Pub Date : 2025-10-01DOI: 10.1016/S1872-5813(25)60547-0
Haibo WANG , Zelin WU , Hui WEN , Zhiyong ZHAO , Chenbo WANG , Tongyu LU , Yuxuan GUO , Congwei WANG , Junying WANG
The utilization of nickel-based catalysts as alternatives to expensive platinum-based (Pt-based) materials for the hydrogen evolution reaction in acidic electrolytes has attracted considerable attention due to their potential for enabling cost-effective industrial applications. However, the unsatisfied cyclic stability and electrochemical activity limit their further application. In this work, nickel-molybdenum (Ni-Mo) alloy catalysts were successfully synthesized through a comprehensive process including electrodeposition, thermal annealing, and electrochemical activation. Owing to the synergistic interaction of molybdenum trinickelide (Ni3Mo) and molybdenum dioxide (MoO2) in Ni-Mo alloy, the catalyst display superior overall electrochemical properties. A low overpotential of 86 mV at 10 mA/cm2 and a Tafel slope of 74.0 mV/dec in 0.5 mol/L H2SO4 solution can be achieved. Notably, remarkable stability with negligible performance degradation even after 100 h could be maintained. This work presents a novel and effective strategy for the design and fabrication of high-performance, non-precious metal electrocatalysts for acidic water electrolysis.
{"title":"Nickel-molybdenum alloy electrodeposited on nickel substrates for optimized hydrogen evolution reaction in acidic electrolytes","authors":"Haibo WANG , Zelin WU , Hui WEN , Zhiyong ZHAO , Chenbo WANG , Tongyu LU , Yuxuan GUO , Congwei WANG , Junying WANG","doi":"10.1016/S1872-5813(25)60547-0","DOIUrl":"10.1016/S1872-5813(25)60547-0","url":null,"abstract":"<div><div>The utilization of nickel-based catalysts as alternatives to expensive platinum-based (Pt-based) materials for the hydrogen evolution reaction in acidic electrolytes has attracted considerable attention due to their potential for enabling cost-effective industrial applications. However, the unsatisfied cyclic stability and electrochemical activity limit their further application. In this work, nickel-molybdenum (Ni-Mo) alloy catalysts were successfully synthesized through a comprehensive process including electrodeposition, thermal annealing, and electrochemical activation. Owing to the synergistic interaction of molybdenum trinickelide (Ni<sub>3</sub>Mo) and molybdenum dioxide (MoO<sub>2</sub>) in Ni-Mo alloy, the catalyst display superior overall electrochemical properties. A low overpotential of 86 mV at 10 mA/cm<sup>2</sup> and a Tafel slope of 74.0 mV/dec in 0.5 mol/L H<sub>2</sub>SO<sub>4</sub> solution can be achieved. Notably, remarkable stability with negligible performance degradation even after 100 h could be maintained. This work presents a novel and effective strategy for the design and fabrication of high-performance, non-precious metal electrocatalysts for acidic water electrolysis.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 10","pages":"Pages 1509-1518"},"PeriodicalIF":0.0,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145324628","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01DOI: 10.1016/S1872-5813(25)60563-9
LI jianyu , NA wei , GAO wengui , HE pengcheng
Perovskite oxide catalysts of copper calcium titanate with lanthanum (La) substituting for calcium sites were prepared by the sol-gel method, and their performance in the photothermal CO2 hydrogenation to methanol was experimentally investigated. Techniques such as XRD, SEM, CO2-TPD, H2-TPR, XPS, UV-Vis DRS, and EIS were employed to evaluate the advantages of La substitution for the copper calcium titanate catalysts. The results showed that after an appropriate amount of La substitution, the catalyst achieved a methanol space-time yield of 5.788 mmol/(g·h) under 0.8 MPa and 250 ℃ with illumination, which represents a significant improvement in catalytic performance compared to the unsubstituted catalyst. This enhancement is attributed to the promotion of oxygen vacancy formation by La substitution, which enhances the photothermal response efficiency of the catalyst and, consequently, its catalytic activity.
