APPLIED CATALYSIS A-GENERAL
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2018
·
IF 4.521
Pengjing Chen,Guofeng Zhao,Ye Liu,Yong Lu
A series of Ni 5 Ga 3 / m -SiO 2 /Al 2 O 3 /Al-fiber ( m = 0, 0.5, 1.0, 3.0 and 5.0 wt%) catalysts have been developed for CO 2 hydrogenation to methanol at ambient pressure. Microfibrous-structured SiO 2 /Al 2 O 3 /Al-fiber supports are obtained though endogenous growth of free-standing boehmite (AlOOH) nanosheets onto a three-dimensional (3D) network of 60 μm-Al-fiber thin felt with the aid of steam-only hydrothermal oxidation reaction between Al metal and H 2 O (2 Al + 4H 2 O → 2 AlOOH + 3H 2 ), followed by calcination and SiO 2 -modification using silica sol. The bimetallic Ni 5 Ga 3 nanoparticles are then placed onto the pore surface of as-obtained SiO 2 /Al 2 O 3 /Al-fiber support by co-impregnation method using Ni and Ga nitrates as precursors followed by reduction in H 2 at 630 °C. The promising Ni 5 Ga 3 /1-SiO 2 /Al 2 O 3 /Al-fiber catalyst is capable of converting 2.3% CO 2 into CH 3 OH with a high selectivity of 86.7% as well as 10.3%/3.0% selectivities to CO/CH 4 at 210 °C, for a feed of CO 2 /H 2 /N 2 (2/6/1, molar ratio). Such microfibrous-structured catalyst design combines the promising catalytic performance of Ni 5 Ga 3 with the enhanced heat transfer and high permeability of the Al 2 O 3 /Al-fiber support. The effect of SiO 2 loading on the formation of Ni 5 Ga 3 alloy nanoparticles is also discussed.
研究领域:
催化化学
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材料科学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Jun Mou,Xingqi Fan,Fei Liu,Xiaodan Wang,Tianxiang Zhao,Peng Chen,Ziwei Li,Chunliang Yang,Jianxin Cao
The direct conversion of CO 2 hydrogenation to lower olefins via methanol as an intermediate is of great significance, but challenges still remain. Herein, we present a binary Mn 2 O 3 -ZnO oxide, which is responsible for catalytic hydrogenation of CO 2 to methanol. After combination of Mn 2 O 3 -ZnO and SAPO-34 molecular sieve, the catalytic reaction displays a markable increase. CO 2 adsorption by alkaline nature, followed by oxygen vacancy activation and synergistic hydrogenation over the binary Mn 2 O 3 -ZnO oxide are the prerequisites for the tandem reaction. However, the tandem spacing between oxide and molecular sieve plays a crucial role, because the suitable intimacy can induce enhanced methanol formation as intermediate via tandem dynamics effect, causing an apparent limitation for reverse water gas shift reaction at high temperature. The optimum mass ratio of 3:1 for two phases demonstrates that more components of binary oxide are needed to improve the rate of CO 2 hydrogenation to methanol, aiming to balance the two-step tandem reaction. Finally, under conditions of 380 ℃, 3 MPa and 3600 mL/g cat /h, 20%Mn 2 O 3 -ZnO/SAPO-34 tandem catalyst is obtained by physical ball milling after 15 min, with excellent stability, sulfur tolerance and catalytic performance with CO 2 conversion at almost 30%, lower olefins selectivity of 80.2% (propylene/ethylene = 5.6:1), and single-pass yield of 10.7%.
研究领域:
催化化学
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能源化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
RSC Advances
·
2019
·Vol. 9
·期 24
·13696-13704
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IF 3.049
Hong Lei,Ruheng Zheng,Yeping Liu,Jiacheng Gao,Xiang Chen,Xiaoliang Feng
Hydrogenation of CO2 to chemicals is of great importance in the reduction of greenhouse gas emission. And the interaction and/or the boundary between Cu and ZnO played a crucial role in the performance of the Cu–ZnO catalyst for CO2 hydrogenation to methanol. In this work, cylindrical shaped ZnO was first synthesized via controlled hydrothermal precipitation of Zn(CO2CH3)2·2H2O, and Cu was further deposited on ZnO via in situ reduction in aqueous solution. Characterizations indicated that the crystallization degree of ZnO decreased with the increasing content of Cu, while the exposed surface area of Cu exhibited a volcano shaped curve. It was found that the cylindrical shaped ZnO combined Cu catalysts were active for the hydrogenation of CO2, and the space time yield of methanol reached 0.50 g-MeOH (g-cat h)−1 at H2/CO2 = 3, 240 °C, 3.0 MPa, and 0.54 mol (g-cat h)−1, but the methanol selectivity decreases with the reduction of the (002) polar plane of ZnO. The conversion of CO2 and methanol selectivity were discussed with the detected exposed Cu surface area and the number of oxygen vacancies.
