Determining Roles of Cu<sup>0</sup> in the Chemosynthesis of Diols via Condensed Diester Hydrogenation on Cu/SiO<sub>2</sub> Catalyst

Wang, Weichao; Wang, Hui; Zhang, Jingwei; Kong, Lingxin; Huang, Huijiang; Liu, Wei; Wang, Shengping; Ma, Xinbin; Zhao, Yujun

doi:10.1002/cctc.202000547

Cited by 9 publications

(3 citation statements)

References 23 publications

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“…A series of CuPSNT catalysts with different Cu/Si ratios (denoted Cu x Si y ) were synthesized by a hydrothermal method. The preparation method was previously reported elsewhere in the literature. , Taking Cu1Si1 as an example, about 10 mmol of Cu(NO 3 ) 2 ·3H 2 O and 40 mmol of NH 4 Cl were dissolved in deionized water. Then, 7.5 mL of NH 3 ·H 2 O was added to obtain a blue solution.…”

Section: Methodsmentioning

confidence: 99%

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Copper Phyllosilicate Nanotube Catalysts for the Chemosynthesis of Cyclohexane via Hydrodeoxygenation of Phenol

et al. 2022

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In the utilization of renewable resources derived from biomass, hydrodeoxygenation (HDO) is one of the most critical steps in the bio-oil upgrading process. Herein, a series of copper phyllosilicate nanotube (CuPSNT) catalysts were successfully prepared and applied in the chemosynthesis of cyclohexane via the phenol HDO reaction. Against the presumption that mono-metal copper was not active for the complete hydrogenation of aromatic compounds, a cyclohexane yield of 97.8% at the total conversion of phenol was achieved at 230 °C on the CuPSNT catalysts with a Cu/Si ratio of 1:1. The kinetic analysis suggested that further conversion of cyclohexanol to cyclohexane is the rate-determining step in the phenol HDO. Cu0 accounts for the hydrogenation, while Cu+ is responsible for the adsorption of phenol and cyclohexanol and in charge of further cyclohexanol dehydration. This conclusion is further confirmed by density functional theory calculations. This work demonstrates that the synergy between Cu0 and Cu+ species of CuPSNT catalysts plays a critical role in the HDO process of phenol, and mono-metal Cu can accomplish both the saturation of aromatic rings and the removal of oxygen groups.

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Section: Methodsmentioning

confidence: 99%

“…The preparation method was previously reported elsewhere in the literature. 26,35 Taking Cu1Si1 as an example, about 10 mmol of Cu(NO 3 ) 2 •3H 2 O and 40 mmol of NH 4 Cl were dissolved in deionized water. Then, 7.5 mL of NH 3 •H 2 O was added to obtain a blue solution.…”

Section: Introductionmentioning

confidence: 99%

Copper Phyllosilicate Nanotube Catalysts for the Chemosynthesis of Cyclohexane via Hydrodeoxygenation of Phenol

et al. 2022

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“…The inexpensive Cu-based catalysts have been reported to exhibit high activities for hydrogenation of esters to alcohols. [9][10][11][12][13] The Cu sites can selectively activate CO bond without catalyzing the hydrogenation of CC bond, thus avoiding the breaking of CC bond. [14] The synergistic effect between Cu 0 and Cu + active sites, in which Cu 0 species activate hydrogen and Cu + species activate CO, are widely applied to enhance the catalytic performance toward hydrogenation of esters.…”

Section: Introductionmentioning

confidence: 99%

Ti³⁺ Tuning the Ratio of Cu⁺/Cu⁰ in the Ultrafine Cu Nanoparticles for Boosting the Hydrogenation Reaction