{"title":"Research on the performance of photothermal catalytic CO2 hydrogenation to methanol using lanthanum- modified copper calcium titanate","authors":"LI jianyu , NA wei , GAO wengui , HE pengcheng","doi":"10.1016/S1872-5813(25)60563-9","DOIUrl":"10.1016/S1872-5813(25)60563-9","url":null,"abstract":"<div><div>Perovskite oxide catalysts of copper calcium titanate with lanthanum (La) substituting for calcium sites were prepared by the sol-gel method, and their performance in the photothermal CO<sub>2</sub> hydrogenation to methanol was experimentally investigated. Techniques such as XRD, SEM, CO<sub>2</sub>-TPD, H<sub>2</sub>-TPR, XPS, UV-Vis DRS, and EIS were employed to evaluate the advantages of La substitution for the copper calcium titanate catalysts. The results showed that after an appropriate amount of La substitution, the catalyst achieved a methanol space-time yield of 5.788 mmol/(g·h) under 0.8 MPa and 250 ℃ with illumination, which represents a significant improvement in catalytic performance compared to the unsubstituted catalyst. This enhancement is attributed to the promotion of oxygen vacancy formation by La substitution, which enhances the photothermal response efficiency of the catalyst and, consequently, its catalytic activity.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 9","pages":"Pages 1320-1329"},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145108403","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01DOI: 10.1016/S1872-5813(25)60545-7
ZHAO Yunrong , WANG Yaozu , NIU Yuqi , BIE Xuan , CHEN Rongjie , LI Qinghai , ZHANG Yanguo , ZHOU Hui
Carbon dioxide (CO2) emitted during the use of fossil fuels contributes to the global warming. Carbon capture, utilization and storage (CCUS) technology based on solid material adsorption is recognized as one of the most important means to effectively control and reduce the concentration of CO2. Magnesium oxide (MgO) is considered as an ideal adsorption material due to its high theoretical adsorption capacity, low regeneration energy consumption and wide temperature applicability. However, its actual adsorption capacity still needs to be further improved. Therefore, the internal reasons restricting the efficient adsorption of CO2 by MgO are introduced in this review. Meanwhile, the research progress on the preparation and modification of MgO based adsorbents in recent years is summarized. The preparation methods for enhancing the CO2 adsorption performance of MgO materials are reviewed, and the modification strategies of adsorbents are highlighted, for instance, microstructure modification of MgO, preparation of MgO composite adsorbents and molten salt doping modification. Furthermore, the mechanism behind different modification strategies is analyzed, moreover, the advantages and limitations of the above modification methods are summarized. Herein, the strategies to improve CO2 capture performance of MgO based adsorbents in recent years are reviewed and summarized. This review would provide insights for the design and preparation of new, cheap and efficient magnesium-based adsorbents in the future.
{"title":"Research progress on strategies to improve the carbon dioxide capture performance of MgO-based adsorbents","authors":"ZHAO Yunrong , WANG Yaozu , NIU Yuqi , BIE Xuan , CHEN Rongjie , LI Qinghai , ZHANG Yanguo , ZHOU Hui","doi":"10.1016/S1872-5813(25)60545-7","DOIUrl":"10.1016/S1872-5813(25)60545-7","url":null,"abstract":"<div><div>Carbon dioxide (CO<sub>2</sub>) emitted during the use of fossil fuels contributes to the global warming. Carbon capture, utilization and storage (CCUS) technology based on solid material adsorption is recognized as one of the most important means to effectively control and reduce the concentration of CO<sub>2</sub>. Magnesium oxide (MgO) is considered as an ideal adsorption material due to its high theoretical adsorption capacity, low regeneration energy consumption and wide temperature applicability. However, its actual adsorption capacity still needs to be further improved. Therefore, the internal reasons restricting the efficient adsorption of CO<sub>2</sub> by MgO are introduced in this review. Meanwhile, the research progress on the preparation and modification of MgO based adsorbents in recent years is summarized. The preparation methods for enhancing the CO<sub>2</sub> adsorption performance of MgO materials are reviewed, and the modification strategies of adsorbents are highlighted, for instance, microstructure modification of MgO, preparation of MgO composite adsorbents and molten salt doping modification. Furthermore, the mechanism behind different modification strategies is analyzed, moreover, the advantages and limitations of the above modification methods are summarized. Herein, the strategies to improve CO<sub>2</sub> capture performance of MgO based adsorbents in recent years are reviewed and summarized. This review would provide insights for the design and preparation of new, cheap and efficient magnesium-based adsorbents in the future.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 9","pages":"Pages 1269-1282"},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145108499","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01DOI: 10.1016/S1872-5813(25)60559-7
SONG Wenqian , WEN Yuxin , KANG Guojun , LI Dekang , HU Haoquan , JIN Lijun , LU Shijian , YAN Zhong , LIU Pengfei
Amine-based solution absorption method, as the most mature CO2 capture technology, requires enhancing CO2 desorption performance while reducing energy consumption in desorption. A series of SO2− 4/TiO2-HZSM-5 catalysts with different TiO2 contents were prepared by sol-gel method using HZSM-5 as carrier and used in CO2 catalytic desorption of N-methyl-diethanolamine and piperazine blended amine solution. Results indicated that catalyst performance can be regulated by changing the loading amount of TiO2. When the mass ratio of TiO2 to HZSM-5 was 2/1, the resultant STH(2/1) catalyst had large mesoporous surface area and abundant acidic sites and exhibited excellent catalytic performance. Compared with non-catalytic system, CO2 desorption amount of the entire desorption increased by 15.38% and relative heat duty decreased by 21.69%. Meanwhile, STH(2/1) exhibited good activity and stability after regeneration cycles and had no impact on CO2 absorption performance. Larger mesoporous surface area of catalyst facilitated sufficient contact between reactants and acidic sites. Abundant amount of strong acid sites and Brønsted acid sites provided a large amount of H+, promoting the decomposition of carbamate and deprotonation of protonated amines. The combined action of mesoporous surface area, strong acid sites and Brønsted acid sites promoted CO2 desorption. In addition, a possible mechanism for CO2 desorption catalyzed by SO2− 4/TiO2-HZSM-5 was proposed.
