TixCe1−xO2 nanocomposites: a monolithic catalyst for the direct conversion of carbon dioxide and methanol to dimethyl carbonate

Chen, Yongdong; Wang, Hong; Qin, Zhaoxian; Tian, Shanli; Ye, Zhongbin; Lin, Yuzhen; Abroshan, Hadi; Li, Gao

doi:10.1039/c9gc00811j

Cited by 73 publications

(76 citation statements)

References 40 publications

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“…Next, Shi et al. controlled and precisely deposited the CuO nanoclusters onto the TiO 2 {101} of the TiO 2 ‐spindle, supported by TEM and photoluminescence and Raman spectroscopy [62] . CH 3 OH‐TPD showed that methanol can be chemisorbed on the CuO/TiO 2 catalyst, meaning that the CuO/TiO 2 should be a good candidate for the methanol oxidations.…”

Section: Methyl Formate (Mf)mentioning

confidence: 99%

“…An over 97 % conversion and 83 % selectivity were achieved over the CuO/TiO 2 ‐P under mild conditions (365 nm irradiation). Interestingly, the catalytic activity has a strong relationship with surface oxygen vacancy (O V ) species during the CuO/TiO 2 ‐P catalyzed reactions, [62,63] Figure 6, indicating that the CuO nanoclusters can optimally tune excitons recombination through O V generation to promote the methanol conversions. Further, in‐situ attenuated total reflection infrared spectroscopic analysis reveals, for the first time, that the methanol oxidation most likely occurs via the pathway from the adsorbed methoxy (CH 3 O*) to adsorbed formaldehyde (CHO*) species, Figure 7.…”

Section: Methyl Formate (Mf)mentioning

confidence: 99%

“…While the oxygen is dissociated on CuO particles with the photo‐generated electrons and then to refill TiO 2 oxygen vacancies. The two processes are the rate‐determining steps for the photo‐oxidation reactions [62,63] . The HCHO* species quickly reacts with a neighboring CH 3 O* to give MF product.…”

Section: Methyl Formate (Mf)mentioning

confidence: 99%

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Recent Advances in Aerobic Photo‐Oxidation of Methanol to Valuable Chemicals

et al. 2021

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The oxidation of photocatalytic methanol into valuable chemicals is of considerable importance to the growth of the chemical industry. TiO2 has been proven to be a catalyst for methanol photocatalytic oxidation to valued chemicals (e. g. methyl formate and dimethoxymethane) at room temperature with an inferior activity. Recently, it has become a hot research topic due to its low interaction temperature with fewer by‐products. Further, the introduction of IB metal particles (i. e. Cu, Ag, and Au) upon the surface of titania can drastically enhance the catalytic activity in the photo‐oxidation, which is mainly due to metal nanoparticles can optimally enhance the efficiency of the isolation of photo‐generated holes and electrons as well as dissociate oxygen molecules. Herein, we review recent progress of the photocatalysis of methanol toward the production of chemicals over different photocatalysts (e. g., TiO2P25, M NPs/TiO2, where M=CuO, Ag2O, Au, PtO, etc). Moreover, we also glean an understanding of the catalytic mechanism and conversion pathway at play, which is confirmed by STM, in‐situ ATR‐IR, DFT simulations, etc. The reaction pathway of photo‐oxidation is different from that in the thermal process. A pivotal intermediate is absorbed formaldehyde (HCHO*), which is formed via an oxidative dehydrogenation over the redox sites of catalysts. Then the generated HCHO* directly reacts with neighboring methanol to give methyl formate (on redox sites) and dimethoxymethane (on acidic sites through a scrambling movement).

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Section: Methyl Formate (Mf)mentioning

confidence: 99%

Section: Methyl Formate (Mf)mentioning

confidence: 99%

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Recent Advances in Aerobic Photo‐Oxidation of Methanol to Valuable Chemicals

et al. 2021

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“…[1][2][3][4][5] Recently, development of effective catalysts to produce DMC through oxidative carbonylation of methanol, which is thermodynamically favorable has received greater attention. [6][7][8][9][10][11][12][13][14][15][16][17][18] Being, chloride-free, CuY zeolite has shown greate potential to obtain high activity and excellent selectivity for oxidative carbonylation reaction. [16][17][18][19][20][21][22][23] Generally, Cu exchanged zeolite Y, CuY was prepared by ion-exchange of NaY zeolite with the ammonia solution of copper nitrate, followed by calcination at high temperatures in an inert atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Role of metal co‐cations in improving CuY zeolite performance for DMC synthesis: A theoretical study

