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Journal articles on the topic 'CO/CO2 hydrogenation'

Author: Grafiati

Published: 1 March 2025

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1

Li, Meng, and Dong Ding. "(Invited) Tuning Selective CO₂ Electrohydrogenation Under Mid Temperature and Pressure." ECS Meeting Abstracts MA2024-01, no. 37 (August 9, 2024): 2184. http://dx.doi.org/10.1149/ma2024-01372184mtgabs.

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To address rising environmental concerns and energy challenges, it is highly desirable to develop green technologies for a sustainable future. Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds. Electrochemical CO2 hydrogenation using renewable electricity is considered one of the most promising pathways to reach the environmental economics. Among various electrochemical devices, a solid state electrolyzer working at intermediate temperatures has the advantages of high reaction rates and low overpotentials. As CO2 molecules is quite stable, it is critical to develop electrocatalysts with high activity to reduce electricity engagement. Also, CO2 hydrogenation has multiple pathways which normally results in low selectivity for a target product. A tunable electrocatalyst with high selectivity to different products is desirable for CO2 conversion reactions. Heterostructured nanomaterials attracts great attentions in electrochemical systems. With careful design, they can show very high activity and selectivity towards an electrochemical reaction pathway. In this work, we combine theoretical simulations, including density functional theory (DFT) and ab initio molecular dynamics (AIMD) calculations, with experimental methods (characterizations and electrochemical measurements) for rational design of highly efficient heterostructured nanomaterials for CO2 hydrogenations. We studied the strong metal-support interaction (SMSI) in a doped CeO2 supported noble metal nanoparticles (NPs) system using theoretical calculations. The results indicate that SMSI largely depends on chemical conditions of the support and particle size of dispersed metal NPs. By tuning the SMSI, we can successfully change the catalytic activity and selectivity towards CO2 hydrogenation reactions. Based on these findings, we designed tunable heterostructured nanomaterials for efficient hydrogenation reactions at intermediate temperatures. These predictions were further confirmed by experimental method. By using a combination of high-throughput theoretical calculations and electrochemical measurements, we successfully developed highly active catalysts for electrochemical CO2 hydrogenation reactions. This framework is also applicable to other electrochemical systems using heterostructured materials.

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2

Konsolakis, Michalis, Maria Lykaki, Sofia Stefa, Sόnia A. C. Carabineiro, Georgios Varvoutis, Eleni Papista, and Georgios E. Marnellos. "CO2 Hydrogenation over Nanoceria-Supported Transition Metal Catalysts: Role of Ceria Morphology (Nanorods versus Nanocubes) and Active Phase Nature (Co versus Cu)." Nanomaterials 9, no. 12 (December 6, 2019): 1739. http://dx.doi.org/10.3390/nano9121739.

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In this work we report on the combined impact of active phase nature (M: Co or Cu) and ceria nanoparticles support morphology (nanorods (NR) or nanocubes (NC)) on the physicochemical characteristics and CO2 hydrogenation performance of M/CeO2 composites at atmospheric pressure. It was found that CO2 conversion followed the order: Co/CeO2 > Cu/CeO2 > CeO2, independently of the support morphology. Co/CeO2 catalysts demonstrated the highest CO2 conversion (92% at 450 °C), accompanied by 93% CH4 selectivity. On the other hand, Cu/CeO2 samples were very selective for CO production, exhibiting 52% CO2 conversion and 95% CO selectivity at 380 °C. The results obtained in a wide range of H2:CO2 ratios (1–9) and temperatures (200–500 °C) are reaching in both cases the corresponding thermodynamic equilibrium conversions, revealing the superiority of Co- and Cu-based samples in methanation and reverse water-gas shift (rWGS) reactions, respectively. Moreover, samples supported on ceria nanocubes exhibited higher specific activity (µmol CO2·m−2·s−1) compared to samples of rod-like shape, disclosing the significant role of support morphology, besides that of metal nature (Co or Cu). Results are interpreted on the basis of different textural and redox properties of as-prepared samples in conjunction to the different impact of metal entity (Co or Cu) on CO2 hydrogenation process.

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3

Priyadarshani, Nilusha, Bojana Ginovska, J. Timothy Bays, John C. Linehan, and Wendy J. Shaw. "Photoswitching a molecular catalyst to regulate CO2 hydrogenation." Dalton Transactions 44, no. 33 (2015): 14854–64. http://dx.doi.org/10.1039/c5dt01649e.

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4

Quan, Fengjiao, Guangming Zhan, Chengliang Mao, Zhihui Ai, Falong Jia, Lizhi Zhang, Honggang Gu, and Shiyuan Liu. "Efficient light-driven CO2 hydrogenation on Ru/CeO2 catalysts." Catalysis Science & Technology 8, no. 24 (2018): 6503–10. http://dx.doi.org/10.1039/c8cy01787e.

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5

Wang, Yushan, Mengting Yu, Xinyi Zhang, Yujie Gao, Jia Liu, Ximing Zhang, Chunxiao Gong, Xiaoyong Cao, Zhaoyang Ju, and Yongwu Peng. "Density Functional Theory Study of CO2 Hydrogenation on Transition-Metal-Doped Cu(211) Surfaces." Molecules 28, no. 6 (March 22, 2023): 2852. http://dx.doi.org/10.3390/molecules28062852.

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The massive emission of CO2 has caused a series of environmental problems, including global warming, which exacerbates natural disasters and human health. Cu-based catalysts have shown great activity in the reduction of CO2, but the mechanism of CO2 activation remains ambiguous. In this work, we performed density functional theory (DFT) calculations to investigate the hydrogenation of CO2 on Cu(211)-Rh, Cu(211)-Ni, Cu(211)-Co, and Cu(211)-Ru surfaces. The doping of Rh, Ni, Co, and Ru was found to enhance CO2 hydrogenation to produce COOH. For CO2 hydrogenation to produce HCOO, Ru plays a positive role in promoting CO dissociation, while Rh, Ni, and Co increase the barriers. These results indicate that Ru is the most effective additive for CO2 reduction in Cu-based catalysts. In addition, the doping of Rh, Ni, Co, and Ru alters the electronic properties of Cu, and the activity of Cu-based catalysts was subsequently affected according to differential charge analysis. The analysis of Bader charge shows good predictions for CO2 reduction over Cu-based catalysts. This study provides some fundamental aids for the rational design of efficient and stable CO2-reducing agents to mitigate CO2 emission.

