Incorporating highly dispersed and stable Cu+ into TiO2 lattice for enhanced photocatalytic CO2 reduction with water

Xiong, Zhuo; Xu, Zuwei; Li, Youzi; Dong, Liangchen; Wang, Junyi; Zhao, Jiangting; Chen, Xiaoxiang; Zhao, Yongchun; Zhao, Haibo; Zhang, Junying

doi:10.1016/j.apsusc.2019.145095

Cited by 36 publications

(27 citation statements)

References 41 publications

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“…Therefore, in the view of both the number and strength of Cu–O bonds, the Cu L in the TiO 2 lattice is endowed with higher stability than the Cu S on the surface, regardless of the removed O atoms around the Cu L . Such a conclusion is also in accordance with the experimental observation that the CuO x /TiO 2 containing a large amount of lattice Cu exhibited excellent stability and recyclability in photoreduction. ,, …”

Section: Results and Discussionsupporting

confidence: 90%

“…However, it was reported that more or less lattice substitution by Cu was possible if considering the relative high calcination temperature and the similar ionic radii of Ti and Cu. − Particularly, the popular one-pot approach would mix Cu and Ti precursors in a molecular level prior to solidification, which facilitates the synthesis of CuO x /TiO 2 with a large amount of lattice doped Cu. Moreover, several works finished by Zhu et al and Xiong et al , recently confirmed that both the surface and lattice Cu played important roles in the promotion of catalysis performance as the surface one was responsible for CO 2 reduction, while the lattice one was able to improve the carrier transfer process efficiently. Hence, CuO x /TiO 2 comprising both surface and lattice Cu was much more superior to those working alone.…”

Section: Introductionmentioning

confidence: 95%

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Mechanistic Understanding on the Role of Cu Species over the CuO_x/TiO₂ Catalyst for CO₂ Photoreduction

et al. 2020

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Incorporation of earth-abundant Cu is one of the most important approaches to improve the practicability of TiO 2 for photoreduction of CO 2 into value-added solar fuels. However, the molecular insight on the role of Cu is complicated and far from understood. We performed a first principle calculation on the anatase (101) surface modified by a single Cu atom deposited on the surface (Cu S ) or doped in the lattice (Cu L ). It is demonstrated the Cu L is clearly more stable than the Cu S and could promote the formation of oxygen vacancy (Vo) greatly. The Cu S plays a role of donor, while the Cu L is electronically deficient and becomes a global electron trapper. If a Vo is introduced, the excess electrons would immigrate to the empty gap state of the Cu L and make it half-filled in some case, which implies its metallic characters and improved conductivity; meanwhile, the formation of Ti 3+ is suppressed. Judging from the adsorption energies, it is the Vo that primarily improves the adsorption of CO 2 in both linear and bent states, and the Cu S could hardly stabilize CO 2 more, while the promotion effect of Vo could even be counteracted by the Cu L due to its electronic deficiency. The reduction pathways (CO 2 * → CO* + O*) show that, with the assistance of the Cu S , linear CO 2 could directly transform into the carbonate-like geometry vertically binding to the surface, and the intermediate configuration of the bent CO 2 horizontally bridging the Vo could be successfully skipped. Therefore, the barrier of the rate-determining transformation could be lowered from 0.75 to 0.39 eV. Furthermore, it is found the strong adsorption of the produced CO by the Cu S might retard the smooth going of the catalytic process.

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Section: Results and Discussionsupporting

confidence: 90%

Section: Introductionmentioning

confidence: 95%

Mechanistic Understanding on the Role of Cu Species over the CuO_x/TiO₂ Catalyst for CO₂ Photoreduction

et al. 2020

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“…In the past two decades, a variety of photocatalysts have been exploited to catalyze this significant energy conversion reaction. Among them, supporters supported metal photocatalysts have become a hot research topic, for their maximum utilization of metal sites, which usually benefits for greatly boosting CO2 photoreduction performance [15][16][17][18]. In this context, tremendous efforts have been devoted to the preparation of atomically dispersed metal photocatalysts.…”

