Catalytic roles of In2O3 in ZrO2-based binary oxides for CO2 hydrogenation to methanol

Wei, Yanling; Liu, Fei; Ma, Jun; Yang, Chunliang; Wang, Xiaodan; Cao, Jian

doi:10.1016/j.mcat.2022.112354

Cited by 17 publications

(28 citation statements)

References 48 publications

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“…The preparation method of In 2 O 3 /ZrO 2 also vitally affects the electronic structure effect, thus to optimize the interaction of In 2 O 3 and ZrO 2 , and the surface exposure degree of In 2 O 3 , four different compositing strategies (liquid-phase coprecipitation, precipitation-coating method, ball milling method, and incipient wetness impregnation, respectively) for the synthesis of In 2 O 3 /ZrO 2 were compared by Gao et al [ 104 ]. It was found that the exposure area of In 2 O 3 prepared by the precipitation-coating method was the highest ( S In = 6.22 m 2 g −1 ), whereas it was lowest ( S In = 1.56 m 2 g −1 ) by the coprecipitation method due to the formation of In 2 O 3 bulk dispersion with ZrO 2 .…”

Section: In 2 O 3 -Based Cataly...mentioning

confidence: 99%

Recent Advances of Indium Oxide-Based Catalysts for CO2 Hydrogenation to Methanol: Experimental and Theoretical

Cai

Tan

et al. 2023

Materials

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Methanol synthesis from the hydrogenation of carbon dioxide (CO2) with green H2 has been proven as a promising method for CO2 utilization. Among the various catalysts, indium oxide (In2O3)-based catalysts received tremendous research interest due to the excellent methanol selectivity with appreciable CO2 conversion. Herein, the recent experimental and theoretical studies on In2O3-based catalysts for thermochemical CO2 hydrogenation to methanol were systematically reviewed. It can be found that a variety of steps, such as the synthesis method and pretreatment conditions, were taken to promote the formation of oxygen vacancies on the In2O3 surface, which can inhibit side reactions to ensure the highly selective conversion of CO2 into methanol. The catalytic mechanism involving the formate pathway or carboxyl pathway over In2O3 was comprehensively explored by kinetic studies, in situ and ex situ characterizations, and density functional theory calculations, mostly demonstrating that the formate pathway was extremely significant for methanol production. Additionally, based on the cognition of the In2O3 active site and the reaction path of CO2 hydrogenation over In2O3, strategies were adopted to improve the catalytic performance, including (i) metal doping to enhance the adsorption and dissociation of hydrogen, improve the ability of hydrogen spillover, and form a special metal-In2O3 interface, and (ii) hybrid with other metal oxides to improve the dispersion of In2O3, enhance CO2 adsorption capacity, and stabilize the key intermediates. Lastly, some suggestions in future research were proposed to enhance the catalytic activity of In2O3-based catalysts for methanol production. The present review is helpful for researchers to have an explicit version of the research status of In2O3-based catalysts for CO2 hydrogenation to methanol and the design direction of next-generation catalysts.

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Section: In 2 O 3 -Based Cataly...mentioning

confidence: 99%

Recent Advances of Indium Oxide-Based Catalysts for CO2 Hydrogenation to Methanol: Experimental and Theoretical

Cai

Tan

et al. 2023

Materials

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“…The catalyst is able to achieve a CO 2 conversion of 7.5 % and space-time yield of methanol reached 0.398 g MeOH •h À 1 •g À 1 cat . [116] However, a precise control of the synthesis condition is required to avoid additional nucleation events or the precipitation of undesired phases. Useful advices include ensuring a complete mixing of the solid precursors of both the active metal and support, and avoiding temperature gradients in the synthesis solution.…”

Section: Co-precipitationmentioning

confidence: 99%

“…with a high In 2 O 3 loading of 10 %. The catalyst is able to achieve a CO 2 conversion of 7.5 % and space‐time yield of methanol reached 0.398 g MeOH ⋅h −1 ⋅g −1 cat [116] . However, a precise control of the synthesis condition is required to avoid additional nucleation events or the precipitation of undesired phases.…”

