CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Yibo Tang,Jiayin Liang,Jiabing Chen,Mengheng Wang,Xinying Liu,Xiaojun Lu
Na- and Mn-promoted Co 2 C-based catalysts have demonstrated promise for the one-step conversion of syngas to olefins via Fischer-Tropsch synthesis to olefins (FTO). However, their consistently low activity limits their industrial applications. Here, we designed a compound catalyst comprising a CoMn composite catalyst and ZSM-5 zeolite, achieving 4.9 times the activity compared to the sole Co 2 C catalyst without compromising olefin selectivity. CO– and H 2 -TPD studies, in-situ DRIFT experiment, and DFT calculation revealed that the surface acidity of ZSM-5 modulated the strong electron effect of Na, subsequently strengthening H 2 adsorption on the Co 2 C catalyst surface. The H-assisted CO dissociation was therefore promoted and the catalyst activity was boosted. Meanwhile, Co 2 C as active site was unaffected, maintaining high selectivity to olefins. Constructing an interface between Co 2 C and ZSM-5 in the compound catalyst is proven to be a successful strategy for enhancing the activity of Co 2 C-based catalysts for FTO.
研究领域:
催化化学
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材料科学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2019
·
IF 7.723
Shunan Zhang,Xiaofang Liu,Zilong Shao,Hui Wang,Yuhan Sun
Direct CO 2 hydrogenation to ethanol is one of the promising and emerging routes for the transformation of CO 2 into value-added chemicals, but it remains a major challenge because of low ethanol selectivity and catalytic stability. In this work, Na-promoted cobalt catalysts supported on different materials (Al 2 O 3 , ZnO, AC, TiO 2 , SiO 2 , and Si 3 N 4 ) were evaluated to elucidate the effects of supports. The SiO 2 - and Si 3 N 4 -supported catalysts exhibited efficient generation of ethanol with 18% CO 2 conversion and 62% selectivity in the alcohol distribution at 250 °C, whereas CH 4 was predominantly produced on other supported catalysts. Characterization results indicated that the Co 2 C active phase only remained intact on SiO 2 and Si 3 N 4 supports during reaction and exhibited excellent durability for 300 h, which was attributed to the existence of a strong metal–support interaction (SMSI) obtained by Si O Co bond formation. In situ DRIFTS results revealed that CO produced on Co 2 C inserted into CH x intermediates to form ethanol. Moreover, CO as the reactive intermediate could induce the regeneration and reconstruction of decomposed Co 2 C on the surface for catalytic sustainability.
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
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Xiaoli Yang,Yalan Wang,Haoxi Ben,Jia Yang,Wei Jiang,Anders Holmen,Yanqiang Huang,De Chen
Fischer–Tropsch synthesis over CoMn oxides is a surface-catalyzed structure-sensitive reaction. Active site changes greatly alter product distribution. The dynamics and essence of the changes in Co species during the reaction have seldom been explored. Herein, multiple characterizations were applied to confirm that two types of active sites, i.e., Co and Co 2 C, coexist on CoMnO x under the reaction conditions. Apart from the direct participation of carbon species in the reaction, the steady-state isotopic transient kinetic analysis also suggested the mutual transformation of carbon species in Co 2 C. The ratio of the two paths altered with the temperature, thus leading to Co 2 C-rich and Co-rich surfaces at intermediate and high temperatures, respectively. Kinetic calculations and microkinetic modeling showed that Co 2 C-rich surfaces facilitated CO adsorption and suppressed hydrogen adsorption. This gave high carbon-chain growth activity. The Co-rich surfaces showed high vacancy and hydrogen coverages, lowering the CO activation and CH 4 formation energies.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Da Wang,Guangbo Liu,Chuanhui Zhang,Chao Feng,Jinhu Wu,Song Chen,Wenjie Xiang,Hao Huang,Zhihao Liu,Noritatsu Tsubaki
The reasons for the too high CO2 selectivity (near 50 C %) in Co2C-based Fischer–Tropsch to olefins (FTO) are not clear. Water–gas-shift (WGS) side reaction is thought to be responsible for this, but in-depth research is lacking. Here, we revealed the mechanism of the too high CO2 selectivity in Co2C-based FTO. Kinetic studies showed that WGS reaction was more likely to occur than the hydrocarbon production reaction. In addition, a too severe WGS reaction would result in the formation of an H2-enriched and CO-deficient environment on the catalyst surface, which was not favorable for the generation of light olefins. Catalyst characterization results proved that the severe WGS reaction could also lead to the transformation of prismatic Co2C to spherical Co2C. Theoretical calculations demonstrated that prismatic Co2C (020) and Co2C (101) facets were dominant crystal facets for both FTO and WGS reactions. Furthermore, in situ diffuse reflectance infrared Fourier transform spectroscopy experiments found that the H2O produced in FTO completely participated in the WGS reaction. This clearly revealed why the CO2 selectivity was close to 50 C % in FTO. Therefore, we believed that accelerating the desorption of H2O on the catalyst surface and preventing its readsorption are the key elements for inhibiting CO2 formation in FTO.
