APPLIED CATALYSIS B-ENVIRONMENTAL
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2020
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IF 16.683
Yu Kang,Yujia Han,Ming Tian,Chuande Huang,Chaojie Wang,Jian Lin,Baolin Hou,Yang Su,Lin Li,Junhu Wang,Xiaodong Wang
Fe-based oxygen carries (OCs) have attracted wide attention due to the low cost and environmental compatibility for chemical looping methane partial oxidation. However, they usually suffer from low CH 4 reactivity mainly due to insufficient synergy between catalytic CH 4 activation and lattice oxygen mobility. In this work, Fe ions with different amount were incorporated into a novel garnet structure (Y 3 Fe x Al 5-x O 12 ), which exhibited drastically increased CH 4 conversion with reduction time. This resulted from in-situ formed Fe 0 sites at the early stage of reduction, which led to a more efficient reaction route involving methane catalytic decomposition on Fe 0 and the resulted carbon oxidation easier by lattice oxygen, compared with methane directly oxidized by OCs. Moreover, the amount of Fe ions in garnet influenced surface exposed Fe 0 sites and oxygen mobility, inducing Y 3 Fe 2 Al 3 O 12 performed the best with almost 94 % methane conversion thanks to the combined advantages of larger surface exposed Fe 0 and higher lattice oxygen mobility.
研究领域:
化学工程
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材料科学
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产品关联
DOI
高影响因子
Chem
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2023
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IF 23.5
Qiao Han,Pan Gao,Kuizhi Chen,Lixin Liang,Zhenchao Zhao,Xinlong Yao,Dong Xiao,Xiuwen Han,Guangjin Hou
The urgent need for efficiency improvement in the oxide-zeolite bifunctional syngas-to-hydrocarbon catalysis necessitates in-depth mechanistic insights into this reaction, especially for the initial syngas conversion over the oxide component, which remains poor. Herein, we comprehensively investigated syngas conversion over a representative ZnAl 2 O 4 spinel oxide with state-of-the-art solid-state NMR technologies. Notably, specific surface dual active sites for syngas activation with –Al IV –OH···Zn III – structure were unambiguously identified. More importantly, the dynamic evolution of the reaction intermediates and active sites during the reaction process was elaborated at atomic level by a series of double resonance and multi-dimensional correlation NMR experiments. In combination with in situ spectroscopic characterizations, we revealed the full cycle of the formate-methoxy-based pathway for the syngas-to-methanol conversion via synergistic interplay of the dual active sites. The in-depth atomic-level understanding of the catalytic mechanism will be beneficial to further rational design of high-performance catalysts for syngas conversion.
研究领域:
催化化学
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表面科学
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材料化学
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物理化学
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能源化学
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多相催化
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产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2021
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IF 8.198
Zhuang Zeng,Zhuoshi Li,Shaoxia Guo,Jing Lv,Shouying Huang,Yue Wang,Xinbin Ma
Higher alcohol synthesis (HAS) direct from syngas using Fe-based catalysts is quite promising, but there are still problems in the construction of intimate-contact and stable dual sites to obtain satisfactory higher alcohol selectivity and space time yield (STY). Herein, a series of Au–Fe2.2C catalysts derived from monodisperse Janus Au–Fe3O4 nanoparticles with different Fe/Au ratios were prepared. The optimal catalyst with a Fe/Au molar ratio of 11.6 achieved the most Janus nanoparticles and exhibited the highest STY toward higher alcohols of 0.195 g gcat–1 h–1 and excellent catalytic stability over 200 h. The superior performance of this catalyst was attributed to the unique Au–Fe2.2C Janus structure, which could enhance both CO insertion and CO dissociation as well as their synergistic effect. The correlation of the CO adsorption behavior and STY toward alcohols was established as well, indicating that the balance between CO nondissociated adsorption and CO dissociated adsorption played an important role in enhancing the alcohol formation. Moreover, the strong interaction between Au and iron species in Janus nanoparticles could facilitate the formation of ε′-Fe2.2C and benefit the stability of the catalyst. These results may provide new ideas for the design and fabrication of high-performance catalysts with dual sites for HAS.