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6

Lykaki, Maria, Sofia Stefa, Georgios Varvoutis, Vassilios D. Binas, George E. Marnellos, and Michalis Konsolakis. "Comparative Assessment of First-Row 3d Transition Metals (Ti-Zn) Supported on CeO2 Nanorods for CO2 Hydrogenation." Catalysts 14, no. 9 (September 11, 2024): 611. http://dx.doi.org/10.3390/catal14090611.

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Herein, motivated by the excellent redox properties of rod-shaped ceria (CeO2-NR), a series of TM/CeO2 catalysts, employing the first-row 3d transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) as active metal phases, were comparatively assessed under identical synthesis and reaction conditions to decipher the role of active metal in the CO2 hydrogenation process. Notably, a volcano-type dependence of CO2 hydrogenation activity/selectivity was disclosed as a function of metal entity revealing a maximum for the Ni-based sample. Ni/CeO2 is extremely active and fully selective to methane (YCH4 = 90.8% at 350 °C), followed by Co/CeO2 (YCH4 = 45.2%), whereas the rest of the metals present an inferior performance. No straightforward relationship was disclosed between the CO2 hydrogenation performance and the textural, structural, and redox properties, whereas, on the other hand, a volcano-shaped trend was established with the relative concentration of oxygen vacancies and partially reduced Ce3+ species. The observed trend is also perfectly aligned with the previously reported volcano-type dependence of atomic hydrogen adsorption energy and CO2 activation as a function of 3d-orbital electron number, revealing the key role of intrinsic electronic features of each metal in conjunction to metal–support interactions.

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7

Li, Xiuping, Jiaqi Wang, Bolin Yin, Kaihong Liu, Jingjing Zhao, Bo Jiang, and Hexing Li. "Plasmonic Cu-supported amorphous RuP for efficient photothermal CO₂ hydrogenation to CO." RSC Advances 15, no. 3 (2025): 1658–64. https://doi.org/10.1039/d4ra07361d.

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8

Liu, Miao, Yanhui Yi, Li Wang, Hongchen Guo, and Annemie Bogaerts. "Hydrogenation of Carbon Dioxide to Value-Added Chemicals by Heterogeneous Catalysis and Plasma Catalysis." Catalysts 9, no. 3 (March 18, 2019): 275. http://dx.doi.org/10.3390/catal9030275.

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Due to the increasing emission of carbon dioxide (CO2), greenhouse effects are becoming more and more severe, causing global climate change. The conversion and utilization of CO2 is one of the possible solutions to reduce CO2 concentrations. This can be accomplished, among other methods, by direct hydrogenation of CO2, producing value-added products. In this review, the progress of mainly the last five years in direct hydrogenation of CO2 to value-added chemicals (e.g., CO, CH4, CH3OH, DME, olefins, and higher hydrocarbons) by heterogeneous catalysis and plasma catalysis is summarized, and research priorities for CO2 hydrogenation are proposed.

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9

Lu, Bowen, Huiying Sang, Liang Liu, Zhijian Yu, Yaqin Guo, and Yongqing Xu. "The Synergistic Effect of CeO2 and Micron-Cu Enhances the Hydrogenation of CO2 to CO." Processes 12, no. 9 (September 6, 2024): 1912. http://dx.doi.org/10.3390/pr12091912.

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The catalytic applications of micron Cu powder are limited due to its large particle size and small specific surface area. Modifying micro-Cu powder to achieve a high catalytic performance is a challenge in the application of micron copper. In this work, micro-Cu was used to synthesize a CeO2–Cu catalyst, and the phase composition and surface pore structure were analyzed using XRD, BET, etc. The CO2 hydrogenation performance of the CeO2–Cu catalyst was analyzed in comparison with CeO2 and Cu, and we found that the CeO2–Cu catalyst exhibited a synergistic effect between Cu and cerium, resulting in a much higher hydrogenation performance at 500 °C than CeO2 or Cu alone. H2-TPR and TEM characterization revealed that the CeO2–Cu catalyst formed interfacial interactions with a relatively large Ce–Cu interface, where cerium oxide could promote the reduction of CuO and lower the reduction temperature. Additionally, cerium oxide formed a confinement structure for Cu, and the CeO2–Cu catalyst exhibited a higher oxygen vacancy concentration, thereby promoting the CO2 hydrogenation performance. Cu–CeO2 interaction provides valuable insights into the catalytic application of micron Cu powder.

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10

Morozova, O. S., A. N. Streletskii, I. V. Berestetskaya, and A. B. Borunova. "Co and Co2 hydrogenation under mechanochemical treatment." Catalysis Today 38, no. 1 (October 1997): 107–13. http://dx.doi.org/10.1016/s0920-5861(97)00044-8.

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11

Yang, Bin, Yifu Wang, Longtai Li, Biao Gao, Lingxia Zhang, and Limin Guo. "Probing the morphological effects of ReO_x/CeO₂ catalysts on the CO₂ hydrogenation reaction." Catalysis Science & Technology 12, no. 4 (2022): 1159–72. http://dx.doi.org/10.1039/d1cy02096j.

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12

Guo, Wei, Jian Jun Wang, Wen Gui Gao, and Hua Wang. "Comparison of Two Different Methods of Preparing Chemical Raw Materials Using Blast Furnace Gas." Advanced Materials Research 511 (April 2012): 96–100. http://dx.doi.org/10.4028/www.scientific.net/amr.511.96.

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This paper studied the preparation of chemical raw materials–methanol using blast furnace gas obtained from steel production process. The energy saving and emission reduction effect and the economic benefit brought by the co-hydrogenation process of a mixture of CO and CO2 (CHP) has been compared with those brought by the respective hydrogenation process of CO and CO2 (RHP). The result shows that the CHP brings more economic benefit than the RHP, and the CHP brings more energy saving and emission reduction effect than the RHP.

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13

Sirikulbodee, Paphatsara, Monrudee Phongaksorn, Thana Sornchamni, Tanakorn Ratana, and Sabaithip Tungkamani. "Effect of Different Iron Phases of Fe/SiO2 Catalyst in CO2 Hydrogenation under Mild Conditions." Catalysts 12, no. 7 (June 25, 2022): 698. http://dx.doi.org/10.3390/catal12070698.

