INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2015
·
IF 2.587
Jie Sun,Shaolong Wan,Fen Wang,Jingdong Lin,Yong Wang
A variety of catalysts for higher alcohol synthesis from syngas have been under development for potential commercial application, which are still facing challenges, including poor carbon efficiency due to low selectivity to desired products. In this contribution, we systematically studied the effects of temperature, loading of K and Cs, space velocity, and CO2 addition on the alkali-promoted Cu/ZnO/Al2O3 catalysts in order to achieve a high yield of desired higher alcohol products. Our particular focus was to maximize the carbon efficiency by restricting the amount of undesired byproducts, such as lower alkanes and CO2 that could be formed. Among K and Cs promoted Cu/ZnO/Al2O3 catalysts studied, Cs-promoted Cu/ZnO/Al2O3 catalysts exhibit better performance to higher alcohols and higher carbon efficiency than K-promoted counterparts under similar conditions studied. 1.64 mol % Cs-promoted Cu/ZnO/Al2O3 catalyst achieves the highest selectivity to higher alcohols (24.9%) at a CO conversion of 41.6% under 290 °C, 1875 mL g–1cat h–1, 5.4 MPa. The presence of a small amount of CO2 of 2.5 mol % in the feed has negligible effect on the productivity of higher alcohols but significantly suppresses the formation of CO2 byproduct. With the further increase of CO2 in the feed, the formation of CO2 can be further suppressed but at the expense of productivity loss of higher alcohols, which is probably due to the neutralization of surface Cs sites. The best carbon efficiency can be achieved at 8% mol CO2 in the feed.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2022
·
IF 13.7
Xuliang Lin,Xing Fei,Dalang Chen,Yi Qi,Quanzhou Xu,Yinchun Liu,Qian Zhang,Sha Li,Tiejun Wang,Yanlin Qin,Xueqing Qiu
The conversion of renewable bioethanol into high-energy-density higher alcohols has become essential for meeting the increasing global demand to achieve carbon neutrality. In this study, Zn- and nitrogen-codoped Ni-based lignin-derived carbon catalysts (NiZn@NC) were prepared by solvent volatile self-assembly and in situ reductive carbonization using pulp and paper waste stream alkali lignin as the carbon source. Lignin amphipathic derivatives with −COOH and −NH2 groups would coordinate with metal ions to form a stable lignin–metal framework; thus, the lignin-derived carbon layer disperses the NiZn bimetallic catalyst and prevents from corroding. At an amination reagent/lignin mass ratio of 1:2, an ethanol conversion of 75.2% and a high alcohol yield of 41.7% were achieved over the Ni20Zn1@NC catalyst. Experimental results and density functional theory calculations showed that Zn doping improved the electronic environment and defect structures of metallic Ni and carbon carrier, which effectively inhibited C–C cleavage and suppressed the byproduct formation, such as methane. Thereby, the synergetic effect between Ni and Zn facilitated the efficient conversion of aqueous ethanol into higher alcohols by the Guerbet reaction. This work provides a strategy of in situ pyrolytic doping and stabilizing of renewable biomass macromolecules as the frameworks for the construction of highly active and cost-efficient catalysts for ethanol upgrading.
研究领域:
催化化学
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可再生资源利用
·
材料科学
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2022
·
IF 4.326
Jiamin Huang,Guanghui Zhang,Jie Zhu,Mingrui Wang,Fanshu Ding,Chunshan Song,Xinwen Guo
The catalytic conversion of CO2 to higher alcohols (HAs, representing ethanol and alcohols with more than two carbon atoms) has been of great interest to mitigating the greenhouse effect and effectively utilizing CO2. However, most present catalysts have disadvantages of poor activity (conversion less than 30%) and selectivity (less than 10%) and high price. Herein, we report a Mn- and K-modified iron carbide catalyst that offers a CO2 conversion higher than 40% and a selectivity of higher alcohols exceeding 10%, and the proportion of propanol and butanol in alcohol products is more than 30%. Unpromoted iron carbide has a strong ability of hydrocarbon chain growth, leading to the fast formation of hydrocarbon products rather than HAs. However, on the Mn- and K-modified iron carbide catalyst, K is used to increase the surface C/H ratio of the catalyst by enhancing the adsorption of CO2 on the catalytic surface. The increased C/H ratio is indispensable to the formation of HAs, and the addition of Mn promoter dramatically improves the production of HAs, especially the formation of propanol and butanol. The synergistic effect between Mn and K on iron carbide is the key to produce HAs. In addition, the Mn- and K-modified iron carbide is of low cost, which can potentially provide an alternative for the hydrogenation of CO2 to produce valuable chemicals.