研究领域:
催化化学
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材料科学
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2021
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IF 7.312
Yan Zhang,Haryo Wibowo,Li Zhong,Mika Horttanainen,Zunbo Wang,Caimeng Yu,Mi Yan
High CO 2 content exists in the raw syngas produced from supercritical water gasification of food waste, CO 2 removal to improve quality of the syngas is necessary before further utilization. In this study, Cu-BTC, Mg/Cu-BTC, Cu-BTC@MWCNT, and Mg/Cu-BTC@MWCNT were synthesized and characterized as CO 2 adsorbents. The adsorption experiments were conducted to investigate the optimal adsorbent and adsorption conditions. The results indicated that Mg 2+ and multi-walled carbon nanotubes (MWCNT) doped into Cu-BTC influenced the physical properties of adsorbents. Among of all studied adsorbents, Mg/Cu-BTC@MWCNT had the maximum CO 2 adsorption capacity (3.63 mmol/g) and selectivity (14.28) at 25 °C and 100 kPa. Analysis of variance (ANOVA) exhibited that adsorption pressure had significant effects on CO 2 adsorption capacity of Mg/Cu-BTC@MWCNT. The influences of different operating parameters on CO 2 adsorption capacity and selectivity were discussed in Mg/Cu-BTC@MWCNT. The adsorption isotherms of gas components on Mg/Cu-BTC@MWCNT can be sorted as follows: CO 2 > CO > CH 4 > H 2 . In additional, the regeneration experiment with 5 times was conducted and the result showed that Mg/Cu-BTC@MWCNT has high stability.
研究领域:
材料科学
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环境工程
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能源技术
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DOI
高影响因子
Small Science
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2023
·Vol. 3
·期 4
·2200085
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IF 12.7
Mingxiong Lin,Weishan Jiang,Tingshi Zhang,Bixia Yang,Zanyong Zhuang,Yan Yu
The design of advanced metal–organic framework (MOF) catalysts for solar-driven conversion of CO 2 into syngas (CO/H 2 mixture) is beneficial. Herein, the design of a joint MOF heterostructure consisting of orderly assembled Co II - and Co III -based Prussian blue analogs (PBAs) driven by their spontaneous lattice match in the growth process is reported. As-prepared H/Co III -PBA@Co II -PBA cage is a mesocrystal and exhibits superior photocatalytic syngas production activity ( V CO up to 50.56 mmol g −1 h −1 , CO/H 2 = 1:1), which is among the best state-of-the-art heterogeneous photocatalysts in the literature. Theoretical calculations and experimental results confirm that Co III -PBA exerts a stronger affinity for CO 2 molecules than Co II -PBA, thus serving as the active site. The built-in electric field in the Co III -PBA@Co II -PBA heterojunction can direct the fast transport of photogenerated electrons from Co II -PBA to the active Co III -PBA. In the present case, the engineering of electronics outweighs morphological engineering to enhance the catalytic properties of Co III -MOF@Co II -MOF for CO 2 -to-syngas conversion.