{"title":"Catalytic desorption performance of CO2-rich amine solution over SO2− 4/TiO2-HZSM-5","authors":"SONG Wenqian , WEN Yuxin , KANG Guojun , LI Dekang , HU Haoquan , JIN Lijun , LU Shijian , YAN Zhong , LIU Pengfei","doi":"10.1016/S1872-5813(25)60559-7","DOIUrl":"10.1016/S1872-5813(25)60559-7","url":null,"abstract":"<div><div>Amine-based solution absorption method, as the most mature CO<sub>2</sub> capture technology, requires enhancing CO<sub>2</sub> desorption performance while reducing energy consumption in desorption. A series of SO2− 4/TiO<sub>2</sub>-HZSM-5 catalysts with different TiO<sub>2</sub> contents were prepared by sol-gel method using HZSM-5 as carrier and used in CO<sub>2</sub> catalytic desorption of <em>N</em>-methyl-diethanolamine and piperazine blended amine solution. Results indicated that catalyst performance can be regulated by changing the loading amount of TiO<sub>2</sub>. When the mass ratio of TiO<sub>2</sub> to HZSM-5 was 2/1, the resultant STH(2/1) catalyst had large mesoporous surface area and abundant acidic sites and exhibited excellent catalytic performance. Compared with non-catalytic system, CO<sub>2</sub> desorption amount of the entire desorption increased by 15.38% and relative heat duty decreased by 21.69%. Meanwhile, STH(2/1) exhibited good activity and stability after regeneration cycles and had no impact on CO<sub>2</sub> absorption performance. Larger mesoporous surface area of catalyst facilitated sufficient contact between reactants and acidic sites. Abundant amount of strong acid sites and Brønsted acid sites provided a large amount of H<sup>+</sup>, promoting the decomposition of carbamate and deprotonation of protonated amines. The combined action of mesoporous surface area, strong acid sites and Brønsted acid sites promoted CO<sub>2</sub> desorption. In addition, a possible mechanism for CO<sub>2</sub> desorption catalyzed by SO2− 4/TiO<sub>2</sub>-HZSM-5 was proposed.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 9","pages":"Pages 1342-1353"},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145108398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01DOI: 10.1016/S1872-5813(25)60566-4
WANG Ji , MA Xu , GUO Hanghao , WANG Huixia , QU Yongping , JIAO Weizhou , MA Zhibin
Coal gasification slag is an excellent raw material for preparation of cementitious materials. Due to the addition of calcium-based additives, the content of non-free calcium in silicon/aluminum-rich coal gasification slag is relatively high. Thus, the influence of non-free calcium on leaching of elemental and formation mechanisms of cementitious phase were investigated by this paper. The results indicate that non-free calcium primarily disrupts the Al−O−Al bridges in the aluminosilicate glass phase, leading to decreased polymerization degree of slag. The compressive strength of cementitious materials is affected by alkali activation concentration and polymerization degree of slag. Under low-alkali conditions, as the calcium content in the gasification slag increases, the compressive strength of the cementitious material increases firstly and then decreases. Increased calcium promotes leaching of Al, however, large amounts of dissolved calcium tend to form cementitious phases and Ca(OH)2, which can hinder leaching of ions and formation of gel. In high-alkali environments, non-free calcium enhances the compressive strength of cementitious material. Glass phase in slag was destroyed by OH⁻, and leaching rates of Si and Al in slag with high-calcium increase, which lead to more C-A-S-H in cementitious material. Additionally, elevated alkalinity promotes the crystallization of sodium-minerals such as zeolites and sodalite.
