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}
Pub Date : 2025-08-01DOI: 10.1016/S1872-5813(25)60543-3
Linyao HUANG , Mi LUO , Tianhua YANG , Chenguang WANG
In this paper, a series of Cr-doped RuO2@NC catalysts (Cr0.1-RuO2@NC, Cr0.2-RuO2@NC, Cr0.4-RuO2@NC) with controlled Cr doping (0.5%, 1%, 3%) were prepared to investigate the mechanistic interplay between transition metal doping, oxygen vacancy (OV) formation and oxygen evolution reaction (OER) performance. Systematic characterization results reveal that the oxygen vacancy concentration follows a volcano-type trend with increasing Cr content, peaking at 1% Cr doping (Cr0.2-RuO2@NC). Combined X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses confirm that Cr doping effectively induces electronic structure reconstruction of RuO2, generating high-density oxygen vacancies that serve as electrochemically active sites. The optimized Cr0.2-RuO2@NC catalyst exhibits exceptional OER performance, achieving a low overpotential of 223 mV at 10 mA/cm2 and a Tafel slope of 63.8 mV/dec, significantly surpassing its 0.5% and 3% doped counterparts. Remarkably, it retains 99.9% of the initial activity after 27 h. Cr doping not only regulates the concentration of oxygen vacancies through lattice distortion. The strong Cr–O covalent bonding enhances the structural stability of the catalyst. This work establishes a general transition metal doping strategy for precise oxygen vacancy engineering, providing new design principles and theoretical foundations for developing high-performance OER electrocatalysts.
{"title":"Tuning oxygen vacancy via transition metal doping for efficient oxygen evolution reaction","authors":"Linyao HUANG , Mi LUO , Tianhua YANG , Chenguang WANG","doi":"10.1016/S1872-5813(25)60543-3","DOIUrl":"10.1016/S1872-5813(25)60543-3","url":null,"abstract":"<div><div>In this paper, a series of Cr-doped RuO<sub>2</sub>@NC catalysts (Cr<sub>0.1</sub>-RuO<sub>2</sub>@NC, Cr<sub>0.2</sub>-RuO<sub>2</sub>@NC, Cr<sub>0.4</sub>-RuO<sub>2</sub>@NC) with controlled Cr doping (0.5%, 1%, 3%) were prepared to investigate the mechanistic interplay between transition metal doping, oxygen vacancy (O<sub>V</sub>) formation and oxygen evolution reaction (OER) performance. Systematic characterization results reveal that the oxygen vacancy concentration follows a volcano-type trend with increasing Cr content, peaking at 1% Cr doping (Cr<sub>0.2</sub>-RuO<sub>2</sub>@NC). Combined X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses confirm that Cr doping effectively induces electronic structure reconstruction of RuO<sub>2</sub>, generating high-density oxygen vacancies that serve as electrochemically active sites. The optimized Cr<sub>0.2</sub>-RuO<sub>2</sub>@NC catalyst exhibits exceptional OER performance, achieving a low overpotential of 223 mV at 10 mA/cm<sup>2</sup> and a Tafel slope of 63.8 mV/dec, significantly surpassing its 0.5% and 3% doped counterparts. Remarkably, it retains 99.9% of the initial activity after 27 h. Cr doping not only regulates the concentration of oxygen vacancies through lattice distortion. The strong Cr–O covalent bonding enhances the structural stability of the catalyst. This work establishes a general transition metal doping strategy for precise oxygen vacancy engineering, providing new design principles and theoretical foundations for developing high-performance OER electrocatalysts.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 8","pages":"Pages 1173-1182"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144886577","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)60534-2
Yan CHEN, Huanhuan HE, Yufeng LI, Bing LIU, Xiaohao LIU
In Fischer-Tropsch synthesis (FTS), iron-based catalysts are prone to deactivation due to carbon deposition. To address this challenge, we developed a simple physical powder-mixing strategy by mechanically mixing iron-based FTS catalysts with oxides such as SiO2, MgO, ZnO, ZrO2, MnO2, Al2O3, and graphene oxide (GO). Experimental results demonstrate that oxide incorporation significantly suppresses carbon deposition in a composition-dependent manner, thereby enhancing catalytic stability. Notably, after mixing with SiO2 or MgO powder, the CO conversion reached 96.6% and 97.6%, respectively, maintaining stability for more than 20 h. In contrast, catalyst mixed with quartz sand particles underwent rapid deactivation within 20, with a decrease in CO conversion from 93.0% to 14.6%, accompanied by a sharp rise in CH4 selectivity. By combining various characterization methods such as XRD, Mossbauer spectroscopy, TGA, XPS and CO-TPD, the promoting mechanism of oxides on reaction stability was deeply studied. The results indicate that the catalyst mixed SiO2 powder reduced the content of active χ-Fe5C2 phases from 97% to 52.1% and effectively suppressed carbon deposition. This enhancement is attributed to the strong interfacial interactions between SiO2 and the iron-based catalyst, which moderately inhibited CO adsorption and dissociation kinetics, decelerated carbonization, and prevented rapid accumulation of carbon species on the catalyst surface. Similar mechanisms were observed over MgO additives, further validating the role of oxide-iron interactions. This work elucidates the mechanism of the interaction between iron-based catalysts and mixed oxides on carbon deposition behavior in Fischer-Tropsch synthesis reactions, providing an innovative strategy and theoretical foundation for designing highly active and stable catalysts.