研究领域:
材料科学
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能源化学
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催化反应
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产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2023
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IF 4.2
Gengrui Zhang,Yan Li,Yong Chen,Xinning Hao,Xianhua Zhang,Shuai Wang,Jingdong Lin,Yong Wang,Shaolong Wan
The development of Ni-based syngas methanation catalysts with superior thermal stability remains a formidable challenge, which typically requires the use of a high Ni loading and a recipe containing very complex components. Herein, a novel Ni catalyst using a ZnAl2O4 spinel support was designed and prepared by an isopropanol-mediated controlled hydrolysis method, which demonstrated excellent reactivity and stability toward the syngas methanation reaction. Moreover, the 35% Ni/ZnAl2O4 catalyst still maintained a high reactivity after steam treatment at 750 °C, while the 35% Ni/Al2O3 counterpart suffered a nearly complete loss of reactivity during such an accelerated test. The detailed characterization reveals that the drastic deactivation of Ni/Al2O3 after steam treatment is attributed to the favored formation of NiAl2O4 under the severe reaction atmosphere, resulting in the loss of active Ni. In contrast, the employment of the highly stable ZnAl2O4 support can not only inhibit the sintering of supported Ni particles due to their strong interaction but also avoid the loss of the active Ni component by preventing the formation of NiAl2O4. This work sheds light on the critical role and the intrinsic mechanism of the spinel support for the construction of the desired methanation catalysts. The mechanistic scenario revealed in this work provides an important and novel solution to overcome the deactivation problem not only useful for methanation catalysts but also valid for most other supported metal catalysts commonly used in the reaction processes that require severe reaction conditions.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
Journal of Cleaner Production
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2023
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IF 11.1
Hao Qi,Qirong Yang,Xinru Ma,Mengyu Wan,Zijun Zhang,Haoxi Ben,Lianghuan Wei,Zhaoying Li
The large-scale flooding of Enteromorpha prolifera (EP) forms “green tide”, which causes severe environmental problems. However, EP, an algal biomass , can be converted into syngas via pyrolysis . In this study, the pyrolysis mechanisms of the main compositional models of EP used to produce syngas are investigated using a combination of molecular dynamics simulations and fixed-bed experiments. Rhamnose (Rha), glucuronic acid (GlcA), aspartic acid (Asp), glutamic acid (Glu), and alanine (Ala) are used as the model compounds. The results indicate that H 2 is primarily produced by Glu (reached 24.68 vol%), followed by Asp and Ala, and CO is produced by Ala (reached 44.94 vol%), Glu, and Asp. The molecular dynamics simulation results indicate that the energy barriers for the pyrolysis of Glu and Ala to produce H 2 and CO, respectively, are the lowest. Three amino acids undergo dehydration, deamination, and decarboxylation . Moreover, the synergistic effect of the three amino acids in co-pyrolysis is reflected in the production of hydrogen groups from Asp; and the hydrogen group then attacks Glu to seize the hydrogen group on it to produce hydrogen . In addition, the H 2 content in the syngas produced by the separate pyrolysis of Rha (17.75 vol%) and GlcA (17.35 vol%) are similar and lower than those of the Rha and GlcA mixtures (19.12 vol%). The CO content in the pyrolysis gas of GlcA is higher than that of Rha. The simulation results prove that the amino acids undergo dicarboxylic and deamination reactions to produce amino acids and CO 2 . Meanwhile, polysaccharide sulfate breaks glycosidic bonds , producing free radicals such as hydrogen and hydroxyl groups at 700 K. When the temperature rises to 1900 K, the products of the previous stage further break the bond, producing small-molecule gases. However, the addition of polysaccharide model compounds promotes the production of CO 2 and C O groups and inhibits the formation of CO. Co-pyrolysis cannot increase H 2 , and the synergistic effect is not significant. Moreover, Ni and SAPO-34 exhibited good catalytic activities , which could increase syngas production. A raw materials to catalyst ratio of 5:1 is a good choice because it improves the H 2 and CO contents and makes economical use of Ni. With the increase of Ni catalyst cycles, H 2 content also shows a decreasing trend, from 22.86 vol% to 16.27 vol% (third cycle). With the number of SAPO-34 cycles, the increase of CO content, from 28.66 vol% to 32.67 vol% is explained by the increase in the specific surface area of the catalyst caused by repeated use, which increases the selectivity of C2 and enhances the ability of decarbonylation. This study focuses on the syngas reaction paths and pyrolysis reactions of different EP model compounds. The pyrolysis mechanism of EP to produce syngas is determined using a combination of experiments and simulations, providing a method for the energy utilization of EP.
