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}
Pub Date : 2025-09-01DOI: 10.1016/S1872-5813(25)60540-8
CHEN Heming , DUAN junrui , YIN Shicheng , JI Jie , LU Jia
In this study, the density functional theory calculations were utilized to reveal the formation mechanisms and pathways of the significant products from α-D-galactose (the model compound of hemicellulose) pyrolysis. For the two main pyrolysis products, furan and furfural, 21 possible detailed reaction pathways were discussed for each product based on the concerted reaction mechanism. The results indicated that the energy barrier for the ring-opening reaction was the lowest at 190.07 kJ/mol in the initial reaction steps of α-D-galactose. The dominant pathway for the formation of furfural from α-D-galactose involves sequential ring-opening, isomerization, hemiacetal formation, two-step dehydration, and combined de-aldehyde and dehydration reactions, with an energy barrier of 291.53 kJ/mol. For furan, two highly competitive dominant pathways were identified, with energy barriers of 287.21 and 288.51 kJ/mol, respectively. In the former pathway, the small molecule volatiles formed are glycolic acid and water. While in the latter pathway, they are formic acid, formaldehyde, and water. In summary, this study could provide an in-depth understanding of the formation mechanisms of furan and furfural during the pyrolysis of α-D-galactose, which is helpful for better design, optimization, and control of biomass conversion.
本研究利用密度泛函理论计算揭示了α- d -半乳糖（半纤维素的模式化合物）热解的重要产物的形成机理和途径。针对呋喃和糠醛这两种主要热解产物，根据协调一致的反应机理，讨论了每种产物21种可能的详细反应途径。结果表明，α- d -半乳糖开环反应的能垒最低，为190.07 kJ/mol。α- d -半乳糖生成糠醛的主要途径包括依次开环、异构化、半缩醛生成、两步脱水和脱醛脱水联合反应，能垒为291.53 kJ/mol。对于呋喃，确定了两条高度竞争的优势途径，其能垒分别为287.21和288.51 kJ/mol。在前一种途径中，形成的小分子挥发物是乙醇酸和水。在后一种途径中，它们是甲酸、甲醛和水。综上所述，本研究可以深入了解α- d -半乳糖热解过程中呋喃和糠醛的形成机理，有助于更好地设计、优化和控制生物质转化。
{"title":"Investigation into the pyrolysis mechanism of α-D-galactose to furfural and furan","authors":"CHEN Heming , DUAN junrui , YIN Shicheng , JI Jie , LU Jia","doi":"10.1016/S1872-5813(25)60540-8","DOIUrl":"10.1016/S1872-5813(25)60540-8","url":null,"abstract":"<div><div>In this study, the density functional theory calculations were utilized to reveal the formation mechanisms and pathways of the significant products from α-D-galactose (the model compound of hemicellulose) pyrolysis. For the two main pyrolysis products, furan and furfural, 21 possible detailed reaction pathways were discussed for each product based on the concerted reaction mechanism. The results indicated that the energy barrier for the ring-opening reaction was the lowest at 190.07 kJ/mol in the initial reaction steps of α-D-galactose. The dominant pathway for the formation of furfural from α-D-galactose involves sequential ring-opening, isomerization, hemiacetal formation, two-step dehydration, and combined de-aldehyde and dehydration reactions, with an energy barrier of 291.53 kJ/mol. For furan, two highly competitive dominant pathways were identified, with energy barriers of 287.21 and 288.51 kJ/mol, respectively. In the former pathway, the small molecule volatiles formed are glycolic acid and water. While in the latter pathway, they are formic acid, formaldehyde, and water. In summary, this study could provide an in-depth understanding of the formation mechanisms of furan and furfural during the pyrolysis of α-D-galactose, which is helpful for better design, optimization, and control of biomass conversion.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 9","pages":"Pages 1385-1398"},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145108500","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)60595-0
PAN Jing , FU Danfei , YANG Hao , LUO Bifu , YANG Zhongjie
The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts, thereby enhancing their electrocatalytic performance. To tackle the unexplored challenge of substantial electrochemical overpotential, surface reconstruction has emerged as a necessary strategy. Focusing on key aspects such as Janus structures, overflow effects, the d-band center displacement hypothesis, and interface coupling related to electrochemical reactions is essential for water electrolysis. Emerging as frontrunners among next-generation electrocatalysts, Mott-Schottky (M-S) catalysts feature a heterojunction formed between a metal and a semiconductor, offering customizable and predictable interfacial synergy. This review offers an in-depth examination of the processes driving the hydrogen and oxygen evolution reactions (HER and OER), highlighting the benefits of employing nanoscale transition metal nitrides, carbides, oxides, and phosphides in M-S heterointerface catalysts. Furthermore, the challenges, limitations, and future prospects of employing M-S heterostructured catalysts for water splitting are thoroughly discussed.