研究领域:
化学工程
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催化科学
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产品关联
DOI
PubMed
高影响因子
NEW JOURNAL OF CHEMISTRY
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2024
·Vol. 48
·期 45
·19220-19228
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IF 2.7
Peng Lu,Qianwen Hu,Kui Wang,Shiyong Chen,Zongxiao Li,Xinjie Chen,Chuang Xing,Yanhong Wang,Ce Du
The efficient CO2 conversion to light olefins through hydrogenation is a feasible strategy to achieve carbon neutrality goals. Herein, a series of bimetallic Zn–Zr/supports are synthesized by a conventional impregnation method. We demonstrate that different supports endow catalysts with various specific surface areas, pore sizes, chemical adsorption performances, and acid densities. The effects of different support-loaded Zn–Zr coupled with SAPO-34 on CO2 hydrogenation to light olefins are investigated systematically. The CO2 conversion of Zn–Zr/Q10-SAPO-34, Zn–Zr/Q50-SAPO-34, Zn–Zr/γAl2O3-SAPO-34, Zn–Zr/MgO-SAPO-34 and Zn–Zr/S-1-SAPO-34 is 11.4%, 9.2%, 24.0%, 8.8%, and 16.2%, respectively, with corresponding light olefin selectivity of 39.0%, 28.1%, 30.4%, 4.8%, and 14.7%, respectively. Significantly, γAl2O3 is more conducive to CO2 conversion, while Q10 tends to produce light olefins. This work provides an effective reference for support selection in CO2 hydrogenation to light olefins.
研究领域:
化学工程
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL PHYSICS LETTERS
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2021
·
IF 2.328
Guanfeng Tian,Youqing Wu,Shiyong Wu,Sheng Huang,Jinsheng Gao
In 2 O 3 , MnO/In 2 O 3 , and MgO/In 2 O 3 catalysts are synthesized by the co-precipitation method and investigated for CO 2 hydrogenation to methanol. The introduction of Mn and Mg oxides dramatically enhances the CO 2 adsorption capacity of In 2 O 3 . The changing trend of methanol selectivity is consistent with the CO 2 adsorption capacity. MnO/In 2 O 3 and MgO/In 2 O 3 catalysts show higher methanol selectivity compared with that of In 2 O 3 .
研究领域:
催化
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化学工程
·
环境化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Sensen Zhou,Yueli Wen,Bin Wang,Maohong Fan,Lu Ren,Zheng Cui,Wei Huang,Jing Li,Jianping Guo
CO 2 hydrogenation to C 2+ OH is an effective way to diminish CO 2 emissions. Although challenges still exist in large-scale applications, CuFeZn catalysts attract extensive attention due to their low-cost. Herein, CuFeZn catalysts are modified by different amounts of K 3 PO 4 , (KP) 0.1 CuFeZn exhibits an excellent catalytic performance (total alcohols selectivity of 15.76 % at CO 2 conversion of 38.10 %, C 2+ OH/ROH fraction of 94.23 %, and C 2+ alcohols space–time-yield (STY) of 53.81 mg·mL −1 ·h −1 ). Combined with a series of characterization results, it is found that the effect of K 3 PO 4 is complex, and the proportion of Fe 2+ , Cu 0 and medium base shows perfect linear relation to STY of C 2+ OH. The significance level of the above three factors is in the following sequence: Cu 0 ＞Fe 2+ ＞medium base. The introduction of K 3 PO 4 decreases the proportion of Fe 2+ (active site for RWGS, the competitive reaction for C–C coupling) and increases the proportion of Cu + /(Cu + +Cu 0 ) (Cu + is the active site for C–C coupling) due to the synergistic effect of Cu 0 and Cu + , thereby improving the synthesis of C 2+ OH. Moreover, conversion of Fe 0 to Fe 3 C or Fe 3 O 4 plays negative roles in the stability of the catalysts.