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The effect of different active phases of Fe/SiO2 catalyst on the physio-chemical properties and the catalytic performance in CO2 hydrogenation under mild conditions (at 220 °C under an ambient pressure) was comprehensively studied in this work. The Fe/SiO2 catalyst was prepared by an incipient wetness impregnation method. Hematite (Fe2O3) in the calcined Fe/SiO2 catalyst was activated by hydrogen, carbon monoxide, and hydrogen followed by carbon monoxide, to form a metallic iron (Fe/SiO2-h), an iron carbide (Fe/SiO2-c), and a combination of a metallic iron and an iron carbide (Fe/SiO2-hc), respectively. All activated catalysts were characterized by XRD, Raman spectroscopy, N2 adsorption–desorption, H2-TPR, CO-TPR, H2-TPD, CO2-TPD, CO-TPD, NH3-TPD, and tested in a CO2 hydrogenation reaction. The different phases of the Fe/SiO2 catalyst are formed by different activation procedures and different reducing agents (H2 and CO). Among three different activated catalysts, the Fe/SiO2-c provides the highest CO2 hydrogenation performance in terms of maximum CO2 conversion, as well as the greatest selectivity toward long-chain hydrocarbon products, with the highest chain growth probability of 0.7. This is owing to a better CO2 and CO adsorption ability and a greater acidity on the carbide form of the Fe/SiO2-c surface, which are essential properties of catalysts for polymerization in FTs.

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14

Novodárszki, Gyula, Ferenc Lónyi, Magdolna R. Mihályi, Anna Vikár, Róbert Barthos, Blanka Szabó, József Valyon, and Hanna E. Solt. "Reaction Pathways of Gamma-Valerolactone Hydroconversion over Co/SiO2 Catalyst." Catalysts 13, no. 7 (July 23, 2023): 1144. http://dx.doi.org/10.3390/catal13071144.

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The hydroconversion of γ-valerolactone (GVL) over Co/SiO2 catalyst proceeds in a complex reaction network, resulting in 2-methyltetrahydrofuran (2-MTHF) as the main product, and C4–C5 alcohol and alkane side-products. The catalyst was shown to contain Co0 sites and Lewis acid (Co2+ ion)/Lewis base (O2− ion) pair sites, active for hydrogenation/dehydrogenation and dehydration reactions, respectively. The initial reaction step was confirmed to be the hydrogenation of GVL to key intermediate 1,4-pentanediol (1,4-PD). Cyclodehydration of 1,4-PD led to the main product 2-MTHF, whereas its dehydration/hydrogenation gave 1-pentanol and 2-pentanol side-products, with about the same yield. In contrast, 2-pentanol was the favored alcohol product of 2-MTHF hydrogenolysis. 2-Butanol was formed by decarbonylation of 4-hydroxypentanal intermediate. The latter was the product of 1,4-PD dehydrogenation. Alkanes were formed from the alcohol side-products via dehydration/hydrogenation reactions.

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15

Sviderskiy, S. A., O. S. Dement'eva, M. I. Ivantsov, A. A. Grabchak, M. V. Kulikova, and A. L. Maksimov. "Hydrogenation of CO2 over Biochar-Supported Catalysts." Нефтехимия 63, no. 2 (April 15, 2023): 239–49. http://dx.doi.org/10.31857/s0028242123020089.

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The study investigates hydrogenation of CO2 over mono- and bimetallic catalysts supported on biochar. In this reaction, bimetallic iron–cobalt catalysts were shown to surpass monometallic iron and cobalt catalysts in terms of catalytic performance. The optimal combination of performance parameters was reached at an iron to cobalt ratio of 3 : 1. The composition and genesis of the active phase in the bimetallic Fe–Co catalyst were identified, and the CO2 hydrogenation mechanism was suggested for an iron-dominated bimetallic catalyst. Using biochar as a support was found to provide an active phase composition favorable for CO2 hydrogenation.

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16

Yang, Chengsheng, Rentao Mu, Guishuo Wang, Jimin Song, Hao Tian, Zhi-Jian Zhao, and Jinlong Gong. "Hydroxyl-mediated ethanol selectivity of CO2 hydrogenation." Chemical Science 10, no. 11 (2019): 3161–67. http://dx.doi.org/10.1039/c8sc05608k.

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17

Jurca, Bogdan, Lu Peng, Ana Primo, Alvaro Gordillo, Amarajothi Dhakshinamoorthy, Vasile I. Parvulescu, and Hermenegildo García. "Promotional Effects on the Catalytic Activity of Co-Fe Alloy Supported on Graphitic Carbon for CO2 Hydrogenation." Nanomaterials 12, no. 18 (September 16, 2022): 3220. http://dx.doi.org/10.3390/nano12183220.

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Starting from the reported activity of Co-Fe nanoparticles wrapped onto graphitic carbon (Co-Fe@C) as CO2 hydrogenation catalysts, the present article studies the influence of a series of metallic (Pd, Ce, Ca, Ca, and Ce) and non-metallic (S in various percentages and S and alkali metals) elements as Co-Fe@C promoters. Pd at 0.5 wt % somewhat enhances CO2 conversion and CH4 selectivity, probably due to H2 activation and spillover on Co-Fe. At similar concentrations, Ce does not influence CO2 conversion but does diminish CO selectivity. A 25 wt % Fe excess increases the Fe-Co particle size and has a detrimental effect due to this large particle size. The presence of 25 wt % of Ca increases the CO2 conversion and CH4 selectivity remarkably, the effect being attributable to the CO2 adsorption capacity and basicity of Ca. Sulfur at a concentration of 2.1% or higher acts as a strong poison, decreasing CO2 conversion and shifting selectivity to CO. The combination of S and alkali metals as promoters maintain the CO selectivity of S but notably increase the CO2 conversion. Overall, this study shows how promoters and poisons can alter the catalytic activity of Co/Fe@C catalysts, changing from CH4 to CO. It is expected that further modulation of the activity of Co/Fe@C catalysts can serve to drive the activity and selectivity of these materials to any CO2 hydrogenation products that are wanted.