{"title":"Mott-Schottky electrocatalysts for water splitting","authors":"PAN Jing , FU Danfei , YANG Hao , LUO Bifu , YANG Zhongjie","doi":"10.1016/S1872-5813(25)60595-0","DOIUrl":"10.1016/S1872-5813(25)60595-0","url":null,"abstract":"<div><div>The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts, thereby enhancing their electrocatalytic performance. To tackle the unexplored challenge of substantial electrochemical overpotential, surface reconstruction has emerged as a necessary strategy. Focusing on key aspects such as Janus structures, overflow effects, the <em>d</em>-band center displacement hypothesis, and interface coupling related to electrochemical reactions is essential for water electrolysis. Emerging as frontrunners among next-generation electrocatalysts, Mott-Schottky (M-S) catalysts feature a heterojunction formed between a metal and a semiconductor, offering customizable and predictable interfacial synergy. This review offers an in-depth examination of the processes driving the hydrogen and oxygen evolution reactions (HER and OER), highlighting the benefits of employing nanoscale transition metal nitrides, carbides, oxides, and phosphides in M-S heterointerface catalysts. Furthermore, the challenges, limitations, and future prospects of employing M-S heterostructured catalysts for water splitting are thoroughly discussed.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 9","pages":"Pages 1300-1319"},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145108402","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)60556-1
YAO Xiaoyan , LI Quan , ZHAO Xiangyu, WU Mingrui, LIU Licheng, WANG Wentai, YAO Shuo
The electrocatalytic nitrogen oxidation reaction (NOR) is a sustainable approach for converting N2 to NO-3 under mild conditions. However, it still faces challenges including inefficient N2 absorption/activation and oxygen evolution competition, sluggish kinetics, low Faradaic efficiency, and limited nitrate yields. In this work, a novel two-dimensional (2D) layered MOF Mn-BCPPy (H2BCPPy=3,5-di(4’-carboxyphenyl) pyridine) has been successfully synthesized. The framework is composed of a rod-manganese motifs and possesses abundant active sites including open metal sites (OMSs) and Lewis base sites (LBSs). The Mn-BCPPy is the first MOF catalyst applied in electrocatalytic NOR which exhibited relatively high activity with a NO-3 yield of 99.75 μg/(h·mg) and a Faraday efficiency (FE) of 32.09%. Furthermore, it can be used as fluorescent sensor for selectively and sensitively detect nitrofuran antibiotics (NFs). Therefore, this work explores the application of MOF materials in the field of electrocatalytic NOR, which reveals that manganese-based MOFs have great potential prospects.
