ACS Catalysis
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2016
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IF 9.307
Jie Sun,Qiuxia Cai,Yan Wan,Shaolong Wan,Li Wang,Jingdong Lin,Donghai Mei,Yong Wang
The promotional effects of a cesium promoter on higher alcohol (C2+OH) synthesis from syngas over Cs2O-Cu/ZnO/Al2O3 catalysts were investigated using a combined experimental and density functional theory (DFT) calculation method. In the presence of a cesium promoter, the C2+OH productivity increases from 77.1 to 157.3 g kgcat–1 h–1 at 583 K due to the enhancement of the initial C–C bond formation. A detailed analysis of chain growth probabilities (CGPs) confirms that initial C–C bond formation is the rate-determining step in the temperature range of 543–583 K. Addition of a cesium promoter significantly increases the productivities of 2-methyl-1-propanol, while the CGP values (C3* to 2-methyl-C3*) are almost unaffected. With the assistance of a cesium promoter, the CGPs of the initial C–C bond formation step (C1* to C2*) increase from 0.13 to 0.25 at 583 K. DFT calculations indicate that the initial C–C bond formation during syngas synthesis over the ZnCu(211) model surface is mainly due to the HCO + HCO coupling. In the presence of Cs2O, the stabilities of key intermediates such as HCO and H2CO are enhanced, which facilitates both HCO + HCO and HCO + H2CO coupling steps with lower activation barriers. In addition, Bader charge analysis suggests that the presence of cesium ions could facilitate nucleophilic coupling between HCO and H2CO for the initial C–C bond formation.
研究领域:
催化化学
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能源化学
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理论化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of CO2 Utilization
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2017
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IF 4.292
Chen Zhang,Haiyan Yang,Peng Gao,He Zhu,Liangshu Zhong,Hui Wang,Wei Wei,Yuhan Sun
A series of Cu/ZnO/Al 2 O 3 catalysts with the total weight percentage of Cu and ZnO from 9.94 wt.% to 44.5 wt.% have been prepared by ammonia deposition −precipitation method and tested for methanol synthesis from CO 2 hydrogenation. A Cu/Zn/Al layered double hydroxides (LDHs) precursor can be formed in situ on the surface of microspherical Al 2 O 3 which acts as both support and sole source of Al 3+ cations. With increase of total Cu and ZnO loading, the dispersion of copper and reducibility of CuO decline continuously, while the exposed copper surface area increases gradually. In addition, the formation of LDHs results in a stronger both basicity and acid strength on the catalyst surface. It is found that the CO 2 conversion increases linearly with increase of the Cu and ZnO loading. The methanol selectivity for the catalyst with low total metal loading (9.94 wt.%) is much lower than those for other catalysts, though it increases with increasing loading, which can be mainly assigned to the much smaller Cu particle size (<5 nm) and the higher ratio of isolated CuO phase. Moreover, the Cu/ZnO/Al 2 O 3 catalyst with relatively high total metal loading (44.50 wt.%) still exhibits a considerable stable catalytic performance due to the formation of LDH structure.
研究领域:
催化
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化学工程
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材料科学
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环境化学
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产品关联
DOI
高影响因子
Journal of the Taiwan Institute of Chemical Engineers
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2026
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IF 6.9
Abrar Hussain,Ndumiso Vukile Mdlovu,Kuen-Song Lin,Chi-Jung Chang,Amin Hussain
Background The conversion of CO 2 into value-added fuels and chemicals remains one of the major challenges in catalysis and sustainable energy research. Developing efficient catalysts for CO₂ hydrogenation to methanol and dimethyl ether (DME) is essential for reducing greenhouse gas emissions and promoting carbon recycling. Methods In this work, a Zr-modified CuO–ZnO–Al₂O₃ (CZZA) catalyst was synthesized via a co-precipitation method for CO 2 hydrogenation. The catalyst systems “CZZA/HZSM-5-L” and “CZZA/com-HZSM-5” represent Zr-modified CZZA physically integrated with loofah-templated and commercial HZSM-5 (Si/Al = 25), respectively. A bio-HZSM-5 catalyst was also prepared using loofah sponge and rice husks as dual biotemplates to promote methanol dehydration into DME. The novelty lies in (i) the dual-biomass templating strategy (silica-rich rice husk vs. low-silica loofah) to achieve macro– meso –micro hierarchies while retaining MFI crystallinity, and (ii) Zr-promotion of the Cu–ZnO–Al₂O₃ matrix to enhance Cu⁺/Cu²⁺ and Cu–Zn interfacial sites, enabling efficient one-pass CO₂ → MeOH → DME conversion at 280 °C and 30 bar. Significant findings Zr incorporation significantly improved the structural and electronic properties of the CZZA catalyst, leading to enhanced surface area, active site dispersion, and CuO–ZnO interfacial synergy. Among all tested catalysts, the CZZA/HZSM-5-L bifunctional catalyst achieved the highest DME yield (13.2 %), DME selectivity (58.6 %), and CO₂ conversion (22.5 %) at 280 °C and 30 bar. An economic evaluation of 5- and 10-ton-per-day (TPD) DME production using refinery waste CO₂ showed payback periods of 2.98 and 2.44 years, respectively. Sensitivity analysis (±20 % variation in H 2 and DME prices) confirmed the payback remained below 4 years, demonstrating the technical and economic viability of the developed Power-to-DME process.