{"title":"Study on the regulation of Fischer-Tropsch synthesis catalytic performance by mixing oxides with iron-based catalysts","authors":"Yan CHEN, Huanhuan HE, Yufeng LI, Bing LIU, Xiaohao LIU","doi":"10.1016/S1872-5813(25)60534-2","DOIUrl":"10.1016/S1872-5813(25)60534-2","url":null,"abstract":"<div><div>In Fischer-Tropsch synthesis (FTS), iron-based catalysts are prone to deactivation due to carbon deposition. To address this challenge, we developed a simple physical powder-mixing strategy by mechanically mixing iron-based FTS catalysts with oxides such as SiO<sub>2</sub>, MgO, ZnO, ZrO<sub>2</sub>, MnO<sub>2</sub>, Al<sub>2</sub>O<sub>3</sub>, and graphene oxide (GO). Experimental results demonstrate that oxide incorporation significantly suppresses carbon deposition in a composition-dependent manner, thereby enhancing catalytic stability. Notably, after mixing with SiO<sub>2</sub> or MgO powder, the CO conversion reached 96.6% and 97.6%, respectively, maintaining stability for more than 20 h. In contrast, catalyst mixed with quartz sand particles underwent rapid deactivation within 20, with a decrease in CO conversion from 93.0% to 14.6%, accompanied by a sharp rise in CH<sub>4</sub> selectivity. By combining various characterization methods such as XRD, Mossbauer spectroscopy, TGA, XPS and CO-TPD, the promoting mechanism of oxides on reaction stability was deeply studied. The results indicate that the catalyst mixed SiO<sub>2</sub> powder reduced the content of active χ-Fe<sub>5</sub>C<sub>2</sub> phases from 97% to 52.1% and effectively suppressed carbon deposition. This enhancement is attributed to the strong interfacial interactions between SiO<sub>2</sub> and the iron-based catalyst, which moderately inhibited CO adsorption and dissociation kinetics, decelerated carbonization, and prevented rapid accumulation of carbon species on the catalyst surface. Similar mechanisms were observed over MgO additives, further validating the role of oxide-iron interactions. This work elucidates the mechanism of the interaction between iron-based catalysts and mixed oxides on carbon deposition behavior in Fischer-Tropsch synthesis reactions, providing an innovative strategy and theoretical foundation for designing highly active and stable catalysts.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 8","pages":"Pages 1212-1222"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144886580","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)60542-1
Hongyi CHEN, Anning ZHOU, Fuxin CHEN, Xinyu JIA, Yagang ZHANG, Mengdan MA, Jie LING, Wenlong LI
To address the issues of low yield and selectivity of benzaldehyde in the photocatalytic CO2-toluene reactions, a ZnTi-LDH photocatalyst with exposed hydroxyl groups was developed and a novel co-photocatalytic reaction system involving O2/CO2-toluene was established. The structure of ZnTi-LDH catalyst was characterized using XRD, FT-IR, N2 adsorption-desorption isotherms, XPS and other techniques. The effects of catalyst composition and O2/CO2 ratio on the yield and selectivity of benzaldehyde in the O2/CO2 co-photocatalytic oxidation of toluene were investigated in a pressurized reactor. The techniques and instruments such as isotope tracing, radical quenching, GC-MS, EPR, and others were employed to elucidate the free radical mechanism underlying the O2/CO2 synergistic photocatalytic oxidation of toluene. The results indicate that under solvent-free conditions, with a ZnTi-LDH catalyst composition of 3:1 (ZT-3:1) and an O2/CO2 ratio of 2:8, the irradiation by xenon light for 12 h yielded CO and benzaldehyde at rates of 121.37 and 947.89 μmol/(g·h), respectively, with selectivities of 96% and 60%. The total yield was 3.02 times higher than that of the CO2-toluene reaction alone. Selectivities for CO and benzaldehyde increased by 7% and 11%, respectively. These improvements are attributed primarily to the abundant −OH groups and high specific surface area of ZT-3:1, which promote the activation of CO2 adsorption on the catalyst, and the synergistic effect of O2 and CO2 expands the pathways for free radical reactions and improves the carrier utilization efficiency. This study provides a new approach to enhancing the CO2 conversion efficiency and co-producing the high-value-added products.