{"title":"High-performance electrocatalytic nitrogen oxidation of two-dimensional MOF based on a rod-manganese motifs","authors":"YAO Xiaoyan , LI Quan , ZHAO Xiangyu, WU Mingrui, LIU Licheng, WANG Wentai, YAO Shuo","doi":"10.1016/S1872-5813(25)60556-1","DOIUrl":"10.1016/S1872-5813(25)60556-1","url":null,"abstract":"<div><div>The electrocatalytic nitrogen oxidation reaction (NOR) is a sustainable approach for converting N<sub>2</sub> to NO<sup>-</sup><sub>3</sub> under mild conditions. However, it still faces challenges including inefficient N<sub>2</sub> absorption/activation and oxygen evolution competition, sluggish kinetics, low Faradaic efficiency, and limited nitrate yields. In this work, a novel two-dimensional (2D) layered MOF Mn-BCPPy (H<sub>2</sub>BCPPy=3,5-di(4’-carboxyphenyl) pyridine) has been successfully synthesized. The framework is composed of a rod-manganese motifs and possesses abundant active sites including open metal sites (OMSs) and Lewis base sites (LBSs). The Mn-BCPPy is the first MOF catalyst applied in electrocatalytic NOR which exhibited relatively high activity with a NO<sup>-</sup><sub>3</sub> yield of 99.75 μg/(h·mg) and a Faraday efficiency (FE) of 32.09%. Furthermore, it can be used as fluorescent sensor for selectively and sensitively detect nitrofuran antibiotics (NFs). Therefore, this work explores the application of MOF materials in the field of electrocatalytic NOR, which reveals that manganese-based MOFs have great potential prospects.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 9","pages":"Pages 1364-1372"},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145108400","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 : 2025-08-01DOI: 10.1016/S1872-5813(25)60549-4
Peiqi PANG , Changjian XU , Ruizhu LI , Na GAO , Xianlong DU , Tao LI , Jianqiang WANG , Guoping XIAO
Electrocatalytic reduction of carbon dioxide (CO2) to carbon monoxide (CO) is an effective strategy to achieve carbon neutrality. High selective and low-cost catalysts for the electrocatalytic reduction of CO2 have received increasing attention. In contrast to the conventional tube furnace method, the high-temperature shock (HTS) method enables ultra-fast thermal processing, superior atomic efficiency, and a streamlined synthesis protocol, offering a simplified method for the preparation of high-performance single-atom catalysts (SACs). The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method, making their application in CO2 reduction reactions (CO2RR) a viable and promising avenue for further exploration. In this study, the effect of heating temperature, metal loading and different nitrogen (N) sources on the catalyst morphology, coordination environment and electrocatalytic performance were investigated. Under optimal conditions, 0.05Ni-DCD-C-1050 showed excellent performance in reducing CO2 to CO, with CO selectivity close to 100% (−0.7 to −1.0 V vsRHE) and current density as high as 130 mA/cm2 (−1.1 V vsRHE) in a flow cell under alkaline environment.
电催化还原二氧化碳（CO2）为一氧化碳（CO）是实现碳中和的有效策略。高选择性、低成本的CO2电催化还原催化剂受到越来越多的关注。与传统的管式炉方法相比，高温冲击（HTS）方法具有超快的热加工、优越的原子效率和简化的合成方案，为制备高性能单原子催化剂（SACs）提供了一种简化的方法。这些研究结果表明，利用高温还原法可以快速、方便地合成镍基SACs，使其在CO2还原反应（CO2RR）中的应用成为进一步探索的可行和有前途的途径。本研究考察了加热温度、金属负载和不同氮源对催化剂形态、配位环境和电催化性能的影响。在最佳条件下，0.05Ni-DCD-C-1050在碱性流动电池中表现出优异的CO还原性能，CO选择性接近100%(−0.7 ~−1.0 V vsRHE)，电流密度高达130 mA/cm2（−1.1 V vsRHE）。
{"title":"High temperature shock synthesis of Ni-N-C single-atom catalysts for efficient CO2 electroreduction to CO","authors":"Peiqi PANG , Changjian XU , Ruizhu LI , Na GAO , Xianlong DU , Tao LI , Jianqiang WANG , Guoping XIAO","doi":"10.1016/S1872-5813(25)60549-4","DOIUrl":"10.1016/S1872-5813(25)60549-4","url":null,"abstract":"<div><div>Electrocatalytic reduction of carbon dioxide (CO<sub>2</sub>) to carbon monoxide (CO) is an effective strategy to achieve carbon neutrality. High selective and low-cost catalysts for the electrocatalytic reduction of CO<sub>2</sub> have received increasing attention. In contrast to the conventional tube furnace method, the high-temperature shock (HTS) method enables ultra-fast thermal processing, superior atomic efficiency, and a streamlined synthesis protocol, offering a simplified method for the preparation of high-performance single-atom catalysts (SACs). The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method, making their application in CO<sub>2</sub> reduction reactions (CO<sub>2</sub>RR) a viable and promising avenue for further exploration. In this study, the effect of heating temperature, metal loading and different nitrogen (N) sources on the catalyst morphology, coordination environment and electrocatalytic performance were investigated. Under optimal conditions, 0.05Ni-DCD-C-1050 showed excellent performance in reducing CO<sub>2</sub> to CO, with CO selectivity close to 100% (−0.7 to −1.0 V <em>vs</em>RHE) and current density as high as 130 mA/cm<sup>2</sup> (−1.1 V <em>vs</em>RHE) in a flow cell under alkaline environment.