研究领域:
化学工程
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of CO2 Utilization
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2018
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IF 5.503
Jianyang Wang,Anfeng Zhang,Xiao Jiang,Chunshan Song,Xinwen Guo
Although many researchers have reported CO 2 hydrogenation to various C1 chemicals, it is still challenging to directly and selectively convert CO 2 to C 2 -C 4 hydrocarbons in terms of overcoming the extreme inertness of CO 2 and a high C C coupling barrier. In the present work, we report an efficient integration of methanol-synthesis and the methanol-to-hydrocarbons with the bifunctional catalyst component of In 2 O 3 -ZrO 2 and SAPO-5. These tandem reactions exhibit an excellent relative selectivity of C 2 -C 4 (83%) with a suppressed CH 4 relative selectivity less than 3% at T = 300 °C. A detailed analysis indicates that the partially reduced indium oxide surface (In 2 O 3 -ZrO 2 ) can better activate CO 2 and promote the synthesis of methanol than In 2 O 3 alone, and C C coupling is subsequently manipulated within the confined acidic pores of SAPO-5 according to XRD, H 2 -TPR, CO 2 -TPD, SEM and TEM. Furthermore, the proximity of two components and the content of Si also play an important role in such outstanding selectivity to C 2 -C 4 . Our study paves a new path for the direct synthesis of lower hydrocarbons.
研究领域:
化学工程
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催化化学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2024
·
IF 13.3
Lixin Song,Guobin Liu,Zhenping Qu
CO 2 hydrogenation to methanol and/or dimethyl ether (DME) holds promise for mitigating greenhouse gas effects and addressing energy scarcity. However, the relationship between product selectivity and the collective nature of the catalysts remains ambiguous due to the intricate reaction network. Here, a series of Cu/Zn x Al y O z catalysts with different surface properties have been engineered by manipulating the Zn/Al ratio to achieve product controllability for CO 2 hydrogenation. The results unveil the pivotal role of the H 2 dissociation capability in governing CO 2 conversion, which is regulated by the concentration of Cu 0 species. Furthermore, the number of surface hydroxyl groups, the proportion of moderately strong basic sites and moderately strong acidic sites show desirable linear correlations with the selectivity of CO, CH 3 OH, and DME, respectively. Importantly, the ZnAl 2 O 4 -Al 2 O 3 or Cu-ZnAl 2 O 4 -Al 2 O 3 interface notably enhances moderately strong acidic sites, aiding methanol dehydration to DME. This work offers a comprehensive guide to the rational design of catalysts for oriented product synthesis from CO 2 hydrogenation.
研究领域:
催化化学
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能源化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2024
·
IF 8.1
Wei Zhou,Mazhar Ahmed Memon,Mengmeng Niu,Xinqiang Fan,Yanan Jiang,Xian Zhang,Yuan Liu
Copper (Cu) based catalysts are frequently used in CO 2 hydrogenation, particularly in reverse water-gas shift (rWGS) and CO 2 -to-methanol reaction. Cu 0 and Cu + are the key species affecting the catalyst performance and product distribution . Therefore, constructing and adjusting Cu 0 /Cu + active pairs is significant for the catalyst design . In this study, Cu 0 /Cu + active pairs are obtained by utilizing the properties of perovskite-type oxides (PTOs). A series of CaTi 1-x Cu x O 3 and Ca 0.8 La 0.2 Ti 1-x Cu x O 3 (x = 0.05, 0.10, 0.15, 0.30, 0.40 and 0.50) were synthesized via citric acid complexing method and part of the Cu species entered the PTOs lattice. After reduction, large Cu particles and highly-dispersed Cu clusters were obtained simultaneously. The dispersed Cu clusters have more interfaces with the PTOs and provide abundant Cu + while large Cu particles tend to aggregate and supply mainly Cu 0 . Cu 0 activates H 2 and CO 2 and plays a vital role in the rWGS reaction . Cu + is the active site for methanol synthesis and it can strongly absorb CO. The ratio of Cu 0 /Cu + varies with different Cu content and doping La can also adjust the chemical state of surface Cu. The performance test demonstrates that both excessively high and low Cu 0 /Cu + ratios are beneficial for CO generation, while a moderate ratio is suitable for methanol synthesis . These insights provide a method for regulating the chemical state of surface metal species and help the catalyst design for CO 2 hydrogenation.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Nano Materials
·
2025
·
IF 5.5
Juanjuan Yang,Dandan Shao
CO2 to methanol is considered a promising method for CO2 conversion and utilization, yet achieving desirable selectivity remains a significant challenge. Herein, efficient CO2 hydrogenation to methanol is achieved by synthesizing Co0.7ZnO with abundant oxygen vacancies (Ov) through the incorporation of a portion of Co into nanoscale ZnO. By tuning the molar ratio of Co/(Co+Zn) in CoxZnO to increase the Ov content to 71%, CO2 adsorption and activation to form formate (COOH*) are enhanced, thereby reducing the CO selectivity. The efficiency of the hydrogenation of CO2 to methanol was optimized with Co0.7ZnO, which exhibited an impressive methanol formation rate of 2.1 mmol/(g h) and a selectivity of up to 96.7%. The unique structure of incorporating partial Co into nanoscale ZnO to increase the level of Ov not only reduces the level of CO selectivity but also inhibits methane formation, thereby contributing to the high methanol selectivity. This study presents an innovative strategic design through partial doping, which is essential for controlling the selectivity of target products in the CO2 hydrogenation.