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18

Wang, Jiaqi, Kaihong Liu, Jingjing Zhao, Xiuping Li, Bolin Yin, Bo Jiang, and Hexing Li. "Tuning the selectivity of the CO₂ hydrogenation reaction using boron-doped cobalt-based catalysts." RSC Advances 14, no. 10 (2024): 6502–7. http://dx.doi.org/10.1039/d3ra07488a.

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19

Dou, Maobin, Minhua Zhang, Yifei Chen, and Yingzhe Yu. "DFT study of In2O3-catalyzed methanol synthesis from CO2 and CO hydrogenation on the defective site." New Journal of Chemistry 42, no. 5 (2018): 3293–300. http://dx.doi.org/10.1039/c7nj04273f.

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20

Khajonvittayakul, Chalempol, Vut Tongnan, Suksun Amornraksa, Navadol Laosiripojana, Matthew Hartley, and Unalome Wetwatana Hartley. "CO2 Hydrogenation to Synthetic Natural Gas over Ni, Fe and Co–Based CeO2–Cr2O3." Catalysts 11, no. 10 (September 26, 2021): 1159. http://dx.doi.org/10.3390/catal11101159.

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CO2 methanation was studied over monometallic catalyst, i.e., Ni, Fe and Co; on CeO2-Cr2O3 support. The catalysts were prepared using one-pot hydrolysis of mixed metal nitrates and ammonium carbonate. Physicochemical properties of the pre- and post-exposure catalysts were characterized by X-Ray Powder Diffraction (XRD), Hydrogen Temperature Programmed Reduction (H2-TPR), and Field Emission Scanning Electron Microscope (FE-SEM). The screening of three dopants over CeO2-Cr2O3 for CO2 methanation was conducted in a milli-packed bed reactor. Ni-based catalyst was proven to be the most effective catalyst among all. Thus, a group of NiO/CeO2-Cr2O3 catalysts with Ni loading was investigated further. 40 % NiO/CeO2-Cr2O3 exhibited the highest CO2 conversion of 97.67% and CH4 selectivity of 100% at 290 °C. The catalytic stability of NiO/CeO2-Cr2O3 was tested towards the CO2 methanation reaction over 50 h of time-on-stream experiment, showing a good stability in term of catalytic activity.

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21

Calizzi, Marco, Robin Mutschler, Nicola Patelli, Andrea Migliori, Kun Zhao, Luca Pasquini, and Andreas Züttel. "CO2 Hydrogenation over Unsupported Fe-Co Nanoalloy Catalysts." Nanomaterials 10, no. 7 (July 11, 2020): 1360. http://dx.doi.org/10.3390/nano10071360.

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The thermo-catalytic synthesis of hydrocarbons from CO2 and H2 is of great interest for the conversion of CO2 into valuable chemicals and fuels. In this work, we aim to contribute to the fundamental understanding of the effect of alloying on the reaction yield and selectivity to a specific product. For this purpose, Fe-Co alloy nanoparticles (nanoalloys) with 30, 50 and 76 wt% Co content are synthesized via the Inert Gas Condensation method. The nanoalloys show a uniform composition and a size distribution between 10 and 25 nm, determined by means of X-ray diffraction and electron microscopy. The catalytic activity for CO2 hydrogenation is investigated in a plug flow reactor coupled with a mass spectrometer, carrying out the reaction as a function of temperature (393–823 K) at ambient pressure. The Fe-Co nanoalloys prove to be more active and more selective to CO than elemental Fe and Co nanoparticles prepared by the same method. Furthermore, the Fe-Co nanoalloys catalyze the formation of C2-C5 hydrocarbon products, while Co and Fe nanoparticles yield only CH4 and CO, respectively. We explain this synergistic effect by the simultaneous variation in CO2 binding energy and decomposition barrier as the Fe/Co ratio in the nanoalloy changes. With increasing Fe content, increased activation temperatures for the formation of CH4 (from 440 K to 560 K) and C2-C5 hydrocarbons (from 460 K to 560 K) are observed.

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22

Seuser, Grant, Raechel Staffel, Yagmur Hocaoglu, Gabriel F. Upton, Elijah S. Garcia, Donald C. Cronauer, A. Jeremy Kropf, Michela Martinelli, and Gary Jacobs. "CO2 Hydrogenation: Na Doping Promotes CO and Hydrocarbon Formation over Ru/m-ZrO2 at Elevated Pressures in Gas Phase Media." Nanomaterials 13, no. 7 (March 24, 2023): 1155. http://dx.doi.org/10.3390/nano13071155.

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Sodium-promoted monoclinic zirconia supported ruthenium catalysts were tested for CO2 hydrogenation at 20 bar and a H2:CO2 ratio of 3:1. Although increasing sodium promotion, from 2.5% to 5% by weight, slightly decreased CO2 conversion (14% to 10%), it doubled the selectivity to both CO (~36% to ~71%) and chain growth products (~4% to ~8%) remarkably and reduced the methane selectivity by two-thirds (~60% to ~21%). For CO2 hydrogenation during in situ DRIFTS under atmospheric pressure, it was revealed that Na increases the catalyst basicity and suppresses the reactivity of Ru sites. Higher basicity facilitates CO2 adsorption, weakens the C–H bond of the formate intermediate promoting CO formation, and inhibits methanation occurring on ruthenium nanoparticle surfaces. The suppression of excessive hydrogenation increases the chain growth probability. Decelerated reduction during H2-TPR/TPR-MS and H2-TPR-EXAFS/XANES at the K-edge of ruthenium indicates that sodium is in contact with ruthenium. A comparison of the XANES spectra of unpromoted and Na-promoted catalysts after H2 reduction showed no evidence of a promoting effect involving electron charge transfer.

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23

Yang, Zhen-Zhen, Hongye Zhang, Bo Yu, Yanfei Zhao, Guipeng Ji, and Zhimin Liu. "A Tröger's base-derived microporous organic polymer: design and applications in CO2/H2 capture and hydrogenation of CO2 to formic acid." Chemical Communications 51, no. 7 (2015): 1271–74. http://dx.doi.org/10.1039/c4cc08295h.

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24

Nasriddinov, Khasan, Ji-Eun Min, Hae-Gu Park, Seung Ju Han, Jingyu Chen, Ki-Won Jun, and Seok Ki Kim. "Effect of Co, Cu, and Zn on FeAlK catalysts in CO₂ hydrogenation to C₅₊ hydrocarbons." Catalysis Science & Technology 12, no. 3 (2022): 906–15. http://dx.doi.org/10.1039/d1cy01980e.

