Improved catalytic activity and stability of Cu/ZnO catalyst by boron oxide modification for low-temperature methanol synthesis

Chen, Fei; Liang, J. Nellie; Wang, Fan; Guo, Xiaoyu; Gao, Wan-Yang; Kugue, Yasuharu; He, Yingluo; Yang, Guohui; Reubroycharoen, Prasert; Vitidsant, Tharapong; Tsubaki, Noritatsu

doi:10.1016/j.cej.2023.141401

Cited by 14 publications

(7 citation statements)

References 53 publications

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“…XRD characterization was performed on each catalyst for 3 h of hydrogen reduction at 400 °C, as shown in Figure b. It could be found that the peaks of CuO disappear, and the peaks at 2θ = 43.3°, 50.3°, and 74.2° were detected, which can be ascribed to Cu (PDF #85–1326) . The peaks of ZnO and ZrO 2 could also be clearly detected, indicating that the carrier was not destroyed after high-temperature reduction.…”

Section: Resultsmentioning

confidence: 99%

Ternary Cu-ZnO-ZrO₂ Nanostructures Prepared by Surface-Assisted Coprecipitation for Catalytic Hydrogenation of Dimethyl Adipate to 1,6-Hexanediol

Gao,

Zhao,

Miao

et al. 2023

ACS Appl. Nano Mater.

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A series of ternary Cu-ZnO-ZrO2 nanostructures was prepared containing either tetrapropylammonium hydroxide (TPAOH, TH), polyoxyethylene lauryl ether carboxylic acid (BRIJ35, B5), poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (P123 P3), decyltrimethylammonium bromide (DB), poly(vinylpyrrolidone) (PVP, PP), or no surfactant. First, based on the characterization results of XPS, H2-TPR, and other characteristics, the Cu species play vital roles in the process of dimethyl adipate (DMA) hydrogenation, and the Cu+ and Cu0 generated after reduction have a synergistic effect in the hydrogenation process. Results showed that changing the surfactant type and surfactant concentration in the catalyst synthesis has a great effect on the catalytic activity of the catalyst. In particular, the HDO selectivity of the CZZ-4-P3 (52%) catalyst treated with poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) was significantly improved compared to the untreated CZZ (29%) catalyst, which is related to the highest concentration and number of oxygen vacancies. The larger amount of Ovac might promote the hydrogenation of DMA through interaction with the carbonyl group and then weaken the CO bond. On the other hand, it also has a more surface basic (strong basic) amount on the CZZ catalyst. This will provide more adsorption sites and thus adsorb more DMA molecule. Furthermore, it has a larger dispersion of the Cu and smaller catalyst particles. This may be more conducive to adequate contact between the feedstock and catalyst, reducing diffusion effects.

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Section: Resultsmentioning

confidence: 99%

Ternary Cu-ZnO-ZrO₂ Nanostructures Prepared by Surface-Assisted Coprecipitation for Catalytic Hydrogenation of Dimethyl Adipate to 1,6-Hexanediol

Gao,

Zhao,

Miao

et al. 2023

ACS Appl. Nano Mater.

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“…The Cu 2p spectra of all spent catalysts are compared in Figure a. The Cu 2p 3/2 and Cu 2p 1/2 peaks located at 932.7 and 952.5 eV were assigned to the Cu 0 /Cu + species, and there were no Cu 2+ peaks. , The binding energy of Er 0.2 CuZnO was 0.19 eV lower than that of CuZnO. By contrast, the binding energy of Er 0.5 CuZnO and Er 1 CuZnO was comparable and higher than that of Er 0.2 CuZnO, indicating that Cu nanoparticles on the latter had a higher electron density, forming Cu δ− species.…”

Section: Resultsmentioning

confidence: 99%

Modulation of Electronic Metal-Support Interaction between Cu and ZnO by Er for Effective Low-Temperature CO₂ Hydrogenation to Methanol

Huang,

Zhang,

Wang

et al. 2024

ACS Catal.

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Methanol produced by CO 2 hydrogenation is an essential carrier for a sustainable carbon cycle. However, achieving an efficient methanol synthesis on traditional CuZnO catalysts at low temperatures remains challenging due to the inertness of CO 2 . Herein, we designed Er−CuZnO catalysts that exhibited remarkable activity for low-temperature methanol synthesis. At 170 °C, the catalyst achieved a methanol selectivity of 89.8% at a CO 2 conversion of 8.5% on Er 0.2 CuZnO, which outperformed most CuZnO-based catalysts. The particle size of ZnO was reduced after Er was added to the lattice, which increased the Cu−ZnO interfaces and created a strong electronic metal-support interaction (EMSI) between Cu and ZnO. The electron was transferred from ZnO to Cu, forming Cu δ− . Cu δ− with more negative charges enhanced CO 2 adsorbed species and intermediates activation, while facilitating surface carbonate activation and the hydrogenation of *CO intermediates into *HCO species, promoting the methanol formation at low temperatures.