研究领域:
催化化学
·
环境科学
·
能源科学
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Jiaxing Hou,Guohao Zou,Xinrui Liu,Mingge Li,Pengyu Yang,Xiaobin Zhang,Yan Chen,Qian Zhang,Xiaoping Wu,Tiejun Wang
The one-step hydrothermal reconstruction of bioethanol into higher alcohols represents a pivotal advancement in green chemistry, addressing both environmental sustainability and energy regeneration. Herein, a rational design of Ni@C-CeO2 catalysts via a sol–gel method for efficient aqueous-phase ethanol C–C coupling was reported. Systematic investigation of Ni loading and precursor carbonization temperature revealed their critical roles in modulating catalyst microstructure and performance. The optimized Ni-2@C-CeO2-500 catalyst demonstrated exceptional activity under 190 °C and 12 h, achieving ethanol conversion of 72.0% and C4+ alcohol yield of 55.6%. Advanced characterization techniques unveiled structure-performance relationships: (1) controlled Ni loading ensured optimal nanoparticle dispersion, while excessive loading induced aggregation; (2) carbonization at 500 °C balanced carbon matrix architecture and CeO2 reducibility. XPS analysis revealed that oxygen vacancy concentration critically modulates strong metal–support interactions through Ce3+-induced charge redistribution, facilitating interfacial electron transfer during reaction. Furthermore, the Ni-2@C-CeO2-500 catalyst demonstrated excellent stability with sustained activity retention over five consecutive cycles. This work establishes a renewable and technologically viable alternative to conventional petroleum-derived chemicals widely utilized in the chemical industry, demonstrating significant potential for applications in green and sustainable chemistry.
研究领域:
绿色化学
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催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Yanqiu Wang,Ying Zhou,Xinxin Zhang,Mingrui Wang,Tangkang Liu,Jinxing Wei,Guanghui Zhang,Xinlin Hong,Guoliang Liu
Direct CO 2 hydrogenation to higher alcohols (HA) is a promising route for high-value utilization of waste CO 2 , but developing active and stable catalysts remains a grand challenge. For this reaction, constructing multifunctional interfaces as active sites is required to fulfill controllable C-C coupling of alkyl and CO*/CH x O* species. Herein, we report a PdFe catalyst with abundant PdFe alloy-Fe 5 C 2 interfaces via a PdFe alloy induced FeO x carbidization process, which can achieve HA yield of 86.5 mg g cat −1 h −1 with 26.5% selectivity at 300 ºC, 5 MPa, and 6000 mL g cat −1 h −1 . The accelerated deactivation test unveils the PdFe catalyst exhibits better durability than the widely studied CuFe based catalysts against harsh conditions. Multiple in-situ characterization results unveil a synergetic mechanism for HA synthesis at the PdFe alloy-Fe 5 C 2 interfaces, where PdFe alloy is responsible for CO formation and non-dissociative activation, while Fe 5 C 2 phase promotes CO dissociation and chain propagation.
研究领域:
化学工程
·
催化科学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2023
·
IF 12.9
Shunan Zhang,Chaojie Huang,Zilong Shao,Haozhi Zhou,Junjun Chen,Lin Li,Junwen Lu,Xiaofang Liu,Hu Luo,Lin Xia,Hui Wang,Yuhan Sun
Revealing and regulating the intricate reaction mechanism of direct CO2 hydrogenation to higher alcohols (C2+OH), especially for the crucial C–C coupling step, is still a great challenge. Herein, the specific reaction network on Co2C and CuZnAl multifunctional tandem catalysts is elucidated by designing subtly surface adsorption–desorption reactions, in situ chemical transient kinetics, and theory calculations. The key C–C coupling step for the formation of C2+OH over the sole Co2C catalyst was the insertion of CO into R-CHx, while the reaction mechanism can be modulated to the coupling of R-CH2 and CHO with a lower energy barrier on the tandem catalyst (Co2C||CuZnAl). R-CH2 was derived from the hydrogenation dissociation of olefins and coupled with the CHO from formate hydrogenation at the Cu/ZnAl2O4 interface. Such multifunctional tandem catalysts exhibited a high space–time yield of C2+OH of 2.2 mmol g–1 h–1. This work provides an effective strategy for studying complex mechanisms, contributing to the precise design of highly efficient catalysts and the optimization of reaction pathways.