煤气化渣是制备胶凝材料的优良原料。由于添加了钙基添加剂，富硅/富铝煤气化渣中的非游离钙含量较高。因此，本文研究了非游离钙对元素浸出的影响及胶凝相的形成机制。结果表明：非游离钙主要破坏铝硅酸盐玻璃相中的Al - O - Al桥，导致熔渣聚合度降低；胶凝材料的抗压强度受碱活化浓度和矿渣聚合程度的影响。低碱条件下，随着气化渣中钙含量的增加，胶凝材料的抗压强度先增大后减小。增加的钙促进Al的浸出，但大量溶解的钙容易形成胶凝相和Ca(OH)2，阻碍离子的浸出和凝胶的形成。在高碱环境下，非游离钙提高了胶凝材料的抗压强度。OH - 9破坏了渣中的玻璃相，高钙渣中Si和Al的浸出率增加，导致胶凝材料中C-A-S-H含量增加。此外，碱度的升高促进了沸石和钠石等钠矿物的结晶。
{"title":"The effect of non-free calcium on dissolution-polymerization reaction mechanism of coal gasification slag","authors":"WANG Ji , MA Xu , GUO Hanghao , WANG Huixia , QU Yongping , JIAO Weizhou , MA Zhibin","doi":"10.1016/S1872-5813(25)60566-4","DOIUrl":"10.1016/S1872-5813(25)60566-4","url":null,"abstract":"<div><div>Coal gasification slag is an excellent raw material for preparation of cementitious materials. Due to the addition of calcium-based additives, the content of non-free calcium in silicon/aluminum-rich coal gasification slag is relatively high. Thus, the influence of non-free calcium on leaching of elemental and formation mechanisms of cementitious phase were investigated by this paper. The results indicate that non-free calcium primarily disrupts the Al−O−Al bridges in the aluminosilicate glass phase, leading to decreased polymerization degree of slag. The compressive strength of cementitious materials is affected by alkali activation concentration and polymerization degree of slag. Under low-alkali conditions, as the calcium content in the gasification slag increases, the compressive strength of the cementitious material increases firstly and then decreases. Increased calcium promotes leaching of Al, however, large amounts of dissolved calcium tend to form cementitious phases and Ca(OH)<sub>2</sub>, which can hinder leaching of ions and formation of gel. In high-alkali environments, non-free calcium enhances the compressive strength of cementitious material. Glass phase in slag was destroyed by OH⁻, and leaching rates of Si and Al in slag with high-calcium increase, which lead to more C-A-S-H in cementitious material. Additionally, elevated alkalinity promotes the crystallization of sodium-minerals such as zeolites and sodalite.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 9","pages":"Pages 1416-1426"},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145108399","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01DOI: 10.1016/S1872-5813(25)60551-2
NIU Mufan, SHEN Baojian
Under the background of rapid consumption of crude oil and the impact of the “dual carbon” policy, utilizing light alkanes, which have a wider range of sources, as starting materials to prepare light olefins through dehydrogenation has become the most promising way to solve the problem of insufficient feedstock supply. Cr-based catalysts are attractive for their high activity and low cost. This paper reviews the current state of research on different process routes for the dehydrogenation of light alkanes to olefins, the reaction mechanism of oxidative dehydrogenation over Cr-based catalysts as well as the active sites were investigated and reviewed. CO2 as a weak oxidant in light alkanes dehydrogenation can alleviate the thermodynamic equilibrium limit, effectively inhibit the coking, decrease the reaction temperature and reduce energy consumption. In addition, Cr-based catalyst supports have been summarized and systematically classified. The interaction between Cr species and supports can be improved by introducing metal additives and modifying the supports, which in turn affects the dispersion and the state of Cr species. Finally, future challenges and directions for developing Cr-based catalysts for further industrial applications are discussed.
{"title":"Research progress on Cr-based catalysts for the CO2-assisted catalytic oxidative dehydrogenation of light alkanes to light olefins","authors":"NIU Mufan, SHEN Baojian","doi":"10.1016/S1872-5813(25)60551-2","DOIUrl":"10.1016/S1872-5813(25)60551-2","url":null,"abstract":"<div><div>Under the background of rapid consumption of crude oil and the impact of the “dual carbon” policy, utilizing light alkanes, which have a wider range of sources, as starting materials to prepare light olefins through dehydrogenation has become the most promising way to solve the problem of insufficient feedstock supply. Cr-based catalysts are attractive for their high activity and low cost. This paper reviews the current state of research on different process routes for the dehydrogenation of light alkanes to olefins, the reaction mechanism of oxidative dehydrogenation over Cr-based catalysts as well as the active sites were investigated and reviewed. CO<sub>2</sub> as a weak oxidant in light alkanes dehydrogenation can alleviate the thermodynamic equilibrium limit, effectively inhibit the coking, decrease the reaction temperature and reduce energy consumption. In addition, Cr-based catalyst supports have been summarized and systematically classified. The interaction between Cr species and supports can be improved by introducing metal additives and modifying the supports, which in turn affects the dispersion and the state of Cr species. Finally, future challenges and directions for developing Cr-based catalysts for further industrial applications are discussed.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 9","pages":"Pages 1283-1299"},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145108397","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01DOI: 10.1016/S1872-5813(25)60557-3
LI Baichao , SHAO Jiabei , FENG Pengcheng , WANG Jianguo , FAN Weibin , DONG Mei