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25

Lushchikova, Olga V., Máté Szalay, Hossein Tahmasbi, Ludo B. F. Juurlink, Jörg Meyer, Tibor Höltzl, and Joost M. Bakker. "IR spectroscopic characterization of the co-adsorption of CO₂ and H₂ onto cationic Cu_n⁺ clusters." Physical Chemistry Chemical Physics 23, no. 47 (2021): 26661–73. http://dx.doi.org/10.1039/d1cp03119h.

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26

Chen, Yun, Jinzhao Liu, Xinyu Chen, Siyao Gu, Yibin Wei, Lei Wang, Hui Wan, and Guofeng Guan. "Development of Multifunctional Catalysts for the Direct Hydrogenation of Carbon Dioxide to Higher Alcohols." Molecules 29, no. 11 (June 4, 2024): 2666. http://dx.doi.org/10.3390/molecules29112666.

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The direct hydrogenation of greenhouse gas CO2 to higher alcohols (C2+OH) provides a new route for the production of high-value chemicals. Due to the difficulty of C-C coupling, the formation of higher alcohols is more difficult compared to that of other compounds. In this review, we summarize recent advances in the development of multifunctional catalysts, including noble metal catalysts, Co-based catalysts, Cu-based catalysts, Fe-based catalysts, and tandem catalysts for the direct hydrogenation of CO2 to higher alcohols. Possible reaction mechanisms are discussed based on the structure–activity relationship of the catalysts. The reaction-coupling strategy holds great potential to regulate the reaction network. The effects of the reaction conditions on CO2 hydrogenation are also analyzed. Finally, we discuss the challenges and potential opportunities for the further development of direct CO2 hydrogenation to higher alcohols.

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27

Li, Yanbing, Yingluo He, Kensei Fujihara, Chengwei Wang, Xu Sun, Weizhe Gao, Xiaoyu Guo, Shuhei Yasuda, Guohui Yang, and Noritatsu Tsubaki. "A Core-Shell Structured Na/Fe@Co Bimetallic Catalyst for Light-Hydrocarbon Synthesis from CO2 Hydrogenation." Catalysts 13, no. 7 (July 11, 2023): 1090. http://dx.doi.org/10.3390/catal13071090.

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The direct CO2 Fischer–Tropsch synthesis (CO2-FTS) process has been proven as one of the indispensable and effective routes in CO2 utilization and transformation. Herein, we present a core-shell structured Na/Fe@Co bimetallic catalyst to boost CO2 conversion and light hydrocarbon (C2 to C4) selectivity, as well as inhibit the selectivity of CO. Compared to the Na/Fe catalyst, our Na/Fe@CoCo-3 catalyst enabled 50.3% CO2 conversion, 40.1% selectivity of light hydrocarbons (C2-C4) in all hydrocarbon products and a high olefin-to-paraffin ratio (O/P) of 7.5 at 330 °C and 3.0 MPa. Through the characterization analyses, the introduction of CoCo Prussian Blue Analog (CoCo PBA) not only increased the reducibility of iron oxide (Fe2O3 to Fe3O4), accelerated the formation of iron carbide (FexCy), but also adjusted the surface basic properties of catalysts. Moreover, the trace Co atoms acted as a second active center in the CO2-FTS process for heightening light hydrocarbon synthesis from CO hydrogenation. This work provides a novel core-shell structured bimetallistic catalyst system for light hydrocarbons, especially light olefin production from CO2 hydrogenation.

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28

de Winter, Tamara M., Jaddie Ho, Christopher J. Alridge, and Philip G. Jessop. "CO₂-Assisted asymmetric hydrogenation of prochiral allylamines." RSC Advances 12, no. 11 (2022): 6755–61. http://dx.doi.org/10.1039/d2ra00263a.

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29

Jiang, Tao, Duy Le, Katerina L. Chagoya, David J. Nash, Richard G. Blair, and Talat S. Rahman. "Catalytic reduction of carbon dioxide to methanol over defect-laden hexagonal boron nitride: insights into reaction mechanisms." Journal of Physics: Condensed Matter 37, no. 13 (February 11, 2025): 135201. https://doi.org/10.1088/1361-648x/adad2b.

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Abstract We present a density functional theory-based mechanistic understanding of CO2 hydrogenation to value-added products on a nitrogen-vacancy (VN) defect in hexagonal boron nitride (dh-BN). Activation occurs through back-donation to the π* orbitals of CO2 from the frontier orbitals (defect state) of the h-BN sheet that are localized near a nitrogen-vacancy. Subsequent hydrogenation to methanol (CH3OH) and formic acid (HCOOH) proceed through vacancy-facilitated co-adsorption of hydrogen and CO2. More importantly, our reaction pathway analyses complimented by microkinetic modeling indicate that dh-BN is potentially a low-temperature, selective catalyst for CO2 reduction to methanol. Our findings are in agreement with experiments conducted in a mechanical reactor that show high selectivity towards methanol formation for CO2 hydrogenation on defect induced h-BN.

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Lu, Xiaoqing, Weili Wang, Shuxian Wei, Chen Guo, Yang Shao, Mingmin Zhang, Zhigang Deng, Houyu Zhu, and Wenyue Guo. "Initial reduction of CO2 on perfect and O-defective CeO2 (111) surfaces: towards CO or COOH?" RSC Advances 5, no. 118 (2015): 97528–35. http://dx.doi.org/10.1039/c5ra17825h.

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CO₂ hydrogenation towards COOH is more favorable on perfect CeO₂ (111) surface, whereas reductive dissociation of CO₂ is predominant on O-defective surface. The O vacancy promotes reductive dissociation of CO₂ on O-defective CeO₂ (111) surface.

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31

BROWNBOURZUTSCHKY, J. "Hydrogenation of CO2 and CO2/CO mixtures over copper-containing catalysts." Journal of Catalysis 124, no. 1 (July 1990): 73–85. http://dx.doi.org/10.1016/0021-9517(90)90104-r.