Zhang

Wang

et al. 2021

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Hydrogenation of diesters to diols is a vital process for chemical industry. The inexpensive Cu+/Cu0‐based catalysts are highly active for the hydrogenation of esters, however, how to efficiently tune the ratio of Cu+/Cu0 and stabilize the Cu+ is a great challenge. In this work, it is demonstrated that doped Ti ions can tune the ratio of Cu+/Cu0 and stabilize the Cu+ by the TiOCu bonds in Ti‐doped SiO2 supported Cu nanoparticle (Cu/Ti–SiO2) catalysts for the high conversion of dimethyl adipate to 1,6‐hexanediol. In the synthesis of the catalysts, the Ti4+OCu2+ bonds promote the reduction of Cu2+ to Cu+ by forming Ti3+OVCu+ (OV: oxygen vacancy) bonds and the amount of Ti doping can tune the ratio of Cu+/Cu0. In the catalytic reaction, the O vacancy activates CO in the ester by forming new Ti3+δORCu1+δ bonds (OR: reactant oxygen), and Cu0 activates hydrogen. After the products are desorbed, the Ti3+δORCu1+δ bonds return to the initial state of Ti3+OVCu+ bonds. The reversible TiOCu bonds greatly improve the activity and stability of the Cu/Ti–SiO2 catalysts. When the content of Ti is controlled at 0.4 wt%, the conversion and selectivity can reach 100% and 98.8%, respectively, and remain stable for 260 h without performance degradation.

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Selective Hydrogenation of Diethyl Malonate to 1,3‐Propanediol Over Ga‐Promoted Cu/SiO₂ Catalysts With Enhanced Activity and Stability

Zhang,

Shi,

Yang

et al. 2024

Chemistry An Asian Journal

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Cu catalysts with different compositions and different Cu and promoter contents were prepared by precipitation‐gel method and studied for the selective hydrogenation of syngas or biomass‐based diethyl malonate (DEM) to valuable 1,3‐propanediol (1,3‐PDO). The Ga‐promoted 70Cu6Ga/SiO2 catalyst was found to exhibit the highest catalytic performance, achieving 100% DEM conversion and 76.6% 1,3‐PDO selectivity under reaction conditions of 160 °C and 8 MPa H2. The 70Cu6Ga/SiO2 bimetallic catalyst also presented obviously better stability than that of the monometallic 70Cu/SiO2 catalyst in a continuous flow reactor over 180 h time‐on stream. Characterization results showed that the incorporation of Ga increased the interaction between Cu and Ga species, hindered the full reduction of Cu2+ species, and thus increased the proportion of Cu+ and the number of Lewis acidic sites on the catalyst surface. The synergistic effect between Cu0 and Cu+ enhanced the adsorption and activation of ester carbonyl groups and their subsequent hydrogenation, eventually contributed to the outstanding performances of the CuGa/SiO2 bimetallic catalysts.

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Determining Roles of Cu⁰ in the Chemosynthesis of Diols via Condensed Diester Hydrogenation on Cu/SiO₂ Catalyst

Cited by 9 publications

References 23 publications

Copper Phyllosilicate Nanotube Catalysts for the Chemosynthesis of Cyclohexane via Hydrodeoxygenation of Phenol

Copper Phyllosilicate Nanotube Catalysts for the Chemosynthesis of Cyclohexane via Hydrodeoxygenation of Phenol

Ti³⁺ Tuning the Ratio of Cu⁺/Cu⁰ in the Ultrafine Cu Nanoparticles for Boosting the Hydrogenation Reaction

Selective Hydrogenation of Diethyl Malonate to 1,3‐Propanediol Over Ga‐Promoted Cu/SiO₂ Catalysts With Enhanced Activity and Stability

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Determining Roles of Cu0 in the Chemosynthesis of Diols via Condensed Diester Hydrogenation on Cu/SiO2 Catalyst

Cited by 9 publications

References 23 publications

Copper Phyllosilicate Nanotube Catalysts for the Chemosynthesis of Cyclohexane via Hydrodeoxygenation of Phenol

Copper Phyllosilicate Nanotube Catalysts for the Chemosynthesis of Cyclohexane via Hydrodeoxygenation of Phenol

Ti3+ Tuning the Ratio of Cu+/Cu0 in the Ultrafine Cu Nanoparticles for Boosting the Hydrogenation Reaction

Selective Hydrogenation of Diethyl Malonate to 1,3‐Propanediol Over Ga‐Promoted Cu/SiO2 Catalysts With Enhanced Activity and Stability

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Product

Resources

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Determining Roles of Cu⁰ in the Chemosynthesis of Diols via Condensed Diester Hydrogenation on Cu/SiO₂ Catalyst

Ti³⁺ Tuning the Ratio of Cu⁺/Cu⁰ in the Ultrafine Cu Nanoparticles for Boosting the Hydrogenation Reaction

Selective Hydrogenation of Diethyl Malonate to 1,3‐Propanediol Over Ga‐Promoted Cu/SiO₂ Catalysts With Enhanced Activity and Stability