Zn-modified HZSM-5 catalyst has been widely used in the aromatization of ethylene, while the effect of reaction temperature on the product distribution remains unclear, a factor that is pivotal for the design of highly efficient aromatization catalysts and the optimization of process parameters. In this work, the structure, composition, and acid properties of various Zn-containing HZSM-5 catalysts prepared via ion exchange, impregnation, and physical mixing were analyzed by XRD, ICP, NH3-TPD, and Py-FTIR. The ethylene aromatization reaction on various catalytic behaviors were carried out at 400−580 ℃. The results on HZSM-5 and ZnAl2O4-pure/HZSM-5 catalysts indicated that, with reaction temperature increasing, the aromatics selectivity and aromatics produced via the dehydrogenation route increased considerably. On Zn(IE)/HZSM-5 and ZnAl1.5O/HZSM-5 catalysts, the aromatics selectivity increased rapidly and then remained basically unchanged. However, the aromatics selectivity increases at first and then remains basically unchanged, while the proportion of dehydrogenation route remains constant, on Zn(IM)/HZSM-5 and Zn(PM)/HZSM-5 catalysts. Combined with cyclohexane dehydrogenation kinetics experiments, it is confirmed that the introduction of Zn species is helpful in reducing the dehydrogenation activation energy. Furthermore, a linear relationship is observed between the dehydrogenation activation energy of the catalysts and its acid strength and type. Interestingly, due to the absence of catalytic activity for spinel-structured ZnAl2O4, the catalytic performance and dehydrogenation activation energy of the ZnAl2O4-pure/HZSM-5 catalyst closely resemble those of HZSM-5.
{"title":"Influence of temperature on the catalytic behaviors of Zn-modified HZSM-5 catalysts for the ethylene aromatization","authors":"LI Baichao , SHAO Jiabei , FENG Pengcheng , WANG Jianguo , FAN Weibin , DONG Mei","doi":"10.1016/S1872-5813(25)60557-3","DOIUrl":"10.1016/S1872-5813(25)60557-3","url":null,"abstract":"<div><div>Zn-modified HZSM-5 catalyst has been widely used in the aromatization of ethylene, while the effect of reaction temperature on the product distribution remains unclear, a factor that is pivotal for the design of highly efficient aromatization catalysts and the optimization of process parameters. In this work, the structure, composition, and acid properties of various Zn-containing HZSM-5 catalysts prepared via ion exchange, impregnation, and physical mixing were analyzed by XRD, ICP, NH<sub>3</sub>-TPD, and Py-FTIR. The ethylene aromatization reaction on various catalytic behaviors were carried out at 400−580 ℃. The results on HZSM-5 and ZnAl<sub>2</sub>O<sub>4</sub>-pure/HZSM-5 catalysts indicated that, with reaction temperature increasing, the aromatics selectivity and aromatics produced via the dehydrogenation route increased considerably. On Zn(IE)/HZSM-5 and ZnAl<sub>1.5</sub>O/HZSM-5 catalysts, the aromatics selectivity increased rapidly and then remained basically unchanged. However, the aromatics selectivity increases at first and then remains basically unchanged, while the proportion of dehydrogenation route remains constant, on Zn(IM)/HZSM-5 and Zn(PM)/HZSM-5 catalysts. Combined with cyclohexane dehydrogenation kinetics experiments, it is confirmed that the introduction of Zn species is helpful in reducing the dehydrogenation activation energy. Furthermore, a linear relationship is observed between the dehydrogenation activation energy of the catalysts and its acid strength and type. Interestingly, due to the absence of catalytic activity for spinel-structured ZnAl<sub>2</sub>O<sub>4</sub>, the catalytic performance and dehydrogenation activation energy of the ZnAl<sub>2</sub>O<sub>4</sub>-pure/HZSM-5 catalyst closely resemble those of HZSM-5.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 9","pages":"Pages 1354-1363"},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145108401","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01DOI: 10.1016/S1872-5813(25)60568-8
DENG Lihua, XIA Wei, YANG Zhikun, ZHANG Wenda, FENG Dongdong, SUN Shaozeng, ZHAO Yijun
The technology for green and macro-conversion of solid waste biomass to prepare high-quality activated carbon demands urgent development. This study proposes a technique for synthesizing carbon adsorbents using trace KOH-catalyzed CO2 activation. Comprehensive investigations were conducted on three aspects: physicochemical structure evolution of biochar, mechanistic understanding of trace KOH-facilitated CO2 activation processes, and application characteristics for CO2 adsorption. Results demonstrate that biochar activated by trace KOH (<10%) and CO2 achieves comparable specific surface area (1244.09 m2/g) to that obtained with 100% KOH activation (1425.10 m2/g). The pore structure characteristics (specific surface area and pore volume) are governed by CO and CH4 generated through K-salt catalyzed reactions between CO2 and biochar. The optimal CO2 adsorption capacities of KBC adsorbent reached 4.70 mmol/g (0 °C) and 7.25 mmol/g (25 °C), representing the maximum values among comparable carbon adsorbents. The 5%KBC-CO2 sample exhibited CO2 adsorption capacities of 3.19 and 5.01 mmol/g under respective conditions, attaining current average performance levels. Notably, CO2/N2 selectivity (85:15, volume ratio) reached 64.71 at 0.02 bar with robust cycling stability. Molecular dynamics simulations revealed that oxygen-containing functional groups accelerate CO2 adsorption kinetics and enhance micropore storage capacity. This technical route offers simplicity, environmental compatibility, and scalability, providing critical references for large-scale preparation of high-quality carbon materials.
