Photocatalytic CO2 reduction to HCOOH over core-shell Cu@Cu2O catalysts

Wang, Hui; Cheng, Shijing; Cai, Xiang; Cheng, Lihua; Zhou, Rujin; Hou, Tingting; Li, Yingwei

doi:10.1016/j.catcom.2021.106372

Cited by 37 publications

(9 citation statements)

References 33 publications

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“…The formic acid formation was also observed in experiments via photoreduction of CO 2 on a core−shell Cu@Cu 2 O catalyst. 35 However, in our calculations to decompose formic acid to CO and H 2 O, we found that the reaction barrier was close to 4.0 eV; similarly, decomposing the formate group to CO and OH is also very unfavorable. Our calculations thus suggest that H-assisted CO 2 dissociation to CO on Cu 2 O is less likely via the formation of formate or carbonyl.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…It is worth noting that, as an alternate reaction path, the H-assisted CO 2 dissociation on the perfect (111) Cu 2 O facet was previously studied, and it was shown that it required more than 3.2 eV to form a carbonyl group (COOH*) on the Cu 2 O(111) surface, while it was easier to form a formate group (HCOO*) and formic acid (HCOOH*). The formic acid formation was also observed in experiments via photoreduction of CO 2 on a core–shell Cu@Cu 2 O catalyst . However, in our calculations to decompose formic acid to CO and H 2 O, we found that the reaction barrier was close to 4.0 eV; similarly, decomposing the formate group to CO and OH is also very unfavorable.…”

Section: Resultsmentioning

confidence: 99%

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Plasmonic Energetic Electrons Drive CO₂ Reduction on Defective Cu₂O

Salavati-fard

Wang

2023

ACS Catal.

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Plasmonic photoreduction of CO 2 is valuable for decarbonization and producing valueadded chemicals. However, insights into the mechanisms of this reaction remain elusive, particularly regarding the roles of structural defects and their interplay with the nonequilibrium charge carriers. Here, we report density functional theory calculations on Cu 2 O, a prototype photocatalyst, through which we investigate CO 2 reduction over three defected facets to reveal the interfacial charge transfer and bond dynamics under plasmonic excitation. We find that the activation barrier of C−O bond cleavage decreases from 3.2 to about 1 eV, assisted by oxygen vacancies, and that the remaining barrier can be further reduced or eliminated at the plasmon-excited states when Cu 2 O is integrated with plasmonic metals. The regeneration of oxygen vacancies (by H 2 to form water) on Cu 2 O to complete the catalysis cycle is feasible and not affected by the energetic electrons. Our calculations thus show the important synergistic effect of energetic electrons and point defects to promote CO 2 reduction.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Plasmonic Energetic Electrons Drive CO₂ Reduction on Defective Cu₂O

Salavati-fard

Wang

2023

ACS Catal.

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“…[ 193 ] The synergistic effect between Cu nanoparticles/clusters and Cu 2 O can positively affect CO 2 reduction. [ 180,194,195 ] Deng et al. loaded Cu nanoparticles on Cu 2 O (111) for photocatalytic reduction of CO 2 to produce methane.…”

Section: Characteristics and Modification Strategies Of Cu2o‐based Ca...mentioning

confidence: 99%

“…prepared a Cu 2 O substrate with 3D porous structure and loaded Cu and UiO‐66‐NH 2 on its surface to construct an indirect Z‐scheme heterojunction. [ 194 ] Under the optimal conditions, the yield of CO reached 4.54 µmol g −1 h −1 , which was 50.4 times and 37.8 times higher than that of Cu 2 O and UiO‐66‐NH 2 , respectively.…”

Section: Application Of Cu2o‐based Catalysts In Co2 Reductionmentioning

confidence: 99%

“…[193] The synergistic effect between Cu nanoparticles/clusters and Cu 2 O can positively affect CO 2 reduction. [180,194,195] Deng et al loaded Cu nanoparticles on Cu 2 O (111) for photocatalytic reduction of CO 2 to produce methane. [150] The load of Cu nanoparticles made Cu 2 O (111)-Cu 0 has a more negative reduction potential and a broader light response range.…”

Section: Surface Engineeringmentioning

confidence: 99%

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Converting CO₂ into Value‐Added Products by Cu₂O‐Based Catalysts: From Photocatalysis, Electrocatalysis to Photoelectrocatalysis

Zhang

et al. 2023

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Considering the high energy demand in modern society and the widespread acceptance of "carbon neutrality" policies, reducing CO 2 into value-added products through "artificial carbon cycling" seems more reasonable and attractive. [3,4] Among the various methods of CO 2 resource utilization, photocatalysis (PC), electrocatalysis (EC) and photoelectrocatalysis (PEC), which can be operated at room temperature and atmospheric pressure, are considered to be a relatively feasible scheme. [5][6][7][8][9] Photocatalysis based on semiconductor materials can directly absorb solar light and generate charge carriers with redox capability, simultaneously accomplishing energy storage and carbon reduction. [10][11][12][13] Electrocatalysis can be driven by multiple forms of renewable energy (solar energy, water energy, wind energy, biomass energy, wave energy, tidal energy, etc.) to realize the conversion of CO 2 at the suitable negative potential. [14][15][16] Photo electrocatalysis is a special combination of photocatalysis and electrocatalysis, using a semiconductor electrode with light response capability to achieve efficient CO 2 reduction. [17,18] However, CO 2 exhibits chemical inertness due to its linear molecular and high CO bond energy, which is owing to the adoption of sp hybrid orbital when C atoms bond with O atoms. [19][20][21] Therefore, it is challenging to activate CO 2 and convert it into desirable products thermodynamically. [22] In addition, the CO 2 reduction reaction involves multi-step electron transfer, hydrogenation and CC bond coupling, which determines it has a complex and stochastic reaction path. Therefore, developing an ideal catalyst with high activity, stability, and economy for CO 2 reduction is necessary.Since Inoue et al. successfully converted CO 2 into formic acid, formaldehyde, methanol and methane under sunlight irradiation, many semiconductor materials for CO 2 reduction have been developed and evaluated. [23][24][25][26] The n-type semiconductors, including TiO 2 , ZnO 2 and SrTiO 3 , have attracted wide attention due to their low cost, high photostability and environmental harmlessness. [27] However, the excessive band gap limits their light response range, making them unsuitable for the CO 2 conversion systems driven by solar light. [28,29] Cuprous oxide (Cu 2 O), as one of the copper-based semiconductors with abundant reserves on the earth, has a suitable band gap to absorb visible light, which occupies 42-43% of the solar spectrum. More Converting CO 2 into value-added products by photocatalysis, electrocatalysis, and photoelectrocatalysis is a promising method to alleviate the global environmental problems and energy crisis. Among the semiconductor materials applied in CO 2 catalytic reduction, Cu 2 O has the advantages of abundant reserves, low price and environmental friendliness. Moreover, Cu 2 O has unique adsorption and activation properties for CO 2 , which is conducive to the generation of C 2+ products through CC coupling. This review introduces the basic principles of CO...

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