Combined experimental and computational study to unravel the factors of the Cu/TiO2 catalyst for CO2 hydrogenation to methanol

Sharma, Sachin Kumar; Banerjee, Arghya; Paul, Bappi; Poddar, Mukesh Kumar; Sasaki, Takehiko; Samanta, Chanchal; Bal, Rajaram

doi:10.1016/j.jcou.2021.101576

Cited by 21 publications

(18 citation statements)

References 70 publications

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“…The details of the catalytic experiment can be found in our published. 27,28 For all the catalytic experiments, initially the catalyst was reduced in H 2 for 2 h, and it was cooled down to the reaction temperature. Then, the required amount of the feed mixture was passed through the catalyst at reaction temperature and pressure.…”

Section: Methodsmentioning

confidence: 99%

“…Recently, we have shown that hydrothermally prepared Cu/ TiO 2 catalyst and Cu/Mg-Al oxide synthesized via the sol−gel method showed good methanol selectivity. 27,28 In this work, we have used CeO 2 as the support material and showed the influence of In on the Cu/CeO 2 catalyst. In the present study, we prepared the nanocrystalline In-Cu/CeO 2 catalyst in a twostep method by using very small amounts (∼1 wt %) of In as a promoter.…”

Section: Introductionmentioning

confidence: 99%

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Influence of Indium as a Promoter on the Stability and Selectivity of the Nanocrystalline Cu/CeO₂ Catalyst for CO₂ Hydrogenation to Methanol

Sharma

Paul

Pal

et al. 2021

ACS Appl. Mater. Interfaces

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Stable catalyst development for CO2 hydrogenation to methanol is a challenge in catalysis. In this study, indium (In)-promoted Cu nanoparticles supported on nanocrystalline CeO2 catalysts were prepared and explored for methanol production from CO2. In-promoted Cu catalysts with ∼1 wt % In loading showed a methanol production rate of 0.016 mol gCu –1 h–1 with 95% methanol selectivity and no loss of activity for 100 h. It is found that the addition of indium remarkably increases Cu dispersion and decreases Cu particle size. In addition led to an increased metal–support interaction, which stabilizes Cu particles against sintering during the reaction, leading to high stability and activity. In addition, density functional theory calculations suggested that the reaction is proceeding via reverse water gas shift (RWGS) mechanism where the presence of In stabilized intermediate species and lowered CO2 activation energy barriers.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Influence of Indium as a Promoter on the Stability and Selectivity of the Nanocrystalline Cu/CeO₂ Catalyst for CO₂ Hydrogenation to Methanol

Sharma

Paul

Pal

et al. 2021

ACS Appl. Mater. Interfaces

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“…A rota que a reação irá seguir dependerá de como o CO2 for hidrogenado. Quando o CO2 é hidrogenado no átomo de oxigênio, produzindo *HOCO, a reação segue pela rota rWGS + hidrogenação do CO. Quando o CO2 é hidrogenado no átomo de carbono, produzindo *HCOO, a reação segue pela rota do formiato (KATTEL et al, 2016;SHARMA et al, 2021). A rota pela qual a reação irá ocorrer e seu sucesso na produção de metanol também irá depender das interações dos reagentes e intermediários de reação com o catalisador utilizado (KATTEL et al, 2016;WANG et al, 2021a).…”

Section: Ativação Do Co 2 E Mecanismos Pelo Qual Acontecem a Hidrogen...unclassified

“…A energia de ativação do CO2 em superfícies mono e bimetálicas geralmente é mais fraca em comparação a superfícies de óxidos e a interfaces compostas por um metal suportado em um óxido (NIE et al, 2019;SHARMA et al, 2021) Fonte: Autoria própria.…”

Section: Ativação Do Co 2 E Mecanismos Pelo Qual Acontecem a Hidrogen...unclassified

“…Para que a reação de hidrogenação do CO2 seja seletiva para metanol tanto pela rota rWGS + Hidrogenação do CO, quanto pela rota do formiato é preciso que os reagentes e intermediários formados tenham interações de força intermediárias com o catalisador, para que não ocorra nem o envenenamento do sítio ativo e nem que o intermediário se dessorva antes de sofrer as hidrogenações (KATTEL et al, 2016). O caso mais comum ocorre com o CO, pois quando a rota segue pela rWGS + Hidrogenação do CO, se o CO estiver muito fortemente ligado a superfície do catalisador ele envenena o sítio e caso a interação seja muito fraca ele se dessorve na forma de CO gasoso (KATTEL et al, 2016;SHARMA et al, 2021). Por isso, um dos principais desafios que imperam nesta reação está em encontrar um catalisador que consiga estabilizar tanto os intermediários como os reagentes.…”

Section: Ativação Do Co 2 E Mecanismos Pelo Qual Acontecem a Hidrogen...unclassified

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Estudo de catalisadores do tipo Ni-Ga para a síntese de metanol a partir da hidrogenação do CO>sub<2>/sub< em baixas pressões