{"title":"Research on biochar prepared by trace KOH catalyzed CO2 activation vs KOH activation as advanced candidate for carbon capture","authors":"DENG Lihua, XIA Wei, YANG Zhikun, ZHANG Wenda, FENG Dongdong, SUN Shaozeng, ZHAO Yijun","doi":"10.1016/S1872-5813(25)60568-8","DOIUrl":"10.1016/S1872-5813(25)60568-8","url":null,"abstract":"<div><div>The technology for green and macro-conversion of solid waste biomass to prepare high-quality activated carbon demands urgent development. This study proposes a technique for synthesizing carbon adsorbents using trace KOH-catalyzed CO<sub>2</sub> activation. Comprehensive investigations were conducted on three aspects: physicochemical structure evolution of biochar, mechanistic understanding of trace KOH-facilitated CO<sub>2</sub> activation processes, and application characteristics for CO<sub>2</sub> adsorption. Results demonstrate that biochar activated by trace KOH (<10%) and CO<sub>2</sub> achieves comparable specific surface area (1244.09 m<sup>2</sup>/g) to that obtained with 100% KOH activation (1425.10 m<sup>2</sup>/g). The pore structure characteristics (specific surface area and pore volume) are governed by CO and CH<sub>4</sub> generated through K-salt catalyzed reactions between CO<sub>2</sub> and biochar. The optimal CO<sub>2</sub> adsorption capacities of KBC adsorbent reached 4.70 mmol/g (0 °C) and 7.25 mmol/g (25 °C), representing the maximum values among comparable carbon adsorbents. The 5%KBC-CO<sub>2</sub> sample exhibited CO<sub>2</sub> adsorption capacities of 3.19 and 5.01 mmol/g under respective conditions, attaining current average performance levels. Notably, CO<sub>2</sub>/N<sub>2</sub> selectivity (85:15, volume ratio) reached 64.71 at 0.02 bar with robust cycling stability. Molecular dynamics simulations revealed that oxygen-containing functional groups accelerate CO<sub>2</sub> adsorption kinetics and enhance micropore storage capacity. This technical route offers simplicity, environmental compatibility, and scalability, providing critical references for large-scale preparation of high-quality carbon materials.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 9","pages":"Pages 1330-1341"},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145108404","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01DOI: 10.1016/S1872-5813(25)60558-5
SUN Hongyang , CHEN Jun , TU Cong , ZHOU Jicheng , XU Wentao
The new technology of direct decomposition of H2S into high value-added H2 and S, as an alternative to the Claus process in industry, is an ideal route that can not only deal with toxic and abundant H2S waste gas but also recover clean energy H2, which has significant socio-economic and ecological advantages. However, the highly effective decomposition of H2S at low temperatures is still a great challenge, because of the stringent thermodynamic equilibrium constraints (only 20% even at high temperature of 1010 °C). Conventional microwave catalysts exhibit unsatisfactory performance at low temperatures (below 600 °C). Herein, Mo2C@CeO2 catalysts with a core-shell structure were successfully developed for robust microwave catalytic decomposition of H2S at low temperatures. Two carbon precursors, para-phenylenediamine (Mo2C-p) and meta-phenylenediamine (Mo2C-m), were employed to tailor Mo2C configurations. Remarkably, the H2S conversion of Mo2C-p@CeO2 catalyst at a low temperature of 550 °C is as high as 92.1%, which is much higher than the H2S equilibrium conversion under the conventional thermal conditions (2.6% at 550 °C). To our knowledge, this represents the most active catalyst for microwave catalytic decomposition of H2S at low temperature of 550 °C. Notably, Mo2C-p demonstrated superior intrinsic activity (84%) compared to Mo2C-m (6.4%), with XPS analysis revealing that its enhanced performance stems from a higher concentration of Mo2+ active sites. This work presents a substitute approach for the efficient utilization of H2S waste gas and opens up a novel avenue for the rational design of microwave catalysts for microwave catalytic reaction at low-temperature.