研究领域:
催化化学
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理论计算
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Guangyuan Luo,Zhuoshi Li,Qingyun Liu,Shaoxia Guo,Xiaofeng Pei,Jing Lv,Shouying Huang,Yue Wang,Xinbin Ma
Higher alcohol synthesis (HAS) from syngas is a promising route for converting non-petroleum fossil energy resources into useful fuels or chemicals, while the design and preparation of highly efficient catalysts remain challenging. Herein, a series of Co 0 -Co 2 C catalysts supported on mesoporous carbon–silica composites were prepared for HAS. The composites were derived from carbon-silica nanocages, consisting of uniformly distributed carbon and silica species, which significantly affected the particle dispersion, phase evolution and catalytic performance. With increasing the carbon content, the initial carburization of cobalt was promoted, and some obtained Co 2 C tended to convert to hexagonal closest packed cobalt (hcp-Co, a highly active site for Fischer-Tropsch), boosting the CO dissociation and catalyst activity. While as the silica content increased, more Co 2 C phases can be stabilized, leading to enhanced Co 2 C/Co 0 ratio and ROH selectivity. As a result, the optimal 15Co/22Si@C catalyst achieved a ROH selectivity of 40.1% where 96.0 wt% was higher alcohols (HA), and a space time yield (STY) towards HA of 26.5 mmol·g cat −1 ·h −1 , which remarkably outperformed most of the reported Co-based catalysts in HAS. Moreover, the superior stability of over 250 h reaction was obtained, owing to the confinement effect and strong metal-support interaction provided by the mesoporous carbon–silica composites. This work may provide guidance for designing high-performance monometallic cobalt catalyst in HAS.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2024
·Vol. 26
·期 6
·3507-3516
·
IF 9.3
Xinqi Zheng,Bo Chen,Juwen Gu,Songbai Qiu,Xiaoping Wu,Qian Zhang,Tiejun Wang
Direct reconstruction of fermentation of ethanol in water with high water content to higher alcohols is a promising way to produce value-added fine chemicals and bio-fuels. In particular, aqueous ethanol reconstruction under near-ambient conditions is a milestone goal, but facing great challenges. Herein, the highly active and thermostable hexagonal-close-packed (hcp) Ni dominated hcp/fcc-Ni@C catalyst was fabricated via a facile surfactant-induced carbonization strategy for direct reconstruction of fermentation of ethanol solution to C4+ higher alcohols at near-ambient temperature (<100 °C). A superior performance of >99% higher alcohol selectivity with 17.6% ethanol conversion was achieved. DFT analysis revealed a low energy barrier of ethanol dehydrogenation (rate-determining step) over hcp-Ni, which is crucial for the ultra-low temperature ethanol reconstruction in water. The induction effect of the amide group in surfactant precursors is the key to the formation of hcp-Ni. This work provides new insight into producing bio-based higher alcohols from readily accessible aqueous fermentation of ethanol under mild reaction conditions, which is very promising for large-scale combined applications in industry.