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DOI
高影响因子
Catalysts
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2023
·Vol. 13
·期 5
·800
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IF 3.9
Zhong Xie,Jinpei Hei,Lei Cheng,Jing Li,Xiaojie Yin,Sugang Meng
CO2hydrogenation to methanol was conducted using a set of activated carbon-supported Cu/ZnO/Al2O3catalysts (CCZA) prepared by an incipient wetness impregnation approach. The effect of the Cu/Al ratio on the physicochemical properties of the catalysts, as well as their catalytic performance, were investigated. As Cu/Al ratio increased, the metallic Cu surface area displayed a reducing trend from 6.88 to 4.18 m2∙gcat−1, while the CO2adsorption capacity exhibited an increasing trend. Meanwhile, aluminum content will have an important effect on the catalysts’ reducibility and, thus, on their catalytic performance. The CCZA-2.7-de catalyst demonstrated the highest selectivity to methanol at 83.75% due to the excellent distribution and synergistic effect of copper and zinc. Although the CO2conversion of CCZA-2.2-de and CCZA-3.5-de exceeded 10%, the CH3OH selectivity was less than 60%, which may be attributed to the larger particle sizes of ZnO and poor interactions in Cu–Zn. The present study offers a novel approach to increase the number of active sites, optimize the activated carbon-aided Cu/ZnO/Al2O3catalyst’s composition, and finally elucidate the mechanism for CO2hydrogenation to methanol.Keywords:CO2hydrogenation;CuO/ZnO/Al2O3catalyst;methanol synthesis;carbon-supported catalyst;thermocatalysis
研究领域:
催化
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化学工程
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环境科学
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DOI
高影响因子
Catalysis Science & Technology
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2020
·Vol. 10
·期 8
·2343-2352
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IF 5.721
Ziheng Zhen,Wenxiang Tang,Wei (Willy) Chu,Tao Zhang,Li Lv,Shengwei Tang
The dispersity and the neighboring degree of different sites play crucial roles in the catalytic performance of dual site catalysts. The solution of precursors was encapsulated into microdroplets by forming a microemulsion. The average diameter of microdroplets was about 45 nm. This guaranteed that the dosage of precursors was at the attogram level and only about a thousand precursor molecules were encapsulated in each microdroplet. An anti-solvent extraction method was applied to extract water from the microdroplets with acetonitrile. The precursors co-precipitated in the microdroplets due to the loss of water. The encapsulated precursors in the microdroplets co-precipitated together in nanoscale space, so the neighboring degree of the two precursors was improved significantly. The prepared catalyst was characterized by ICP-OES, BET, XRD, H2-TPR, TEM and XPS. Compared with the Cu–ZnO/Al2O3 (CZA) catalysts prepared by the conventional impregnation method, the CZA catalysts prepared by the proposed strategy had much stronger interaction and a better neighboring degree of the dual active sites. They also showed very good catalytic performance for the reverse water gas shift (RWGS) reaction. The CO2 conversion of the designed CZA catalysts was about 1–2 times higher than that of the CZA catalysts prepared by the conventional impregnation method at 0.1 MPa, 300–400 °C and a CO2/H2 mole ratio of 1.
研究领域:
催化化学
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材料科学
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环境工程
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产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2026
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IF 7.3
Wenjun Zhang,Zijiang Zhao,Yonggang Gang,Xiaosong An,Liboting Gao,Siyi Bao,Xuping Ren,Jun Wang,Jianhua Yan,Hao Zhang
Cu/ZnO/Al2O3 (CZA) catalyst remains the benchmark for methanol synthesis but suffers from active-site sintering and insufficient CO2 activation. In this study, we proposed a dual strategy to enhance and regulate the active sites of CZA: hydrothermal treatment induces Cu–Zn coordination to create high-density Cu–ZnO1–x interfaces that promote CO2 conversion, while subsequent La doping regulates Cu0/Cu+ species to favor methanol selectivity. As a result, the maximum space-time yield (STY) of methanol over the designed CZA&5%La-LRCP (prepared by the ligand-regulated coprecipitation method) catalyst improved significantly from 283.0 gMeOH·kgcat–1·h–1 for the conventional coprecipitation-prepared CZA to 400.4 gMeOH·kgcat–1·h–1 under the tested conditions, surpassing most literature reports on La-doped Cu-based catalysts. Comprehensive characterizations and kinetic studies revealed that high-density Cu–ZnO1–x interfaces enhance CO2 adsorption and activation, while uniformly distributed electron-enriched Cu0/Cu+ species promote H2 dissociation and facilitate formate formation and transformation, together establishing an efficient pathway for CO2 activation and hydrogenation. This study demonstrates a promising strategy for the rational design of CO2hydrogenation catalysts through the synergistic modulation of interfacial structure and electronic properties.
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DOI
高影响因子
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