Coordination Environment Dependent Surface Cu State for CO<sub>2</sub> Hydrogenation to Methanol

Song, Mengyang; Liu, Tangkang; Hong, Xia; Guo-liang, Liu

doi:10.1021/acssuschemeng.3c03163

Cited by 13 publications

(6 citation statements)

References 53 publications

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“…Generally, Cu 0 is exposed to the surface of the catalyst and played a fundamental role in the adsorption and activation of H 2 , while Cu + produced by the strong interaction between Cu and the carrier plays a positive role in the adsorption of CO, which effectively improves the selectivity of methanol. ( Samson et al, 2014 ; Song et al, 2023a ). Figure 10B shows the relationship between STY CH3OH and the ratio of Cu + /(Cu + +Cu 0 ), and the relationship between the two was linear, which indicated that Cu + had a greater influence on the performance of the catalyst.…”

Section: Results and Discussion Headingsmentioning

confidence: 99%

“…Cu-based catalysts have been widely used in the study of CO 2 hydrogenation to methanol. Scholars generally believe that relatively lowcost copper-based catalysts are promising candidates for carbon dioxide hydrogenation to methanol (Song et al, 2023a;Han et al, 2023;Zhang et al, 2023). However, Cu-based catalysts still face the problem of low activity and low stability (Xu et al, 2022;Chen et al, 2023).…”

Section: Introductionmentioning

confidence: 99%

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The influence of Mg/Al molar ratio on the performance of CuMgAl-x catalysts for CO2 hydrogenation to methanol

Liu,

Huang,

et al. 2024

Front. Chem.

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The CuMgAl-x catalysts derived from hydrotalcite precursors with different Mg/Al molar ratios were synthesized and applied to CO2 hydrogenation to methanol reaction. In this study, the effects of Mg/Al molar ratio on the structure and surface properties of CuMgAl-x catalysts were investigated by XRD, N2 adsorption-desorption, SEM, TEM, H2-TPR, CO2-TPD, XPS, and in situ DRIFTS characterization methods. The results showed that an appropriate Mg/Al molar ratio can enhance the Cu-MgO interaction, increasing the basic sites and obtaining suitable acid sites. The dispersion of active Cu on the CuMgAl-x catalysts can be improved by strong Cu-MgO interaction, which enhances the adsorption capacity of CO2 and makes H2 activation easier, accelerates the conversion of intermediate species CO3* and HCO3*to HCOO*, and facilitates further conversion to CH3O* and CH3OH. The strong interaction between Cu and MgO was conducive to the formation of Cu+, which can inhibit the desorption of CO in the reverse water gas shift reaction. The CuMgAl-3 catalyst showed the highest CO2 Conversion rate (14.3%), methanol selectivity (94.5%), and STY of methanol (419.3 g⋅kgcat.−1⋅h−1) at 240°C and 2.5 MPa. The results obtained in this paper can provide a new idea for the design of high-performance catalysts for CO2 hydrogenation to methanol.

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Section: Results and Discussion Headingsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The influence of Mg/Al molar ratio on the performance of CuMgAl-x catalysts for CO2 hydrogenation to methanol

Liu,

Huang,

et al. 2024

Front. Chem.

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“…One distinct advantage of carbon materials is their ability to act as reducing agents during thermal treatments while securing the metallic particles . This feature is crucial since the metallic phase often serves as the active sites for CO hydrogenation . Iron and cobalt catalysts anchored on carbon structures have demonstrated superior FTS activity when juxtaposed with their oxide-supported counterparts, resulting from the potential electron transfer between carbon and the metals …”

Section: Introductionmentioning

confidence: 99%

Harnessing the Synergy of Fe and Co with Carbon Nanofibers for Enhanced CO₂ Hydrogenation Performance

Arizapana,

Schossig,

Wildy

et al. 2024

ACS Sustainable Chem. Eng.

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Amid growing concerns about climate change and energy sustainability, the need to create potent catalysts for the sequestration and conversion of CO 2 to value-added chemicals is more critical than ever. This work describes the successful synthesis and profound potential of high-performance nanofiber catalysts, integrating earth-abundant iron (Fe) and cobalt (Co) as well as their alloy counterpart, FeCo, achieved through electrospinning and judicious thermal treatments. Systematic characterization using an array of advanced techniques, including SEM, TGA-DSC, ICP-MS, XRF, EDS, FTIR−ATR, XRD, and Raman spectroscopy, confirmed the integration and homogeneous distribution of Fe/Co elements in nanofibers and provided insights into their catalytic nuance. Impressively, the bimetallic FeCo nanofiber catalyst, thermally treated at 1050 °C, set a benchmark with an unparalleled CO 2 conversion rate of 46.47% at atmospheric pressure and a consistent performance over a 55 h testing period at 500 °C. Additionally, this catalyst exhibited prowess in producing high-value hydrocarbons, comprising 8.01% of total products and a significant 31.37% of C 2+ species. Our work offers a comprehensive and layered understanding of nanofiber catalysts, delving into their transformations, compositions, and structures under different calcination temperatures. The central themes of metal−carbon interactions, the potential advantages of bimetallic synergies, and the importance of structural defects all converge to define the catalytic performance of these nanofibers. These revelations not only deepen our understanding but also set the stage for future endeavors in designing advanced nanofiber catalysts with bespoke properties tailored for specific applications.