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32

Sh.F.Tagiyeva, Sh F. Tagiyeva. "HYDROGENATION OF CARBON DIOXIDE ON SIRAL ALUMINOSILICATES MODIFIED WITH COBALT AND PALLADIUM." Azerbaijan Journal of Chemical News 04, no. 01 (May 30, 2022): 81–86. http://dx.doi.org/10.32010/ajcn05012022-81.

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The reaction of hydrogenation of CO2 in flow mode at atmospheric pressure on Siral aluminosilicates with 1, 10, and 40 wt.% SiO2 and containing Co and Co-Pd has been studied. The synthesized catalysts were characterized by XRD and EPR spectroscopy. It has been established that on catalysts containing only cobalt, at a reaction temperature of ≤ 300oC, practically only methane is formed, and at a reaction temperature of T ≥ 300oC, methane and no more than 1% CO are formed. It is shown that with an increase in the SiO2/Al2O3 ratio, a decrease in the methane yield is observed. The introduction of palladium into the composition of the Co/Siral catalyst stimulates the formation of methanol, the yield of which increases with an increase in the reaction temperature and reaches its maximum value at a reaction temperature of 500°C for the Co,Pd/Siral-10 catalyst. The mechanism of the reaction of CO2 hydrogenation to methanol and the role of palladium in this reaction are discussed. Keywords: carbon dioxide, hydrogenation, methane, methanol, Siral, Pd, Co.

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33

Seo, Boseok, Eun Hee Ko, Jinho Boo, Minkyu Kim, Dohyung Kang, and No-Kuk Park. "CO2 Hydrogenation on NixMg1−xAl2O4: A Comparative Study of MgAl2O4 and NiAl2O4." Catalysts 11, no. 9 (August 24, 2021): 1026. http://dx.doi.org/10.3390/catal11091026.

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Due to the increasing attention focused on global warming, many studies on reducing CO2 emissions and developing sustainable energy strategies have recently been performed. One of the approaches is CO2 methanation, transforming CO2 into methane. Such transformation (CO2 + 4H2 → CH4 + 2H2O) provides advantages of carbon liquification, storage, etc. In this study, we investigated CO2 methanation on nickel–magnesium–alumina catalysts both experimentally and computationally. We synthesized the catalysts using a precipitation method, and performed X-ray diffraction, temperature-programmed reduction, and N2 adsorption–desorption tests to characterize their physical and chemical properties. NiAl2O4 and MgAl2O4 phases were clearly observed in the catalysts. In addition, we conducted CO2 hydrogenation experiments by varying with temperatures to understand the reaction. Our results showed that CO2 conversion increases with Ni concentration and that MgAl2O4 exhibits high selectivity for CO. Density functional theory calculations explained the origin of this selectivity. Simulations predicted that adsorbed CO on MgAl2O4(100) weakly binds to the surface and prefers to desorb from the surface than undergoing further hydrogenation. Electronic structure analysis showed that the absence of a d orbital in MgAl2O4(100) is responsible for the weak binding of CO to MgAl2O4. We believe that this finding regarding the origin of the CO selectivity of MgAl2O4 provides fundamental insight for the design methanation catalysts.

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Frontera, Patrizia, Anastasia Macario, Angela Malara, Vincenza Modafferi, Maria Cristina Mascolo, Sebastiano Candamano, Fortunato Crea, and Pierluigi Antonucci. "CO2 and CO hydrogenation over Ni-supported materials." Functional Materials Letters 11, no. 05 (October 2018): 1850061. http://dx.doi.org/10.1142/s1793604718500613.

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This work reports on the fundamental properties of nanostructured catalysts active in the main carbon oxides’ conversion processes for sustainable energy supply: methanation and co-methanation of CO2. Transition metals (e.g. Ni, Pd, Pt, Co, Ru, Rh) are active species in both reactions. Ni has been the most studied because of its cheapness. Monometallic and bi-metallic Ni and Ni3Fe catalysts supported on Gadolinia-doped ceria (GDC) have been synthesized, characterized and tested in the temperature range 200–600[Formula: see text]C. In the methanation reaction, the monometallic catalyst showed higher performance with respect to the bi-metallic catalyst. At 400[Formula: see text]C, the CO2 conversion overcomes 90% with CH4 selectivity of 100%. In co-methanation, the highest CO2, CO and H2 conversion values over monometallic Ni/GDC catalyst were obtained at 300[Formula: see text]C; at higher temperatures, conversion decreases. The GDC support plays a pivotal role in both reactions, enhancing the basicity of the catalyst and improving the dissociation of carbon oxide species adsorbed on Ni sites.

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35

Baussart, Hervé, René Delobel, Michel Le Bras, and Jean-Marie Leroy. "Hydrogenation of CO2 over Co/Cu/K catalysts." Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases 83, no. 6 (1987): 1711. http://dx.doi.org/10.1039/f19878301711.

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36

Sun, Yanyang, Linfei Xiao, and Wei Wu. "In Situ Carbon-Confined MoSe2 Catalyst with Heterojunction for Highly Selective CO2 Hydrogenation to Methanol." Molecules 29, no. 10 (May 8, 2024): 2186. http://dx.doi.org/10.3390/molecules29102186.

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The synthesis of methanol from CO2 hydrogenation is an effective measure to deal with global climate change and an important route for the chemical fixation of CO2. In this work, carbon-confined MoSe2 (MoSe2@C) catalysts were prepared by in situ pyrolysis using glucose as a carbon source. The physico-chemical properties and catalytic performance of CO2 hydrogenation to yield methanol were compared with MoSe2 and MoSe2/C. The results of the structure characterization showed MoSe2 displayed few layers and a small particle size. Owing to the synergistic effect of the Mo2C-MoSe2 heterojunction and in situ carbon doping, MoSe2@C with a suitable C/Mo mole ratio in the precursor showed excellent catalytic performance in the synthesis of methanol from CO2 hydrogenation. Under the optimal catalyst MoSe2@C-55, the selectivity of methanol reached 93.7% at a 9.7% conversion of CO2 under optimized reaction conditions, and its catalytic performance was maintained without deactivation during a continuous reaction of 100 h. In situ diffuse infrared Fourier transform spectroscopy studies suggested that formate and CO were the key intermediates in CO2 hydrogenation to methanol.