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
Science Advances
·
2023
·Vol. 9
·期 24
·
IF 13.6
Mingrui Wang,Peng Wang,Guanghui Zhang,Zening Cheng,Mengmeng Zhang,Yulong Liu,Rongtan Li,Jie Zhu,Jianyang Wang,Kai Bian,Yi Liu,Fanshu Ding,Thomas P. Senftle,Xiaowa Nie,Qiang Fu,Chunshan Song,Xinwen Guo
The decomposition of cobalt carbide (Co 2 C) to metallic cobalt in CO 2 hydrogenation results in a notable drop in the selectivity of valued C 2+ products, and the stabilization of Co 2 C remains a grand challenge. Here, we report an in situ synthesized K-Co 2 C catalyst, and the selectivity of C 2+ hydrocarbons in CO 2 hydrogenation achieves 67.3% at 300°C, 3.0 MPa. Experimental and theoretical results elucidate that CoO transforms to Co 2 C in the reaction, while the stabilization of Co 2 C is dependent on the reaction atmosphere and the K promoter. During the carburization, the K promoter and H 2 O jointly assist in the formation of surface C * species via the carboxylate intermediate, while the adsorption of C * on CoO is enhanced by the K promoter. The lifetime of the K-Co 2 C is further prolonged from 35 hours to over 200 hours by co-feeding H 2 O. This work provides a fundamental understanding toward the role of H 2 O in Co 2 C chemistry, as well as the potential of extending its application in other reactions.
研究领域:
催化化学
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化学工程
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材料科学
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可持续能源
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多相催化
✓ 已验证
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
ADVANCED MATERIALS
·
2024
·Vol. 36
·期 35
·2404046
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IF 27.4
Xiaoling Hong,Qiao Zhao,Yanping Chen,Zhibin Yu,Mengzhen Zhou,Yan Chen,Wenhao Luo,Chang Wang,Na Ta,Haitao Li,Runping Ye,Xiaotao Zu,Wei Liu,Jian Liu
Cobalt carbide (Co 2 C) possesses high catalytic efficiency Fischer–Tropsch synthesis (FTS), while the products selectivity appears sensitive to crystallography geometry. Since the Anderson–Schulz–Flory (ASF) distribution in FTS is broken through fabricating facetted Co 2 C nanocrystals, yet the underlying mechanism of Co 2 C crystallization remains unclarified suffering from sophisticated catalyst composition involving promoter agents. Herein, the synthesis of high-purity single-crystal nanoprisms (Co 2 C-p) for highly efficient FTS is reported to lower olefins. Through comprehensive microstructure analysis, e.g., high-resolution TEM, in situ TEM and electron diffraction, as well as finite element simulation of gas flow field, for the first time the full roadmap of forming catalytic active cobalt carbides is disclosed, starting from reduction of Co 3 O 4 precursor to CoO intermediate, then carburization into Co 2 C-s and subsequent ripening growth into Co 2 C-p. This gas-induced engineering of crystal phase provides a new synthesis strategy, with many new possibilities for precise design of metal-based catalyst for diverse catalytic applications.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Physical Chemistry C
·
2026
·
IF 3.4
Zhilin Yang,Weimin Huang,Hua Yang
To address the issues of energy depletion and environmental pollution caused by the combustion of fossil fuels, electrocatalytic overall water splitting for hydrogen production is one of the very promising approaches. The key to the large-scale application of electrocatalytic overall water splitting lies in the search for low-cost, high-content, and high-performance electrocatalysts. In this paper, through a two-step process of carbonization followed by phosphination, the P-modified Co2C@Co/NF composite material (P–Co2C@Co/NF) was successfully designed and synthesized. P–Co2C@Co/NF exhibits excellent performance in hydrogen evolution reactions (HER) and oxygen evolution reactions (OER). Under alkaline conditions, the overpotential for HER and OER can reach 10 mA cm–2 current density with only 75 mV and 246 mV respectively. P–Co2C@Co/NF demonstrates excellent overall water splitting capability, requiring only 1.63 V of driving voltage to achieve 10 current density. This provides a new method for enhancing the electrocatalytic performance of heteroatom-modified transition metal compounds.
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2024
·
IF 8.1
Fang Li,Haili Lin,Huiqin Yu,Xuemei Jia,Shifu Chen,Jing Cao
Replacing the sluggish oxygen evolution reaction with the oxidation of benzyl alcohol to construct the hybrid water electrolysis system has been attractive for its merits of environmentally friendly and economically efficient. However, the activity of the catalyst to oxidize alcohols needs to be further improved. Tailoring the d-band center (E d ) has been proven as an effective method to promote the hydrogen evolution reaction (HER). How feasible is this strategy in the oxidation of benzyl alcohol? Here, using Co 2 C as a research platform, the doping nonmetal heteroatom (P, S, N) engineering is adopted to promote its electrocatalytic BA oxidation and HER performance. The results of electrochemical tests show that the P-doped Co 2 C (P–Co 2 C) only requires a low potential of 1.33 and 1.38 V vs. RHE to achieve current densities of 20 and 100 mA cm −2 for BA oxidation, which is superior to that of S–Co 2 C, N–Co 2 C, and pristine Co 2 C. The conversation and faradaic efficiency for BA is up to 98.1% and 93.8% during ten consecutive cycle tests. The P–Co 2 C also exhibited outstanding activity and stability toward HER. The density functional theory (DFT) calculation revealed that specified P doping could modify the d-band center of Co 2 C approaching the peak of the volcano map (electrochemical overpotentials ∼ E d ). The Gibbs free energy of the BA oxidation was also reduced, thus optimizing the adsorption and desorption process of intermediates. On the other hand, the catalyst surface physical properties of Co 2 C such as hydrophilicity was promoted by the doped heteroatoms which was favorable for the gas-liquid-solid triphase electrocatalytic reaction. This work offers a facial perception of regulating the d-band to design advanced bifunctional electrocatalysts for organic matter oxidation and HER.