Section: Introductionmentioning

confidence: 99%

Facile synthesis of C3N4-supported metal catalysts for efficient CO2 photoreduction

et al. 2021

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Facile synthesis of photocatalysts with highly dispersed metal centers is a high-priority target yet still a significant challenge. In this work, a series of Co-C 3 N 4 photocatalysts with different Co contents atomically dispersed on g-C 3 N 4 have been prepared via one-step thermal treatment of cobalt-based metal-organic frameworks (MOFs) and urea in the air. Thanks to the highly dispersed and rich exposed Co sites, as well as good charge separation efficiency and abundant mesopores, the optimal 25-Co-C 3 N 4 , in the absence of noble metal catalysts/sensitizers, exhibits excellent performance for photocatalytic CO 2 reduction to CO under visible light irradiation, with a high CO evolution rate of 394.4 μmol•g -1 •h -1 , over 80 times higher than that of pure g-C 3 N 4 (4.9 μmol•g -1 •h -1 ). In addition, by this facile synthesis strategy, the atomically dispersed Fe and Mn anchoring on g-C 3 N 4 (Fe-C 3 N 4 and Mn-C 3 N 4 ) have been also obtained, indicating the reliability and universality of this strategy in synthesizing photocatalysts with highly dispersed metal centers. This work paves a new way to develop cost-effective photocatalysts for photocatalytic CO 2 reduction.

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“…But excessive metals form new recombination centers inhibit the interfacial charge transfer and abate the activity. 28 , 32 …”

Section: Resultsmentioning

confidence: 99%

Cu/ZnV₂O₄ Heterojunction Interface Promoted Methanol and Ethanol Generation from CO₂ and H₂O under UV–Vis Light Irradiation

Gao

et al. 2022

ACS Omega

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Adopting the concurrent reduction of Cu 2 O during hydrothermal preparation of ZnV 2 O 4 , metal–semiconductor heterojunction Cu/ZnV 2 O 4 nanorods were synthesized and applied to the catalytic generation of methanol and ethanol from CO 2 aerated water under UV–vis light irradiation. 10Cu/ZnV 2 O 4 obtained from 10 wt % composite amount of Cu 2 O exhibited a total carbon yield of 6.49 μmol·g –1 ·h –1 . The yield of CH 3 OH and C 2 H 5 OH reached 3.30 and 0.86 μmol·g –1 ·h –1 , respectively. 2.5Cu/ZnV 2 O 4 displayed the highest ethanol yield of 1.58 μmol·g –1 ·h –1 due to the strong absorption in the visible light. Cu/ZnV 2 O 4 was characterized using X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy (XPS), ultraviolet–visible (UV–vis) spectra, photoluminescence (PL) spectra, transient photocurrent response, and electrochemical impedance spectroscopy (EIS). Results showed that composite Cu 0 -ZnV 2 O 4 increased the surface area and tuned the energy band position, which matches the reaction potential toward methanol and ethanol. The photocatalytic activity toward CH 3 OH and C 2 H 5 OH on Cu/ZnV 2 O 4 is attributed to faster transmission and a slow recombination rate of photogenerated carriers at the heterojunction interface. Multielectron reactions for the production of CH 3 OH and C 2 H 5 OH are promoted. Free radical capture experiments indicated that the active species boost the reaction in the order of • OH > e – > h + .

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Incorporating highly dispersed and stable Cu+ into TiO2 lattice for enhanced photocatalytic CO2 reduction with water

Cited by 36 publications

References 41 publications

Mechanistic Understanding on the Role of Cu Species over the CuO_x/TiO₂ Catalyst for CO₂ Photoreduction

Mechanistic Understanding on the Role of Cu Species over the CuO_x/TiO₂ Catalyst for CO₂ Photoreduction

Facile synthesis of C3N4-supported metal catalysts for efficient CO2 photoreduction

Cu/ZnV₂O₄ Heterojunction Interface Promoted Methanol and Ethanol Generation from CO₂ and H₂O under UV–Vis Light Irradiation

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Incorporating highly dispersed and stable Cu+ into TiO2 lattice for enhanced photocatalytic CO2 reduction with water

Cited by 36 publications

References 41 publications

Mechanistic Understanding on the Role of Cu Species over the CuOx/TiO2 Catalyst for CO2 Photoreduction

Mechanistic Understanding on the Role of Cu Species over the CuOx/TiO2 Catalyst for CO2 Photoreduction

Facile synthesis of C3N4-supported metal catalysts for efficient CO2 photoreduction

Cu/ZnV2O4 Heterojunction Interface Promoted Methanol and Ethanol Generation from CO2 and H2O under UV–Vis Light Irradiation

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Mechanistic Understanding on the Role of Cu Species over the CuO_x/TiO₂ Catalyst for CO₂ Photoreduction

Mechanistic Understanding on the Role of Cu Species over the CuO_x/TiO₂ Catalyst for CO₂ Photoreduction

Cu/ZnV₂O₄ Heterojunction Interface Promoted Methanol and Ethanol Generation from CO₂ and H₂O under UV–Vis Light Irradiation