Rasteiro¹

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Given the industrial development and large population growth in the last years, the uncontrolled emission of greenhouse gases, especially CO2, has generated great concern for the environment and life on Earth. Thereby, policies for containment and CO2 utilization began to be widely studied, as in the case of some reactions where CO2 is converted into value-added products. Among several options for its use, the hydrogenation of CO2 to produce methanol has drawn a lot of attention because methanol is an important raw material for the industry and has a growing demand in the world market. Cu-based catalysts are the most used catalyst in this reaction, but more recently the discovery of Ni-Ga type catalysts with good activity at low pressures has grabbed the attention of the scientific community. Despite being promising, little has been studied about these catalysts and how they act in the reaction. In this context, this work aims to study supported and unsupported Ni-Ga alloy catalysts in methanol synthesis through CO2 hydrogenation at low pressures. The first part of this work seeks to understand the behavior of the unsupported Ni5Ga3 alloy, for example, which physicochemical characteristics of the alloy exert the biggest influence on the reaction, and which intermediates and reaction mechanisms take place on it. In this step, it was noticed that the particle size exerts a strong influence on the catalytic activity and that the reaction takes place through two reaction routes on the alloy, rWGS, and formate. The second part of the work explored the Ni5Ga3 alloy supported on basic oxides, in order to improve the catalytic activity, since the conversions and selectivity were low in the unsupported alloy. The use of supports improved the catalytic activity and the alloy supported on ZrO2 showed the best result, and it was concluded that it is due to the interaction strengths of the reaction intermediates and reagents with the Ni5Ga3-ZrO2 interface. In the third step, the behavior of the alloy on mesoporous inert supports with high surface area (MCM-41 and SBA-15) was studied. It was observed through in situ analysis techniques that the decrease in the density of metallic sites disfavored the adsorption of CO on the surface and, therefore, lower selectivity and conversion to methanol was obtained compared to the reference sample. The fourth and last part of the work united the best basic support used in the second part with the best among the high-area mesoporous supports used in the third part, preparing new catalysts through the ALD technique of ZrO2 on pure SBA-15 or an already impregnated SBA-15 with Ni5Ga3. Among the two groups of prepared materials, it was noted that more ALD cycles were favorable to produce methanol intermediates and that the impregnation of Ni5Ga3 after ALD of ZrO2 on SBA-15 led the reaction to follow only the formate route, different from what happened with the other group, being very desirable for a high selectivity for methanol.

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Effect of Preparation Method on the Performance of Cu−Mn−(La)−Zr Catalysts for CO₂ Hydrogenation to Methanol

et al. 2022

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A series of CuÀ MnÀ (La)À Zr catalysts with molecular ratios of 6 : 3 : (0.35) : 1 was synthesized by sol-gel (CMLZÀ S), co-precipitation (CMLÀ CP, CMLZÀ CP) and hydrothermal (CMLZÀ H) methods, respectively. The effects of the Mn and La on the activity of catalysts were investigated. It was found that the addition of La promoted the formation of the medium basic sites. Mn acted as an electronic promotor that transfer electrons through redox reactions, causing other metals to exhibit different valence states, thus promoting the adsorption and activation of H 2 and CO 2 . At a certain temperature, methanol selectivity decreased in the order of CMLZÀ H > CMLZÀ S > CMLZÀ CP > CMZÀ CP. The selectivity of methanol is correlated with the distribution of basic sites. For the CMLZÀ H catalyst, the highest percentage of moderate basic sites facilitated the activation of CO 2 , resulting in the highest selectivity of methanol. The CO 2 conversion was correlated with the Cu specific surface area.

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Combined experimental and computational study to unravel the factors of the Cu/TiO2 catalyst for CO2 hydrogenation to methanol

Cited by 21 publications

References 70 publications

Influence of Indium as a Promoter on the Stability and Selectivity of the Nanocrystalline Cu/CeO₂ Catalyst for CO₂ Hydrogenation to Methanol

Influence of Indium as a Promoter on the Stability and Selectivity of the Nanocrystalline Cu/CeO₂ Catalyst for CO₂ Hydrogenation to Methanol

Estudo de catalisadores do tipo Ni-Ga para a síntese de metanol a partir da hidrogenação do CO>sub<2>/sub< em baixas pressões

Effect of Preparation Method on the Performance of Cu−Mn−(La)−Zr Catalysts for CO₂ Hydrogenation to Methanol

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Combined experimental and computational study to unravel the factors of the Cu/TiO2 catalyst for CO2 hydrogenation to methanol

Cited by 21 publications

References 70 publications

Influence of Indium as a Promoter on the Stability and Selectivity of the Nanocrystalline Cu/CeO2 Catalyst for CO2 Hydrogenation to Methanol

Influence of Indium as a Promoter on the Stability and Selectivity of the Nanocrystalline Cu/CeO2 Catalyst for CO2 Hydrogenation to Methanol

Estudo de catalisadores do tipo Ni-Ga para a síntese de metanol a partir da hidrogenação do CO>sub<2>/sub< em baixas pressões

Effect of Preparation Method on the Performance of Cu−Mn−(La)−Zr Catalysts for CO2 Hydrogenation to Methanol

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Influence of Indium as a Promoter on the Stability and Selectivity of the Nanocrystalline Cu/CeO₂ Catalyst for CO₂ Hydrogenation to Methanol

Influence of Indium as a Promoter on the Stability and Selectivity of the Nanocrystalline Cu/CeO₂ Catalyst for CO₂ Hydrogenation to Methanol

Effect of Preparation Method on the Performance of Cu−Mn−(La)−Zr Catalysts for CO₂ Hydrogenation to Methanol