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“…3). In a very recent study using co‐fed CH 3 OH as a “promoter”, the selectivity to methyl formate (up to 2.5 %) was observed in the course of CO/CO 2 hydrogenation to CH 3 OH at 200 °C and 70 bar [25] .

\vcenter{\openup.5em\halign{$\displaystyle{#}$\cr {\rm CH}{_{3}}{\rm OH}+{\rm HCOO}^{\ast }{\stackrel{{\leftarrow}} {{\rightarrow} } }{\rm HCOOCH}{_{3}}+{\rm HO}^{\ast }\hfill\cr}}

\vcenter{\openup.5em\halign{$\displaystyle{#}$\cr {\rm HCOOCH}{_{3}}+{\rm 2H}{_{2}}{\stackrel{{\leftarrow}} {{\rightarrow} } }{\rm 2CH}{_{3}}{\rm OH}{\rm \char44 }\ \Delta {\rm H}{_{25\mskip2mu {\circ}{\rm C}}}=- 46.5\mskip4mu {\rm kJ}\mskip2mu {\rm mol}{^{- 1}}\hfill\cr}}

…”

Section: Co2 Hydrogenation To Ch3oh Over Cu‐based Catalystsmentioning

confidence: 99%

CO₂ Hydrogenation to CH₃OH over Cu‐Based Catalysts: Primary and Side Reactions

Zhao,

Han,

Kondratenko

2023

ChemCatChem

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Carbon dioxide (CO2) hydrogenation to methanol (CH3OH) is one of the most promising approaches to provide this platform chemical and to close carbon cycles. In this minireview, we systematically analyze primary and secondary reactions which can take place in this reaction over Cu‐based catalysts. In addition to repeatedly discussed reverse water gas shift reaction (RWGS) and CH3OH production directly from CO2, we consider decomposition, dehydration, dehydrogenation, and steam reforming of the desired alcohol. These reactions are usually ignored in the studies dealing with CO2 hydrogenation to CH3OH but can worsen the catalyst efficiency. Apart from the corresponding thermodynamic analysis, proposed reaction mechanisms and active sites are described and discussed. The effects of co‐fed water, CH3OH and methyl formate on catalyst performance are critically scrutinized, too. We also provide several criteria for unambiguous comparison of different catalysts in terms of CH3OH selectivity and their activity.

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Improved catalytic activity and stability of Cu/ZnO catalyst by boron oxide modification for low-temperature methanol synthesis

Cited by 14 publications

References 53 publications

Ternary Cu-ZnO-ZrO₂ Nanostructures Prepared by Surface-Assisted Coprecipitation for Catalytic Hydrogenation of Dimethyl Adipate to 1,6-Hexanediol

Ternary Cu-ZnO-ZrO₂ Nanostructures Prepared by Surface-Assisted Coprecipitation for Catalytic Hydrogenation of Dimethyl Adipate to 1,6-Hexanediol

Modulation of Electronic Metal-Support Interaction between Cu and ZnO by Er for Effective Low-Temperature CO₂ Hydrogenation to Methanol

CO₂ Hydrogenation to CH₃OH over Cu‐Based Catalysts: Primary and Side Reactions

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Improved catalytic activity and stability of Cu/ZnO catalyst by boron oxide modification for low-temperature methanol synthesis

Cited by 14 publications

References 53 publications

Ternary Cu-ZnO-ZrO2 Nanostructures Prepared by Surface-Assisted Coprecipitation for Catalytic Hydrogenation of Dimethyl Adipate to 1,6-Hexanediol

Ternary Cu-ZnO-ZrO2 Nanostructures Prepared by Surface-Assisted Coprecipitation for Catalytic Hydrogenation of Dimethyl Adipate to 1,6-Hexanediol

Modulation of Electronic Metal-Support Interaction between Cu and ZnO by Er for Effective Low-Temperature CO2 Hydrogenation to Methanol

CO2 Hydrogenation to CH3OH over Cu‐Based Catalysts: Primary and Side Reactions

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Ternary Cu-ZnO-ZrO₂ Nanostructures Prepared by Surface-Assisted Coprecipitation for Catalytic Hydrogenation of Dimethyl Adipate to 1,6-Hexanediol

Ternary Cu-ZnO-ZrO₂ Nanostructures Prepared by Surface-Assisted Coprecipitation for Catalytic Hydrogenation of Dimethyl Adipate to 1,6-Hexanediol

Modulation of Electronic Metal-Support Interaction between Cu and ZnO by Er for Effective Low-Temperature CO₂ Hydrogenation to Methanol

CO₂ Hydrogenation to CH₃OH over Cu‐Based Catalysts: Primary and Side Reactions