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“…Metal–organic frameworks (MOFs) have been considered as reliable materials consisting of metal ions or metal-oxo clusters coordinated with organic ligands with their uniform tunable porosity and better-defined local structure, opening new opportunities across several remarkable functions, including the gas sensor, capture, separation, and catalysis. − Taking advantage of their diversities in synthetic tunability, devising permanently porous structures bearing functional catalytically active units that confine and interact well with specific reactants has become a novel strategy for catalyst design. , Recently, MOF-based catalysts have been employed for the low-cost and rational design of catalytic sites and widely used in various reactions, particularly, in the catalytic hydrogenation of CO 2 . − …”

Section: Introductionmentioning

confidence: 99%

Enhancing CO₂ Hydrogenation Using a Heterogeneous Bimetal NiAl-Deposited Metal–Organic Framework NU-1000: Insights from First-Principles Calculations

Ma,

Wei,

et al. 2023

Inorg. Chem.

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The hydrogenation of CO 2 to high-value-added liquid fuels is crucial for greenhouse gas emission reduction and optimal utilization of carbon resources. Developing supported heterogeneous catalysts is a key strategy in this context, as they offer well-defined active sites for in-depth mechanistic studies and improved catalyst design. Here, we conducted extensive first-principles calculations to systematically explore the reaction mechanisms for CO 2 hydrogenation on a heterogeneous bimetal NiAl-deposited metal−organic framework (MOF) NU-1000 and its catalytic performance as atomically dispersed catalysts for CO 2 hydrogenation to formic acid (HCOOH), formaldehyde (H 2 CO), and methanol (CH 3 OH). The present results reveal that the presence of the NiAl-oxo cluster deposited on NU-1000 efficiently activates H 2 , and the facile heterolysis of H 2 on Ni and adjacent O sites serves as a precursor to the hydrogenation of CO 2 into various C1 products HCOOH, H 2 CO, and CH 3 OH. Generally, H 2 activation is the ratedetermining step in the entire CO 2 hydrogenation process, the corresponding relatively low free energy barriers range from 14.5 to 15.9 kcal/mol, and the desorption of products on NiAl-deposited NU-1000 is relatively facile. Although the Al atom does not directly participate in the reaction, its presence provides exposed oxygen sites that facilitate the heterolytic cleavage of H 2 and the hydrogenation of C1 intermediates, which plays an important role in enhancing the catalytic activity of the Ni site. The present study demonstrates that the catalytic performance of NU-1000 can be finely tuned by depositing heterometal-oxo clusters, and the porous MOF should be an attractive platform for the construction of atomically dispersed catalysts.

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Coordination Environment Dependent Surface Cu State for CO₂ Hydrogenation to Methanol

Cited by 13 publications

References 53 publications

The influence of Mg/Al molar ratio on the performance of CuMgAl-x catalysts for CO2 hydrogenation to methanol

The influence of Mg/Al molar ratio on the performance of CuMgAl-x catalysts for CO2 hydrogenation to methanol

Harnessing the Synergy of Fe and Co with Carbon Nanofibers for Enhanced CO₂ Hydrogenation Performance

Enhancing CO₂ Hydrogenation Using a Heterogeneous Bimetal NiAl-Deposited Metal–Organic Framework NU-1000: Insights from First-Principles Calculations

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Coordination Environment Dependent Surface Cu State for CO2 Hydrogenation to Methanol

Cited by 13 publications

References 53 publications

The influence of Mg/Al molar ratio on the performance of CuMgAl-x catalysts for CO2 hydrogenation to methanol

The influence of Mg/Al molar ratio on the performance of CuMgAl-x catalysts for CO2 hydrogenation to methanol

Harnessing the Synergy of Fe and Co with Carbon Nanofibers for Enhanced CO2 Hydrogenation Performance

Enhancing CO2 Hydrogenation Using a Heterogeneous Bimetal NiAl-Deposited Metal–Organic Framework NU-1000: Insights from First-Principles Calculations

Contact Info

Product

Resources

About

Coordination Environment Dependent Surface Cu State for CO₂ Hydrogenation to Methanol

Harnessing the Synergy of Fe and Co with Carbon Nanofibers for Enhanced CO₂ Hydrogenation Performance

Enhancing CO₂ Hydrogenation Using a Heterogeneous Bimetal NiAl-Deposited Metal–Organic Framework NU-1000: Insights from First-Principles Calculations