{"title":"Robust microwave catalytic decomposition of H2S into H2 and S at low temperature over Mo2C@CeO2 catalysts","authors":"SUN Hongyang , CHEN Jun , TU Cong , ZHOU Jicheng , XU Wentao","doi":"10.1016/S1872-5813(25)60558-5","DOIUrl":"10.1016/S1872-5813(25)60558-5","url":null,"abstract":"<div><div>The new technology of direct decomposition of H<sub>2</sub>S into high value-added H<sub>2</sub> and S, as an alternative to the Claus process in industry, is an ideal route that can not only deal with toxic and abundant H<sub>2</sub>S waste gas but also recover clean energy H<sub>2</sub>, which has significant socio-economic and ecological advantages. However, the highly effective decomposition of H<sub>2</sub>S at low temperatures is still a great challenge, because of the stringent thermodynamic equilibrium constraints (only 20% even at high temperature of 1010 °C). Conventional microwave catalysts exhibit unsatisfactory performance at low temperatures (below 600 °C). Herein, Mo<sub>2</sub>C@CeO<sub>2</sub> catalysts with a core-shell structure were successfully developed for robust microwave catalytic decomposition of H<sub>2</sub>S at low temperatures. Two carbon precursors, para-phenylenediamine (Mo<sub>2</sub>C-<em>p</em>) and meta-phenylenediamine (Mo<sub>2</sub>C-<em>m</em>), were employed to tailor Mo<sub>2</sub>C configurations. Remarkably, the H<sub>2</sub>S conversion of Mo<sub>2</sub>C-<em>p</em>@CeO<sub>2</sub> catalyst at a low temperature of 550 °C is as high as 92.1%, which is much higher than the H<sub>2</sub>S equilibrium conversion under the conventional thermal conditions (2.6% at 550 °C). To our knowledge, this represents the most active catalyst for microwave catalytic decomposition of H<sub>2</sub>S at low temperature of 550 °C. Notably, Mo<sub>2</sub>C-<em>p</em> demonstrated superior intrinsic activity (84%) compared to Mo<sub>2</sub>C-<em>m</em> (6.4%), with XPS analysis revealing that its enhanced performance stems from a higher concentration of Mo<sup>2+</sup> active sites. This work presents a substitute approach for the efficient utilization of H<sub>2</sub>S waste gas and opens up a novel avenue for the rational design of microwave catalysts for microwave catalytic reaction at low-temperature.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 9","pages":"Pages 1399-1415"},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145108498","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-01DOI: 10.1016/S1872-5813(25)60555-X
WANG Yuxuan , GUO Fenfen , JIANG Zhicheng , TU Youjing , ZHANG Xingyu , TANG Aoyi , WANG Junxia , LIANG Yuan , YAN Lishi , KONG Lingzhao
Fully utilizing renewable biomass energy is important for saving energy, reducing carbon emissions, and mitigating climate change. As the main hydrolysate of cellulose, a primary component of lignocellulose, glucose could be employed as a starting material to prepare some other functional derivatives for improving the value of biomass resources. The isomerization of glucose to produce fructose is an important intermediate process during numerous high-value-added chemical preparations. Therefore, the development of efficient and selective catalysts for glucose isomerization is of great significance. Currently, glucose isomerase catalysts are limited by the harsh conditions required for microbial activity, which restricts further improvements in fructose yield. Additionally, heterogeneous Brønsted-base and Lewis-acid catalysts commonly employed in chemical isomerization methods often lead to the formation of undesirable by-products, resulting in reduced selectivity toward fructose. This study has demonstrated that lithium-loaded heterogeneous catalysts possess excellent isomerization capabilities under mild conditions. A highly efficient Li-C3N4 catalyst was developed, achieving a fructose selectivity of 99.9% and a yield of 42.6% at 60 °C within 1.0 h—comparable to the performance of the enzymatic method. Characterization using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), proton nuclear magnetic resonance (1H NMR), and inductively coupled plasma (ICP) analyses confirmed that lithium was stably incorporated into the g-C3N4 framework through the formation of Li−N bonds. Further investigations using CO2 temperature-programmed desorption (CO2-TPD), in situ Fourier-transform infrared spectroscopy (FT-IR) and 7Li magic angle spinning nuclear magnetic resonance (7Li MAS NMR) indicated that the isomerization proceeded via a base-catalyzed mechanism. The Li species were found to interact with hydroxyl groups generated through hydrolysis and simultaneously coordinated with nitrogen atoms in the C3N4 matrix, resulting in the formation of Li-N6-H2O active sites. These active sites facilitated the deprotonation of glucose to form an enolate intermediate, followed by a proton transfer step that generated fructose. This mechanism not only improved the efficiency of fructose production but also provided valuable insight into the catalytic role of lithium within the isomerization process.