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 8","pages":"Pages 1162-1172"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144886576","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}
A series of CeZnxO2 catalysts with different Zn doping contents were prepared by a reflux method and used in the direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol; various characterization techniques were employed to investigate the influence of the structure and surface properties on the catalytic performance of CeZnxO2 in the DMC synthesis. The results demonstrate that Zn2+ is incorporated into the CeO2 lattice, forming a solid solution. The Zn/Ce molar ratio can significantly modulate the Ce3+/Ce4+ redox equilibrium in CeZnxO2; with an increase of the Zn doping content, the oxygen vacancy concentration initially rises and then declines. A moderate Zn doping level (Zn/Ce = 0.5) can promote the redox process of 2Ce4+ + Zn0 = 2Ce3+ + Zn2+, resulting in the highest Ce3+ proportion and a substantial increase of the oxygen vacancy concentration. In contrast, excessive Zn doping (Zn/Ce ≥ 0.75) leads to a reduction in both the Ce3+ content and oxygen vacancy concentration. There is a strong positive correlation between the catalytic activity and the number of weak base sites, as well as a linear relationship with the surface oxygen vacancy concentration. In particular, CeZn0.5O2 with a Zn/Ce molar ratio of 0.5 exhibits the best catalytic performance in the DMC synthesis, owing to its high oxygen vacancy concentration and well-balanced distribution of basic sites.
{"title":"Influence of the structure and surface properties of CeZnxO2 on its catalytic performance in the synthesis of dimethyl carbonate from CO2 and methanol","authors":"Jingbo HUA, Jiajun PENG, Kehao LIU, Xiaoling XU, Qingmei TIAN, Yanshen LIU","doi":"10.1016/S1872-5813(25)60562-7","DOIUrl":"10.1016/S1872-5813(25)60562-7","url":null,"abstract":"<div><div>A series of CeZn<sub><em>x</em></sub>O<sub>2</sub> catalysts with different Zn doping contents were prepared by a reflux method and used in the direct synthesis of dimethyl carbonate (DMC) from CO<sub>2</sub> and methanol; various characterization techniques were employed to investigate the influence of the structure and surface properties on the catalytic performance of CeZn<sub><em>x</em></sub>O<sub>2</sub> in the DMC synthesis. The results demonstrate that Zn<sup>2+</sup> is incorporated into the CeO<sub>2</sub> lattice, forming a solid solution. The Zn/Ce molar ratio can significantly modulate the Ce<sup>3+</sup>/Ce<sup>4+</sup> redox equilibrium in CeZn<sub><em>x</em></sub>O<sub>2</sub>; with an increase of the Zn doping content, the oxygen vacancy concentration initially rises and then declines. A moderate Zn doping level (Zn/Ce = 0.5) can promote the redox process of 2Ce<sup>4+</sup> + Zn<sup>0</sup> = 2Ce<sup>3+</sup> + Zn<sup>2+</sup>, resulting in the highest Ce<sup>3+</sup> proportion and a substantial increase of the oxygen vacancy concentration. In contrast, excessive Zn doping (Zn/Ce ≥ 0.75) leads to a reduction in both the Ce<sup>3+</sup> content and oxygen vacancy concentration. There is a strong positive correlation between the catalytic activity and the number of weak base sites, as well as a linear relationship with the surface oxygen vacancy concentration. In particular, CeZn<sub>0.5</sub>O<sub>2</sub> with a Zn/Ce molar ratio of 0.5 exhibits the best catalytic performance in the DMC synthesis, owing to its high oxygen vacancy concentration and well-balanced distribution of basic sites.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 8","pages":"Pages 1243-1254"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144886496","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}
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