研究领域:
生物化学
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催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2017
·
IF 4.601
Peng Wang,Shuyao Chen,Yunxing Bai,Xiaofeng Gao,Xiaoli Li,Kai Sun,Hongjuan Xie,Guohui Yang,Yizhuo Han,Yisheng Tan
Two series of supported Co-based catalysts were prepared using a facile co-impregnation method. The catalysts were examined in a fixed bed for their ability to selectively convert syngas into higher alcohols. Co–Cu and Co–CeO 2 −x sites have an excellent synergistic effect, which could terminate the growth of the carbon chain effectively for the synthesis of alcohols. Furthermore, the Co–CeO 2 −x site is more beneficial for the synthesis of higher alcohols than the Cu–Co centre. The selectivity for the formation of ethanol and C 1 –C 3 alcohols achieved using the 10Co5Ce/carbon nanotubes catalyst were 29.7% and 89.5%, respectively. In addition, the separation of the Co and CeO 2 −x sites weakens the synergistic effect, and thus, causes the formation of long chain hydrocarbons. The structure–performance correlation studies suggest that the geometric structure of the catalyst likely plays an important role in determining the formation of the Co–CeO 2 −x site, which influences the selectivity towards higher alcohols and higher aliphatic hydrocarbons.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
Frontiers in Energy Research
·
2023
·
IF 3.4
Huang Jiamin,Zhang Guanghui,Wang Mingrui,Zhu Jie,Ding Fanshu,Song Chunshan,Guo Xinwen
The catalytic production of higher alcohols (HAs) is a promising path for converting CO2 into value-added chemical products. The application is still limited by the low selectivity of HAs (less than 10%) on most catalysts. Here, we report a tandem catalyst consisting of Mn-Cu-K modified iron carbide and CuZnAlZr catalyst. The modification of iron carbide with Mn, Cu and K promoters improves the formation of HAs (13.5% Sel.), and the construction of tandem catalysts with CuZnAlZr can further enhance the catalytic performance. By examining different catalyst filling methods and the filling ratio of the tandem catalyst, it was found that the powder mixing resulted in a higher selectivity of HAs with a mass ratio of the two components of 1:1, and a synergistic effect leads to a higher selectivity of HAs (15.5%) with about 40% of propanol and butanol among HAs.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2025
·
IF 4.9
Dongmin Zhao,Zhe Hong,Jiantao Liu,Lingling Yin,Hui Bai,Xiaodong Wang,Zhihua Gao,Wei Huang
The valence state and size of copper species play a critical role in the conversion of syngas to higher alcohols. In this study, CuAl binary catalysts with tunable Cu + -Cu 0 ratios and broad size distributions were successfully synthesized by adjusting the heat-treatment pressure of complete liquid-phase method, and their performance in CO hydrogenation was evaluated. The characterization results demonstrated that increasing heat-treatment pressure led to a general increase in both the Cu species size and the Cu⁺/(Cu⁺+Cu 0 ) ratio. Additionally, heat-treated under high pressure significantly enhanced the interaction between the Cu and Al components, promoted the formation of oxygen vacancies on AlOOH, and facilitated electron transfer. Notably, the oxygen vacancy content exhibited a linear correlation with the Cu + /(Cu + +Cu 0 ) ratio. The catalytic performance revealed a synergistic effect between the valence state and size of copper species in promoting higher alcohol synthesis. The percentage of C 2+ OH increased with the rise in Cu + /(Cu + +Cu 0 ) ratio and the size of Cu 0 and Cu 2 O. Among the catalysts, C-4 exhibited the largest Cu 0 and Cu 2 O sizes and the highest Cu⁺/(Cu⁺+Cu 0 ) ratio, achieving the highest proportion of higher alcohols (53.52 %). In-situ DRIFTS experiments also confirmed the synergistic effect of both factors. Larger Cu particles facilitated the dissociative adsorption of CO, while Cu⁺ sites favored the non-dissociative adsorption of CO. This work significantly expands the understanding of the role of Cu + -Cu 0 ratios and larger copper species in syngas conversion, offering valuable insights for the design of Cu-based catalysts with a high selectivity toward C 2+ OH.
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
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2021
·
IF 3.764
Xing Fei,Quanzhou Xu,Lijing Xue,Xiaowen Zhong,Ze Zhang,Kunyi Liu,Xuliang Lin,Tiejun Wang,Yanlin Qin,Xueqing Qiu
An efficient and stable catalyst to produce higher alcohols with a higher heat value and cetane number and less corrosive to engines from aqueous ethanol is still facing challenges. Here, a novelty of NiSn bimetallic catalysts encapsulated in a nitrogen-doped lignin-based carbon material (NiSn@NC) was prepared by modified biorefinery lignin and further precisely coordinated with metal ions to form a lignin-metal supramolecular material followed by in situ calcining. Results showed that the optimized Ni20Sn1@NC catalyst exhibited a superior ethanol conversion (68.5%), a C4+ higher alcohol yield of 31.8%, and a ratio of iso to normal alcohol of 0.52. Moreover, it also exhibited excellent stability even after four-cycle runs. Structural analysis revealed that the Sn/N-doping lignin-based carbon material improved the Ni dispersion and basic site density, which adjusted efficiently the electronic structure of the metallic active site. Therefore, the NiSn@NC bimetallic catalysts showed satisfactory conversion and stability of aqueous ethanol upgrading to C4+ higher alcohols.
研究领域:
催化化学
·
可再生能源
·
材料科学
✓ 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）