Section: Catalyst Synthesismentioning

confidence: 99%

Heterogeneous Catalytic Systems for Carbon Dioxide Hydrogenation to Value‐Added Chemicals

et al. 2023

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Utilizing renewable energy to hydrogenate carbon dioxide into fuels eliminates massive CO2 emissions from the atmosphere and diminishes our need for using fossil fuels. This review presents the most recent developments for designing heterogeneous catalysts for the hydrogenation of CO2 to formate, methanol, and C2+ hydrocarbons. Thermodynamic challenges and mechanistic insights are discussed, providing a strong foundation to propose a suitable catalyst. The main body of this review focuses on nanostructured catalysts for constructing efficient heterogeneous systems. The most important factors affecting catalytic performance are highlighted, including active metals, supports and promoters that can potentially be used. The summary of the results and the outlook are presented in the final section. During the past few decades, heterogeneous CO2 hydrogenation has gained much attention and made tremendous progress. Thus, many highly efficient catalysts have been studied to discover their active sites and provide mechanistic insights. This paper summarizes recent advances in CO2 hydrogenation and its conversion into various hydrocarbons such as formate, methanol, and C2+ products. As for formate production, Au and Ru nanocatalysts show superior activity. However, considering the catalyst cost, Cu‐based catalysts have an excellent prospect for methanol production, among other catalysts. Ultra‐small nanoparticles and nanoclusters appear promising to provide highly active cost‐effective catalysts. A growing number of researchers are investigating the possibility of directly synthesizing C2+ products through CO2 hydrogenation. The major challenge in producing heavy hydrocarbons is breaking the ASF limitations, which have been achieved over bifunctional catalysts using zeolites. Using suitable support and promoter can lead to a superior activity, ascribed to structural, electronic, and chemical promotional effects.

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“…The O 1s peaks of all samples can be separated into three peaks at around 529.6, 531.1, and 532.3 eV, which are denoted as lattice oxygen (O lattice ), defect oxygen (O defect ), and adsorbed oxygen species (O OH ), respectively. 38 The percentage of defect oxygen in the total oxygen content represents the oxygen vacancy concentration. In order to quantitatively calculate the oxygen vacancy concentration, all O 1s peaks were processed by peak area calculation, and the results obtained are reported in Table 3: prolonging the reflux time, the proportion of defect oxygen on the surface of the catalysts increases first and then decreases, and the Cu/ZrO 2 -18h catalyst has the highest density of oxygen vacancy.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Effect of Reflux Time on the Performance of the Cu/ZrO₂ Catalyst for CO₂ Hydrogenation to Methanol

Dai,

Meng,

et al. 2023

ACS Appl. Energy Mater.

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The hydrogenation of CO2 into methanol was investigated by means of the Cu/ZrO2 catalyst to analyze the effect of reflux time on catalytic performance. A series of high-activity Cu/ZrO2 catalysts were prepared by introducing the support pretreated with ammonia reflux. The effect of reflux time on the structure and performance of all catalysts was systematically studied. Combined with various characterizations such as X-ray diffraction (XRD), N2 physisorption, temperature-programmed reduction by H2 (H2-TPR), temperature-programmed desorption of H2 and CO2, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM), it can be seen that the catalysts after reflux exhibited a stable amorphous structure with more medium and strong basic sites. Moreover, the proportion of defect oxygen and surface Cu+ species for Cu/ZrO2 catalysts increased, and the metal–support interaction was strengthened, which effectively increased active sites and promoted CO2 activation, and thus, the catalyst with stronger activity and better stability was obtained. The CO2 conversion dramatically increased by 4–5 times (from 5.4 to 22.1%) after reflux treatment, and the Cu/ZrO2-18h catalyst had the highest catalytic activity and a methanol space time yield of 394 gMeOH h–1 kgcat –1 at 260 °C.

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Catalytic roles of In2O3 in ZrO2-based binary oxides for CO2 hydrogenation to methanol

Cited by 17 publications

References 48 publications

Recent Advances of Indium Oxide-Based Catalysts for CO2 Hydrogenation to Methanol: Experimental and Theoretical

Recent Advances of Indium Oxide-Based Catalysts for CO2 Hydrogenation to Methanol: Experimental and Theoretical

Heterogeneous Catalytic Systems for Carbon Dioxide Hydrogenation to Value‐Added Chemicals

Effect of Reflux Time on the Performance of the Cu/ZrO₂ Catalyst for CO₂ Hydrogenation to Methanol

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Catalytic roles of In2O3 in ZrO2-based binary oxides for CO2 hydrogenation to methanol

Cited by 17 publications

References 48 publications

Recent Advances of Indium Oxide-Based Catalysts for CO2 Hydrogenation to Methanol: Experimental and Theoretical

Recent Advances of Indium Oxide-Based Catalysts for CO2 Hydrogenation to Methanol: Experimental and Theoretical

Heterogeneous Catalytic Systems for Carbon Dioxide Hydrogenation to Value‐Added Chemicals

Effect of Reflux Time on the Performance of the Cu/ZrO2 Catalyst for CO2 Hydrogenation to Methanol

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Effect of Reflux Time on the Performance of the Cu/ZrO₂ Catalyst for CO₂ Hydrogenation to Methanol