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37

Li, Shang Gui, Hai Jun Guo, Hai Rong Zhang, Jun Luo, Lian Xiong, Cai Rong Luo, and Xin De Chen. "The Reverse Water-Gas Shift Reaction and the Synthesis of Mixed Alcohols over K/Cu-Zn Catalyst from CO₂ Hydrogenation." Advanced Materials Research 772 (September 2013): 275–80. http://dx.doi.org/10.4028/www.scientific.net/amr.772.275.

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The K/Cu-Zn catalyst has been synthesized by the co-precipitation method coupling with impregnation method and the catalytic performances for the reverse water gas shift (RWGS) reaction and mixed alcohols synthesis from CO2 hydrogenation have been investigated. The catalytic activity and product distribution depend strongly on reaction temperature, pressure, space velocity and the molar ratio of H2/CO2. These results indicated that the optimal conditions for CO2 hydrogenation over K/Cu-Zn catalyst were as follows: 350 K, 6.0 MPa, 5000 h-1 and H2/CO2 = 3.0, under which the selectivity of CO and mixed alcohols reach 84.27 wt% and 7.56 wt%, respectively. The outstanding performances for RWGS reaction and mixed alcohols synthesis of K/Cu-Zn catalyst can be due to the well dispersion of Cu active component.

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38

Portillo, Ander, Onintze Parra, Andrés T. Aguayo, Javier Ereña, Javier Bilbao, and Ainara Ateka. "Setting up In2O3-ZrO2/SAPO-34 Catalyst for Improving Olefin Production via Hydrogenation of CO2/CO Mixtures." Catalysts 13, no. 7 (July 14, 2023): 1101. http://dx.doi.org/10.3390/catal13071101.

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The adequate configuration and the effect of the reduction was studied for the In2O3-ZrO2/SAPO-34 catalyst with the aim of improving its performance (activity and selectivity in the pseudo-steady state) for the hydrogenation of CO, CO2 and CO2/CO (COx) mixtures into olefins. The experiments were carried out in a packed bed reactor at 400 °C; 30 bar; a H2/COx ratio of 3; CO2/COx ratios of 0, 0.5 and 1; a space time (referred to as In2O3-ZrO2 catalyst mass) of 3.35 gInZr h molC−1; and a time on stream up to 24 h. The mixture of individual catalyst particles, with an SAPO-34 to In2O3-ZrO2 mass ratio of 1/2, led to a better performance than hybrid catalysts prepared via pelletizing and better than the arrangement of individual catalysts in a dual bed. The deactivation of the catalyst using coke deposition and the remnant activity in the pseudo-steady state of the catalyst were dependent on the CO2 content in the feed since the synergy of the capabilities of the SAPO-34 catalyst to form coke and of the In2O3-ZrO2 catalyst to hydrogenate its precursors were affected. The partial reduction of the In2O3-ZrO2/SAPO-34 catalyst (corresponding to a superficial In0/In2O3 ratio of 0.04) improved its performance over the untreated and fully reduced catalyst in the hydrogenation of CO to olefins, but barely affected CO2/CO mixtures’ hydrogenation.

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Xie, Fengqiong, Shiyu Xu, Lidan Deng, Hongmei Xie, and Guilin Zhou. "CO2 hydrogenation on Co/CeO2-δ catalyst: Morphology effect from CeO2 support." International Journal of Hydrogen Energy 45, no. 51 (October 2020): 26938–52. http://dx.doi.org/10.1016/j.ijhydene.2020.05.260.

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40

Chuang, Steven S. C., Mark A. Brundage, Michael W. Balakos, and Girish Srinivas. "Transient in Situ Infrared Methods for Investigation of Adsorbates in Catalysis." Applied Spectroscopy 49, no. 8 (August 1995): 1151–63. http://dx.doi.org/10.1366/0003702953964994.

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This paper reports the details of a high-pressure and -temperature in situ transmission infrared reactor cell and experimental approaches for investigation of the nature of adsorbates in CO hydrogenation and NO-CO reaction on Rh/SiO2 catalyst. The infrared cell used in this study allows easy assembling and reliable operation up to 773 K and 6.0 MPa. The structure and coverage of adsorbates during reaction are determined by an infrared spectrometer, and the composition of gaseous effluent from the infrared cell is monitored by a mass spectrometer. The steady-state 13CO step transient shows that gaseous CO rapidly exchanges with adsorbed CO, which is slowly converted to CH4 during CO hydrogenation at 513 K and 0.1 MPa. The pulsing CO study reveals that linear CO is more reactive than bridged CO during methane and CO2 formation, and bridged CO sites are blocked from CO disproportionation. Steady-state 13CO pulse transients show that the CO2 response leads the CO response, and Rh-NCO and Si-NCO are not involved in the formation of CO2 from CO during NO-CO reaction. The advantages and limitations of the in situ infrared and transient approaches for catalysis research will be discussed.

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41

Shan, Xuekai, Guolin Zhang, Ying Zhang, Shuobo Zhang, Fang Guo, and Qi Xu. "Photothermal CO2 Hydrogenation to Methanol over Ni-In2O3/g-C3N4 Heterojunction Catalysts." Catalysts 14, no. 11 (October 26, 2024): 756. http://dx.doi.org/10.3390/catal14110756.

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Selective CO2 hydrogenation faces significant technical challenges, although many efforts have been made in this regard. Herein, a Ni-doped In2O3 catalyst supported by g-C3N4 was prepared using the co-precipitation method, and its composition, morphology, specific surface area, and band gap were characterized using TEM, XPS, BET, XRD, CO2-TPD, H2-TPR, UV-Vis, etc. The catalytic hydrogenation reduction of CO2 to produce methanol was tested. Under low-photothermal conditions (1.0 MPa), the hydrogenation of carbon dioxide to methanol is stable, effective, and highly selective, with a spatiotemporal yield of 86.0 gMeOHh−1 kgcat−1, which is 30.9% higher than that of Ni-In2O3 without g-C3N4 loading under the same conditions.

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42

Mandal, Shyama Charan, Kuber Singh Rawat, Surajit Nandi, and Biswarup Pathak. "Theoretical insights into CO2 hydrogenation to methanol by a Mn–PNP complex." Catalysis Science & Technology 9, no. 8 (2019): 1867–78. http://dx.doi.org/10.1039/c9cy00114j.