充分利用可再生生物质能，对节约能源、减少碳排放、减缓气候变化具有重要意义。作为木质纤维素的主要成分纤维素的主要水解产物，葡萄糖可以作为原料制备其他功能衍生物，以提高生物质资源的价值。葡萄糖异构化制果糖是许多高附加值化学制剂的重要中间过程。因此，开发高效、选择性的葡萄糖异构化催化剂具有重要意义。目前，葡萄糖异构酶催化剂受到微生物活动所需的苛刻条件的限制，这限制了果糖产量的进一步提高。此外，化学异构化方法中常用的多相Brønsted-base和Lewis-acid催化剂通常会导致不良副产物的形成，导致对果糖的选择性降低。本研究表明，负载锂的非均相催化剂在温和条件下具有优异的异构化能力。开发了一种高效的Li-C3N4催化剂，在60°C条件下，1.0 h内的果糖选择性为99.9%，产率为42.6%，与酶法的性能相当。利用x射线光电子能谱（XPS）、x射线衍射（XRD）、质子核磁共振（1H NMR）和电感耦合等离子体（ICP）分析证实，锂通过形成Li−N键稳定地结合到g-C3N4骨架中。利用CO2程序升温解吸（CO2- tpd）、原位傅里叶变换红外光谱（FT-IR）和7Li魔角自旋核磁共振（7Li MAS NMR）进一步研究表明，异构化是通过碱催化机制进行的。在C3N4基质中，Li与水解生成的羟基相互作用，同时与氮原子配位，形成Li- n6 - h2o活性位点。这些活性位点促进葡萄糖的去质子化，形成烯酸酯中间体，然后是质子转移步骤，产生果糖。这一机制不仅提高了果糖生产的效率，而且为锂在异构化过程中的催化作用提供了有价值的见解。
{"title":"Elucidating the catalytic role of lithium (Li) in the glucose-to-fructose isomerization over Li-C3N4 catalyst at 60 °C in water","authors":"WANG Yuxuan , GUO Fenfen , JIANG Zhicheng , TU Youjing , ZHANG Xingyu , TANG Aoyi , WANG Junxia , LIANG Yuan , YAN Lishi , KONG Lingzhao","doi":"10.1016/S1872-5813(25)60555-X","DOIUrl":"10.1016/S1872-5813(25)60555-X","url":null,"abstract":"<div><div>Fully utilizing renewable biomass energy is important for saving energy, reducing carbon emissions, and mitigating climate change. As the main hydrolysate of cellulose, a primary component of lignocellulose, glucose could be employed as a starting material to prepare some other functional derivatives for improving the value of biomass resources. The isomerization of glucose to produce fructose is an important intermediate process during numerous high-value-added chemical preparations. Therefore, the development of efficient and selective catalysts for glucose isomerization is of great significance. Currently, glucose isomerase catalysts are limited by the harsh conditions required for microbial activity, which restricts further improvements in fructose yield. Additionally, heterogeneous Brønsted-base and Lewis-acid catalysts commonly employed in chemical isomerization methods often lead to the formation of undesirable by-products, resulting in reduced selectivity toward fructose. This study has demonstrated that lithium-loaded heterogeneous catalysts possess excellent isomerization capabilities under mild conditions. A highly efficient Li-C<sub>3</sub>N<sub>4</sub> catalyst was developed, achieving a fructose selectivity of 99.9% and a yield of 42.6% at 60 °C within 1.0 h—comparable to the performance of the enzymatic method. Characterization using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), proton nuclear magnetic resonance (<sup>1</sup>H NMR), and inductively coupled plasma (ICP) analyses confirmed that lithium was stably incorporated into the g-C<sub>3</sub>N<sub>4</sub> framework through the formation of Li−N bonds. Further investigations using CO<sub>2</sub> temperature-programmed desorption (CO<sub>2</sub>-TPD), <em>in situ</em> Fourier-transform infrared spectroscopy (FT-IR) and <sup>7</sup>Li magic angle spinning nuclear magnetic resonance (<sup>7</sup>Li MAS NMR) indicated that the isomerization proceeded via a base-catalyzed mechanism. The Li species were found to interact with hydroxyl groups generated through hydrolysis and simultaneously coordinated with nitrogen atoms in the C<sub>3</sub>N<sub>4</sub> matrix, resulting in the formation of Li-N<sub>6</sub>-H<sub>2</sub>O active sites. These active sites facilitated the deprotonation of glucose to form an enolate intermediate, followed by a proton transfer step that generated fructose. This mechanism not only improved the efficiency of fructose production but also provided valuable insight into the catalytic role of lithium within the isomerization process.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 9","pages":"Pages 1373-1384"},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145108396","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号