研究领域:
环境科学
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能源科学
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生物化学
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DOI
高影响因子
FUEL
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2025
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IF 7.5
Qicheng Li,Xihu Zhao,Xiaobo Song,Juan Dong,Zhitong Zhao,Pan Hao,Qi Shi,Xuekuan Li
Benzene alkylation with syngas is attractive for alkylbenzene production, which use metals/metal oxides combining H-ZSM-5 zeolites as the catalyst. Herein, the H-ZSM-5 zeolites with three different morphologies—spindle-, flake-, and nano-sized—were synthesized. Subsequently, crystal structural, textural and acidic properties of three H-ZSM-5 zeolites and their corresponding bifunctional catalysts were characterized and the catalytic reaction activity and stability of the benzene alkylation with syngas were investigated. The bifunctional catalyst derived from nano-sized zeolites demonstrates an initial benzene conversion rate of 46.7% and reduces by 71.78% after 51 h of continuous operation, owing to abundant acid sites, large surface area and mesopores diameters, and balanced acidity to promote reactant and product diffusion. The spindle-shaped zeolite catalyst delivers the highest initial benzene conversion rate (53.77%) due to abundant acid sites. However, the benzene conversion rate drops to 12.12% of the initial value after 39 h due to limited micropore volume and relatively small mesopore diameters of the catalyst. The flake-shaped zeolite catalyst exhibits the lowest initial conversion rate and the shortest lifetime (30 h) owing to the fewest accessible acid sites and the peculiar pore structure. Three cases indicate that increasing mesopore volume is conducive to improve ratio of Brønsted to Lewis acid sites (B/L), resulting in enhancement of the catalytic activity. Meanwhile, the huge micropore volume and increased mesopore diameter are positive to alleviate pore blockage and coverage of active sites due to high mass-transfer efficiency within the zeolitic channels. These textural advantages collectively contribute to a delayed catalyst deactivation process and sustained catalytic activity. This work highlights the pivotal role of the H-ZSM-5 morphology in the benzene alkylation process with syngas and facilitates the efficient development of production process for non-oil alkylbenzene.
研究领域:
催化化学
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材料化学
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石油化工
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多相催化
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纳米材料
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产品关联
DOI
高影响因子
FUEL
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2020
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IF 5.578
Hao Qu,Sihui He,Yue Su,Yulong Zhang,Haiquan Su
Direct synthesis of ethanol from syngas (a mixture of H 2 and CO) is considered as an eco-friendly and industrially important process to produce renewable fuels and chemicals. The current non-noble metal catalyst systems suffer from either low selectivity or multiple processes with high energy consumption. Here, we report a novel molybdenum diselenide-based catalyst system for high-selective conversion of syngas into ethanol. For a series of K-promoted MoSe 2 catalysts with different K/Mo ratios (K x -MoSe 2 , x = 0.25-1.00), K 1.00 -MoSe 2 surprisingly exhibits excellent ethanol selectivity up to 58.7 C mol % in total alcohols and 31.1 C mol % in the total product, which is higher than the highest selectivity value for the non-noble metal catalysts reported in the literature. The high ethanol selectivity is attributed to the formation of K-Mo-Se active phase and the synergistic effect of the Mo IV , Mo V and Mo VI multivalent species in the active phase. This study opens up a highly selective non-noble metal catalyst system for the direct synthesis of ethanol by syngas, which is of practical significance for the catalytic conversion of hydrogen-poor syngas.