研究领域:
化学工程
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2020
·
IF 12.35
Feng Jiang,Shanshan Wang,Bing Liu,Jie Liu,Li Wang,Yang Xiao,Yuebing Xu,Xiaohao Liu
CeO2 is an excellent potential material for CO2 hydrogenation attributed to the highly tunable properties including metal–support interaction and abundant oxygen vacancy. In this work, four CeO2 supports with structurally well-defined different shapes and crystal facets are hydrothermally prepared, and their effects on the composition of Pd species and oxygen vacancy over Pd/CeO2 catalysts have been intensively investigated in the reduction of CO2 to methanol. The 2Pd/CeO2-R (rods) shows the highest concentration and number of oxygen vacancies, where the (110) facet with high surface oxygen mobility and low oxygen vacancy formation energy is exposed over the CeO2-R surface. The oxygen mobility at the interface of (111) and (100) facets mainly observed on 2Pd/CeO2-P (polyhedrons) is higher than the single (111) and (100) facets mainly observed on 2Pd/CeO2-O (octahedrons) and 2Pd/CeO2-C (cubs), respectively. The presence of Pd highly promotes the formation of oxygen vacancies by providing dissociated H atoms to facilitate the removal of surface O in ceria support under a H2 atmosphere. Both the PdxCe1–xOδ solid solution dominated on CeO2-R and the PdO species dominated on CeO2-O are reduced to metallic Pd after reduction with 6–10 nm average particle size. As revealed by density functional theory (DFT) calculations, in contrast to the single Pd0 atom on CeO2 and the thermodynamically most unstable PdxCe1−xOδ solid solution, the Pd0 nanoparticles are the most stable species under the realistic reaction conditions. The 2Pd/CeO2-R shows the highest catalytic activity as the abundantly available oxygen vacancies function as CO2 adsorption and activation sites. Moreover, oxygen vacancy reactivity is correlated with its formation energy. The lower formation energy facilitates the formation of oxygen vacancy; however, the reactivity of each oxygen vacancy is lower as the TOFoxygen vacancy of 2Pd/CeO2-O is 15 times as that of 2Pd/CeO2-R. Thus, a suitable oxygen vacancy formation energy is likely favorable for enhancing CO2 reactivity. DFT calculations indicate that the CH3OH formation is most probably from the formate (HCOO*) pathway via the C–O bond cleavage in H2COOH*, with the reduction of HCOO* to HCOOH* as the rate-limiting step. These results would provide experimental and theoretical insights into the rational design of an effective catalyst for CO2 hydrogenation.
研究领域:
催化化学
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材料科学
·
理论计算
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS TODAY
·
2020
·
IF 5.825
Junhui Liu,Guanghui Zhang,Xiao Jiang,Junhu Wang,Chunshan Song,Xinwen Guo
Iron-based catalysts have been widely used to synthesize value-added hydrocarbons through CO 2 hydrogenation. Fe carbide, Fe 5 C 2 , was proposed as the active phase responsible for C C coupling during the chain growth. However, the reaction mechanism over iron-based catalysts is still under debate due to the presence of multiple phases of Fe species. In this work, Fe 5 C 2 and K-modified Fe 5 C 2 were prepared and used to study the relationship between the Fe phase, catalytic performance and reaction pathways. CH 4 and CO selectivities of 46.1 C-mol% and 2.8 C-mol% were obtained on Fe 5 C 2 at a CO 2 conversion of 49.8 %, with the main hydrocarbon products being alkanes. With the addition of the promoter K, the C 2 -C 4 = selectivity increased to above 38.0 C-mol%, and the selectivity to C 5+ hydrocarbons increased to 23.9 C-mol% at a similar CO 2 conversion. CH 4 and C 2+ hydrocarbons formed through the CO 2 →CO→hydrocarbons (indirect) route over K-modified Fe 5 C 2 , whereas the direct hydrogenation route occurred on unmodified Fe 5 C 2 in addition to the indirect route of CO 2 to CO to hydrocarbons through Fischer-Tropsch synthesis (FTS) processes. This work offers insights in direct CO 2 hydrogenation over Fe 5 C 2 and Fe 3 O 4 -Fe 5 C 2 catalysts, which advances the understanding of the functions of active phases and reaction pathways of CO 2 hydrogenation over iron-based catalysts.
研究领域:
化学工程
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）