Zheng

Narkhede

Zhang

et al. 2020

Applied Organom Chemis

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First principle calculations based on density functional theory are conducted to investigate the influence of metal cations including Mg2+, Ca2+, Sr2+, Ba2+, La (OH)2+ and Ce (OH)2+ in the small cage of zeolite on the electronic environment of adjacent active center, Cu+ in CuY zeolite as well as the process of CO insertion into CH3O to form CH3OCO for oxidative carbonylation of methanol. The study explains the theoretical reasons for the effects of metal cations on the catalytic activity of zeolites. It was found that, the presence of co‐cations in the small cage can affect the electronic properties and also the catalytic activity in two ways. Firstly, the presence of co‐cations, viz., Ca2+, Sr2+, Mg2+, Ba2+ and La species in small cage hinders the migration of active Cu+ cations from the super cage to small cage. Secondly, the co‐cations greatly affect the charge transfer from zeolite framework to Cu+ present in the adjacent super cage, leading to the increase of the net charge and binding energy of Cu+. The findings can improve the CO adsorption and insertion efficiencies, and the stability of transition states, which results in the enhanced catalytic activity of corresponding zeolites.

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“…There is a popular belief that the greater the proportion of Ce 3+ , the higher the degree of unsaturated of ceria, which may be beneficial to catalyst performance. Doping metal ions into ceria could create more oxygen vacancies 21,22 . Li et al studied the role of oxygen vacancy in DMC formation by doping Zr into CeO 2, 22 and they found that CO 2 could be adsorbed and activated on the oxygen vacancy sites.…”

Section: Introductionmentioning

confidence: 99%

Influence of valence state of cerium ion on dimethyl carbonate synthesis from methanol and carbon dioxide over CeO₂

Zhang

Zhao

et al. 2020

Asia-Pacific J Chem Eng

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The relationship between valence state of cerium ion and the catalytic activity for dimethyl carbonate (DMC) synthesis directly from carbon dioxide and methanol was investigated by using four CeO2 catalysts calcined at the different temperatures, which showed different concentrations of Ce4+ analyzed by XPS. In situ Fourier transform infrared spectroscopy (FTIR) was used to probe CO2 and methanol adsorption species on ceria surface. With the calcination temperature increasing from 323 to 973 K, the concentration of Ce4+ increased, leading to larger proportion of active methanol adsorptions (Types I and II methoxy) and CO2 adsorptions (bidentate carbonate). Meanwhile, high‐calcination temperature also led to small surface area and more –OH group dehydration, which resulted in the less formation of active Types I and II methoxy and bidentate carbonate. As a result, the ceria calcined at 773 K showed the highest activity and the one calcined at 973 K performed the lowest.

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Ti_xCe_1−xO₂ nanocomposites: a monolithic catalyst for the direct conversion of carbon dioxide and methanol to dimethyl carbonate

Abstract: Dimethyl carbonate (DMC) is widely employed as a versatile reagent and solvent for green organic synthesis and fuel additives.

Cited by 73 publications

References 40 publications

Recent Advances in Aerobic Photo‐Oxidation of Methanol to Valuable Chemicals

Recent Advances in Aerobic Photo‐Oxidation of Methanol to Valuable Chemicals

Role of metal co‐cations in improving CuY zeolite performance for DMC synthesis: A theoretical study

Influence of valence state of cerium ion on dimethyl carbonate synthesis from methanol and carbon dioxide over CeO₂

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TixCe1−xO2 nanocomposites: a monolithic catalyst for the direct conversion of carbon dioxide and methanol to dimethyl carbonate

Abstract: Dimethyl carbonate (DMC) is widely employed as a versatile reagent and solvent for green organic synthesis and fuel additives.

Cited by 73 publications

References 40 publications

Recent Advances in Aerobic Photo‐Oxidation of Methanol to Valuable Chemicals

Recent Advances in Aerobic Photo‐Oxidation of Methanol to Valuable Chemicals

Role of metal co‐cations in improving CuY zeolite performance for DMC synthesis: A theoretical study

Influence of valence state of cerium ion on dimethyl carbonate synthesis from methanol and carbon dioxide over CeO2

Contact Info

Product

Resources

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Ti_xCe_1−xO₂ nanocomposites: a monolithic catalyst for the direct conversion of carbon dioxide and methanol to dimethyl carbonate

Influence of valence state of cerium ion on dimethyl carbonate synthesis from methanol and carbon dioxide over CeO₂