Cooperation between inside and outside of TiO2: Lattice Cu+ accelerates carrier migration to the surface of metal copper for photocatalytic CO2 reduction

Zhu, Sai; Chen, Xiaofeng; Li, Zhangcheng; Ye, Xingyu; Liu, Ying; Chen, Yao; Yang, Li; Chen, Ming; Zhang, Dieqing; Li, Guisheng; Li, Hexing

doi:10.1016/j.apcatb.2019.118515

Cited by 106 publications

(57 citation statements)

References 65 publications

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“… 62 , 63 In this aspect, several works also disclosed that TiO 2 exhibited a relatively higher photocurrent response and smaller charge transfer resistance after the modification of CuO x . 39 , 54 , 64 On the other hand, we also notice that the introduction of a Vo would have the Cu L only gain charges of 0.21 e – in Cu/PS, but both the Ti 5c-1 and Ti 6c-1 sites in PS or Cu-PS accept more than 0.2 e – (see Figure 3 ). Such a discrepancy could be partially illustrated by the PDOS of O 2c ready to be removed.…”

Section: Results and Discussionmentioning

confidence: 88%

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 Discussionmentioning

confidence: 88%

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 fact, for many semiconductor photocatalysts, it is quite normal that various metal ions are doped into the semiconductors to promote the separation of electrons and holes. The metal ions usually include Cu + (Zhu et al, 2020 ), Si 4+ (Cesar et al, 2006 ), Zn 2+ (Ingler et al, 2004 ), and Pt 2+ (Xing et al, 2013 ; Lian et al, 2017 ; Liu et al, 2019 ). For example, for the Pt-Ti 3+ /TiO 2 system (Lian, Wang D. et al, 2017 ), the introduction of Pt ions greatly enhances the photocatalytic efficiency.…”

Section: Resultsmentioning

confidence: 99%

A Ti-MOF Decorated With a Pt Nanoparticle Cocatalyst for Efficient Photocatalytic H2 Evolution: A Theoretical Study

Zhong

Wang

et al. 2020

Front. Chem.

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Pt nanoparticles (NPs) are often used as cocatalysts to enhance the photocatalytic hydrogen production catalyzed by the metal organic framework (MOF) materials. The catalytic efficiency of many Pt/MOF systems can be greatly improved when Pt NPs are used as cocatalysts. In this work, the Pt/20%-MIL-125-(SCH 3) 2 was chosen as the template material to understand the functional role of a Pt metal cocatalyst in the catalytic process. Experimentally, the catalytic activity of Pt/20%-MIL-125-(SCH 3) 2 is more than 100 times that of the system without the help of Pt NPs. Firstly, we proposed a searching algorithm, which is based on the combined Monte Carlo (MC) method and principal component analysis (PCA) algorithm, to find that the most probable adsorption site of the Pt 13 nanocluster loaded on the (001) surface of 20%-MIL-125-(SCH 3) 2. Next, by using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, we revealed that the accumulation of some positive charges on the Pt 13 cluster and proton adsorbed on the Pt 13 cluster, which can promote the separation of photogenerated electrons and holes, thus improving the photocatalytic efficiency. This work not only provides a method to obtain the adsorption configuration of metal clusters on various MOFs but also provides a new insight into increasing photocatalytic efficiency for H 2 production in Pt/MOF systems.

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“…The Cu + inside of TiO 2 lattice can form the Cu + −O bridge to enhance the electron transfer and the outside Cu 0 functions as the active sites for CO 2 adsorption and activation. [ 53 ] Therefore, the skillful use of variable−valence metal can make a great contribution on improving the activity and selectivity of CO 2 conversion.…”

Section: Photocatalytic Co2 Conversionmentioning

confidence: 99%

The Active Sites Engineering of Catalysts for CO₂ Activation and Conversion

Tang

Wang

2020

Solar RRL

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Catalytic CO2 conversion is considered to be a promising way to simultaneously reduce greenhouse gas emission and realize carbon resource recycling. Several typical reactions including hydrogenation, carboxylation, carboxylic cyclization, and cycloaddition have been extensively studied for yielding high value‐added products. During the process of CO2 conversion, the introduction of light energy and electricity will dramatically lower the energy consumption for CO2 activation so that the whole reaction can efficiently take place at room temperature and atmospheric pressure. For traditional chemical, photochemical, and electrochemical conversions, the processes can be effectively promoted by the rational engineering of active sites on the catalysts. Herein, the most recent advances on the active site engineering of catalysts involving metal or alloy sites, Lewis sites, defect sites, and elemental doping sites are focused on. The influencing mechanisms on the CO2 activation and selective conversion are further discussed according to the structural properties and the interactions with different active sites. Finally, a brief perspective on the future opportunities and challenges in this field is also presented. Researchers who attempt to explore more efficient catalysts for CO2 activation and selective conversion will be guided.

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Cooperation between inside and outside of TiO2: Lattice Cu+ accelerates carrier migration to the surface of metal copper for photocatalytic CO2 reduction

Cited by 106 publications

References 65 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

A Ti-MOF Decorated With a Pt Nanoparticle Cocatalyst for Efficient Photocatalytic H2 Evolution: A Theoretical Study

The Active Sites Engineering of Catalysts for CO₂ Activation and Conversion

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Cooperation between inside and outside of TiO2: Lattice Cu+ accelerates carrier migration to the surface of metal copper for photocatalytic CO2 reduction

Cited by 106 publications

References 65 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

A Ti-MOF Decorated With a Pt Nanoparticle Cocatalyst for Efficient Photocatalytic H2 Evolution: A Theoretical Study

The Active Sites Engineering of Catalysts for CO2 Activation and Conversion

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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

The Active Sites Engineering of Catalysts for CO₂ Activation and Conversion