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43

Qu, Ya Kun, Xiao Guang Zhao, Li Xin Wang, and Yu Wu. "Na₂O Promotion on CO₂ Hydrogenation on the χ-Fe₅C₂(2 0 0) Surface." Key Engineering Materials 872 (January 2021): 85–89. http://dx.doi.org/10.4028/www.scientific.net/kem.872.85.

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Understanding the origin of the high activity of Na2O promotion on the χ-Fe5C2(2 0 0) surface during CO2 hydrogenation is imperative. In this work, we revealed how Na2O promoted the catalytic performance of χ-Fe5C2 during CO2 hydrogenation. Detailed analyses confirmed that Na2O addition facilitated the adsorption of CO2 and promoted the desorption of product (C2H4). Electronic structure calculations suggested that the electron donating ability of Na could enhance the dissociation of CO2, which is essential for producing hydrocarbons from CO2.

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44

Qu, Ya Kun, Xiao Guang Zhao, Li Xin Wang, and Yu Wu. "Na₂O Promotion on CO₂ Hydrogenation on the χ-Fe₅C₂(2 0 0) Surface." Key Engineering Materials 872 (January 2021): 85–89. http://dx.doi.org/10.4028/www.scientific.net/kem.872.85.

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Understanding the origin of the high activity of Na2O promotion on the χ-Fe5C2(2 0 0) surface during CO2 hydrogenation is imperative. In this work, we revealed how Na2O promoted the catalytic performance of χ-Fe5C2 during CO2 hydrogenation. Detailed analyses confirmed that Na2O addition facilitated the adsorption of CO2 and promoted the desorption of product (C2H4). Electronic structure calculations suggested that the electron donating ability of Na could enhance the dissociation of CO2, which is essential for producing hydrocarbons from CO2.

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45

Geri, Jacob B., Joanna L. Ciatti, and Nathaniel K. Szymczak. "Charge effects regulate reversible CO2 reduction catalysis." Chemical Communications 54, no. 56 (2018): 7790–93. http://dx.doi.org/10.1039/c8cc04370a.

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Modular but geometrically constrained ligands were used to investigate the impact of key ligand design parameters (charge and bite angle) on CO₂ hydrogenation and formic acid dehydrogenation activity.

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46

Bahruji, Hasliza, Mshaal Almalki, and Norli Abdullah. "Highly Selective Au/ZnO via Colloidal Deposition for CO2 Hydrogenation to Methanol: Evidence of AuZn Role." Bulletin of Chemical Reaction Engineering & Catalysis 16, no. 1 (January 19, 2021): 44–51. http://dx.doi.org/10.9767/bcrec.16.1.9375.44-51.

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Gold, Au nanoparticles were deposited on ZnO, Al2O3, and Ga2O3 via colloidal method in order to investigate the role of support for CO2 hydrogenation to methanol. Au/ZnO was also produced using impregnation method to investigate the effect of colloidal method to improve methanol selectivity. Au/ZnO produced via sol immobilization showed high selectivity towards methanol meanwhile impregnation method produced Au/ZnO catalyst with high selectivity towards CO. The CO2 conversion was also influenced by the amount of Au weight loading. Au nanoparticles with average diameter of 3.5 nm exhibited 4% of CO2 conversion with 72% of methanol selectivity at 250 °C and 20 bar. The formation of AuZn alloy was identified as active sites for selective CO2 hydrogenation to methanol. Segregation of Zn from ZnO to form AuZn alloy increased the number of surface oxygen vacancy for CO2 adsorption to form formate intermediates. The formate was stabilized on AuZn alloy for further hydrogenation to form methanol. The use of Al2O3 and Ga2O3 inhibited the formation of Au alloy, and therefore reduced methanol production. Au/Al2O3 showed 77% selectivity to methane, meanwhile Au/Ga2O3 produced 100% selectivity towards CO. Copyright © 2021 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

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Jiang, Feng, Yu Yang, Li Wang, Yufeng Li, Zhihao Fang, Yuebing Xu, Bing Liu, and Xiaohao Liu. "Dependence of copper particle size and interface on methanol and CO formation in CO₂ hydrogenation over Cu@ZnO catalysts." Catalysis Science & Technology 12, no. 2 (2022): 551–64. http://dx.doi.org/10.1039/d1cy01836a.

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48

Xi, Yongjie, Tingting Wang, Jia Wang, Jinlei Li, and Fuwei Li. "Essential role of CO coverage in CO₂ hydrogenation over Pt(111)." Catalysis Science & Technology, 2023. http://dx.doi.org/10.1039/d3cy01134h.

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Hydrogenation of CO2 to ethanol is a promising process among various CO2 valorization processes. However, this process is challenging due to the difficulty of steering the hydrogenation reaction towards C–C...

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49

Men, Yu‐Long, Peng Liu, Dang‐Guo Cheng, Chong Peng, Yiyi Zhao, and Yun‐Xiang Pan. "Enhanced selective hydrogenation of CO₂ to CH₄ on molybdenum carbide hollow sphere catalyst." AIChE Journal, August 2, 2024. http://dx.doi.org/10.1002/aic.18555.

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AbstractHerein, methane (CH4) production in carbon dioxide (CO2) hydrogenation by hydrogen (H2) is enhanced by reducing surface carbon deposits on molybdenum carbide (Mo2C) hollow spheres. When surface carbon deposits present on Mo2C hollow spheres, CO2 conversion is 9.9%, and CO and CH4 are both produced from CO2 hydrogenation, with CO and CH4 selectivity of 58.4% and 41.6%, respectively. When surface carbon deposits absent on Mo2C hollow spheres, CO2 conversion increases to 18.6%, and CO2 hydrogenation to CH4 is enhanced, with a 100% CH4 selectivity. Reducing surface carbon deposits on Mo2C hollow spheres changes the CO2 adsorbed on Mo2C hollow spheres from a monodentate structure to a bidentate structure which prefers to undergo hydrogenation to CH4, thus enhancing CH4 formation from CO2 hydrogenation. These results open a new way to fabricate more efficient noble‐metal‐free catalysts for selective CO2 hydrogenation.

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Cui, Aixin, Man Wu, Tuo Guo, Xiunan Sun, Yulong Chen, and Qingjie Guo. "Potassium-modified calcium-ferrate-catalyzed hydrogenation of carbon dioxide to produce light olefins." New Journal of Chemistry, 2024. http://dx.doi.org/10.1039/d4nj01579g.

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