanation with 100% Selectivity

Rapid Charge Transfer Endowed by Hollow‐structured Z‐Scheme Heterojunction for Coupling Benzylamine Oxidation With CO₂ Reduction

Achieving Almost 100% Selectivity in Photocatalytic CO₂ Reduction to Methane via In‐Situ Atmosphere Regulation Strategy