研究领域:
电化学
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材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2021
·
IF 6.707
Jiaming Wang,Guilong Liu,Huixian Zhong,Pengfei Song,Kang An,Ziyang Zhang,Ang Cao,Yuan Liu
In this work, Co δ+ -Co 2 C decorated-Co-Ni alloy nanoparticles (NPs) loaded on Mg-Al-O complex oxides were fabricated via an in-situ reduction and topochemical carbonization strategy by using hydrotalcite as the precursor. The Co δ+ -Co 2 C decorated-Co-Ni alloys were obtained via the following process: (I) after reduction, Co-Ni alloy was obtained and Co could donate electrons to Ni in the Co-Ni alloy NPs; (II) in syngas atmosphere, some of cobalt atoms on the surface of Co-Ni NPs reacted with CO and were converted to Co 2 C. Resultantly, in the reaction process, Co-Ni alloy NPs were transformed into Ni-Co alloy@Co-Co 2 C, a core-shell structure with Ni-Co alloy core and Co-Co 2 C shell. When used as the catalysts for direct ethanol synthesis (DES) from syngas, the bimetallic Co-Ni alloy@Co-Co 2 C catalyst performed excellent selectivity to ethanol, owing to the regulation of dissociatively and associatively adsorbed CO by Co δ+ -Co 2 C active sites formed on the surface of Co-Ni alloy NPs. Moreover, the mutual dilution between Co and Ni in the Co-Ni alloy NPs inhibited the generation of heavy hydrocarbons, further improving the selectivity to alcohols. The total alcohol selectivity of 43.0% and ethanol occupied 45.2 wt% could be reached over the optimal catalyst.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Zhilin Yang,Kechang Li,Daguang Zhang,Hua Yang
In order to solve the problem of environmental pollution caused by fossil fuel emissions, electrocatalytic overall water splitting is a very promising energy conversion device. In the field of large-scale overall water splitting, it is particularly important to develop new non-precious metal electrocatalysts. In this paper, we successfully prepared CoFe@Co 2 C@Co/NF by hydrothermal synthesis of CoFe-LDH as the precursor and small molecule amine ethylenediamine as the C source. CoFe@Co 2 [email protected] /NF shows excellent electrocatalytic performance in alkaline environment. CoFe@Co 2 [email protected] /NF can provide low overpotential of 53 mV and 246 mV to reach 10 mA cm −2 current density in hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. In addition, CoFe@Co 2 [email protected] /NF was used as the anode and cathode of the electrolytic cell system for overall water splitting, and the current density of 10 mA cm −2 can be reached with a voltage of only 1.57 V, which is superior to the commercial electrolytic cell system composed of Pt/C and RuO 2 . The material exhibits a good coupling effect of soft and hard magnetic exchange. This provides new insights into the development of transition metal carbides as high-performance electrocatalysts.
✓ 已验证
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2022
·
IF 7.392
Minhua Zhang,Haipeng Yu,Yuzhe Sun,Yingzhe Yu,Yifei Chen,Lingtao Wang
Cobalt carbide (Co 2 C) has been discovered as the promising active phase for Fischer–Tropsch to olefins (FTO) process and higher alcohols synthesis (HAS) from syngas, in the form of nanoprisms and nanospheres, respectively. However, CO 2 formation is inevitable on Co 2 C catalysts, especially in FTO process. So far, the mechanism of CO 2 formation on Co 2 C surfaces is less understood. This work provides fundamental insights into CO 2 formation on Co 2 C nanospheres and nanoprisms through computational and experimental study. DFT calculations demonstrate that: Co 2 C (1 0 1) and (0 2 0) surfaces exposed on Co 2 C nanoprisms are basically not active for water gas shift (WGS) reactions but the introduction of Na greatly promotes CO 2 formation. CO 2 is less favored on Co 2 C(1 1 1) surface which is dominant on Co 2 C nanospheres, however, the reverse WGS activities can be promoted with Na addition. The experimental results confirmed removing Na from Co 2 C can efficiently suppress WGS activity, thus reducing CO 2 selectivity while the selectivity of light olefins retained. Though previous studies focused on Na addition to promote the yield of light olefins, our work indicates that Na also promotes undesired CO2 formation. Our results suggest that Na is crucial for active phase formation but not necessarily beneficial during the CO hydrogenation reactions.
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
危险品化学品经营许可证（带存储）