研究领域:
化学工程
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催化科学
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DOI
高影响因子
Catalysis Science & Technology
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2018
·Vol. 8
·期 17
·4338-4348
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IF 5.365
Xiaoli Yang,Xiong Su,Binglian Liang,Yaru Zhang,Hongmin Duan,Junguo Ma,Yanqiang Huang,Tao Zhang
The oxide–zeolite process has been attracting widespread attention due to its promising performance in syngas conversion to hydrocarbons with high selectivity and stability. Here, a composite catalyst containing Zn–Cr oxide and ZSM-5 zeolite provides a competitive option in the one-step conversion of syngas into C5+ hydrocarbons. In order to figure out the influence of the pore structure and acidity of zeolite on the oxide–zeolite process, alkali treatments on ZSM-5 are carried out. The treated ZSM-5 shows increased selectivity for gasoline fractions. With a set of structural and morphological characterization techniques, the formation of a hierarchical porous structure is demonstrated, which is favorable for the diffusion of heavy products. Furthermore, an increase in the number of Lewis acid sites, acting as the main active sites for the polymerization, cyclization and aromatization reactions, also contributes to the promotion of C5+ hydrocarbon production. It must be noted, however, that a certain amount of Brønsted acid sites is necessary for the tandem transformation of CH3OCH3 intermediates, which may further affect the CO conversion.
研究领域:
催化化学
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材料科学
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DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2018
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IF 5.091
Mingsheng Luo,Shun Xu,Qingyang Gu,Zuoxing Di,Qinglong Liu,Zhijun Zhao
Layered double hydroxides (LDHs) were innovatively employed in this study as catalyst for synthesis gas conversion to chemicals, such as oxygenates. Cobalt-aluminium layered double hydroxides (Co-Al LDHs) was prepared at different temperatures. and lactate was successfully intercalated into the LDHs by ion-exchange method and then the material was further delaminated in water at ambient temperature. The samples were characterized by SEM, TEM and AFM, and separately dispersed nanosheets can be clearly observed. The prepared lamellas were applied in aqueous-phase synthesis gas conversion reaction. The catalysts generated a superior activity of 0.055–0.675 mol CO · mol Co - 1 · h - 1 and greater oxygenated product (acetaldehyde) selectivity (S Oxy = 75–88%) than conventional cobalt Fisher-Tropsch (FT) synthesis catalysts. Ammonium ion showed some effect of the selectivity of the acetaldehyde. The original research results suggested a promising application of the mono-dispersed ultrathin cobalt-bearing LDHs nanosheets in the aqueous phase syngas conversion to valuable oxygenate products.
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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纳米技术
✓ 已验证
DOI
PubMed
高影响因子
Journal of Energy Chemistry
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2026
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IF 15.6
Haoran Jia,Le Lin,Xiaohui Feng,Xiaoyue Wang,Rentao Mu,Qiang Fu
Competitive adsorption between H 2 and CO x ( x = 1, 2) on oxide catalysts represents a primary limitation in hydrogenation reactions, where mutual site blocking suppresses activity and selectivity. This constraint hampers syngas conversion and CO 2 hydrogenation, yet strategies to decouple adsorbates remain elusive. Here, we show that competitive adsorption can be overcome through a partial-site-occupation mechanism that prevents surface saturation and enables independent activation. For a model ZnCr 2 O 4 @ZnO x system, in situ infrared spectroscopy directly reveals the simultaneous adsorption of H 2 with CO or CO 2 , in contrast to the mutually exclusive adsorption observed on pristine ZnO. Kinetic measurements link this decoupling to suppressed inhibition effects and altered reaction orders, driving improved catalytic performance. Density functional theory combined with temperature-programmed analyses further demonstrates that homolytic H 2 dissociation becomes thermodynamically self-limiting, resulting in intrinsically unsaturated surface coverages. These findings indicate competitive adsorption from an inherent constraint to a tunable surface property and establish practical design strategies for cooperative activation in ZnO-based oxide-catalyzed hydrogenation reactions. The ZnCr 2 O 4 -confined ZnO x catalyst decouples the competitive adsorption between CO/CO 2 and H 2 , enabling the co-adsorption and co-activation of these small molecules. Download: Download high-res image (182KB) Download: Download full-size image
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DOI
高影响因子
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