针对苯甲醛在光催化co2 -甲苯反应中产率低、选择性差的问题，研制了一种羟基暴露的ZnTi-LDH光催化剂，建立了一种新的O2/ co2 -甲苯共光催化反应体系。采用XRD、FT-IR、N2吸附-脱附等温线、XPS等技术对ZnTi-LDH催化剂的结构进行了表征。在加压反应器中研究了O2/CO2共光催化氧化甲苯反应中催化剂组成和O2/CO2比对苯甲醛收率和选择性的影响。采用同位素示踪、自由基猝灭、GC-MS、EPR等技术和仪器对O2/CO2协同光催化氧化甲苯的自由基机理进行了研究。结果表明，在无溶剂条件下，在ZnTi-LDH催化剂配比为3:1 （ZT-3:1）、O2/CO2比为2:8的条件下，氙灯照射12 h， CO和苯甲醛的产率分别为121.37和947.89 μmol/(g·h)，选择性分别为96%和60%。总产率是co2 -甲苯单独反应的3.02倍。对CO和苯甲醛的选择性分别提高了7%和11%。这些改善主要是由于丰富的−OH基团和ZT-3:1的高比表面积促进了CO2在催化剂上吸附的活化，O2和CO2的协同作用扩展了自由基反应的途径，提高了载体的利用效率。该研究为提高CO2转化效率和协同生产高附加值产品提供了一条新途径。
{"title":"Photocatalytic oxidation of toluene to benzaldehyde over exposed hydroxyl ZnTi-LDH nanosheets with O2/CO2","authors":"Hongyi CHEN, Anning ZHOU, Fuxin CHEN, Xinyu JIA, Yagang ZHANG, Mengdan MA, Jie LING, Wenlong LI","doi":"10.1016/S1872-5813(25)60542-1","DOIUrl":"10.1016/S1872-5813(25)60542-1","url":null,"abstract":"<div><div>To address the issues of low yield and selectivity of benzaldehyde in the photocatalytic CO<sub>2</sub>-toluene reactions, a ZnTi-LDH photocatalyst with exposed hydroxyl groups was developed and a novel co-photocatalytic reaction system involving O<sub>2</sub>/CO<sub>2</sub>-toluene was established. The structure of ZnTi-LDH catalyst was characterized using XRD, FT-IR, N<sub>2</sub> adsorption-desorption isotherms, XPS and other techniques. The effects of catalyst composition and O<sub>2</sub>/CO<sub>2</sub> ratio on the yield and selectivity of benzaldehyde in the O<sub>2</sub>/CO<sub>2</sub> co-photocatalytic oxidation of toluene were investigated in a pressurized reactor. The techniques and instruments such as isotope tracing, radical quenching, GC-MS, EPR, and others were employed to elucidate the free radical mechanism underlying the O<sub>2</sub>/CO<sub>2</sub> synergistic photocatalytic oxidation of toluene. The results indicate that under solvent-free conditions, with a ZnTi-LDH catalyst composition of 3:1 (ZT-3:1) and an O<sub>2</sub>/CO<sub>2</sub> ratio of 2:8, the irradiation by xenon light for 12 h yielded CO and benzaldehyde at rates of 121.37 and 947.89 μmol/(g·h), respectively, with selectivities of 96% and 60%. The total yield was 3.02 times higher than that of the CO<sub>2</sub>-toluene reaction alone. Selectivities for CO and benzaldehyde increased by 7% and 11%, respectively. These improvements are attributed primarily to the abundant −OH groups and high specific surface area of ZT-3:1, which promote the activation of CO<sub>2</sub> adsorption on the catalyst, and the synergistic effect of O<sub>2</sub> and CO<sub>2</sub> expands the pathways for free radical reactions and improves the carrier utilization efficiency. This study provides a new approach to enhancing the CO<sub>2</sub> conversion efficiency and co-producing the high-value-added products.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 8","pages":"Pages 1148-1161"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144886495","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)60541-X
Hongxing WANG , Lifeng CUI , Jie ZHANG , Shuhao WU , Shuai ZHANG , Ye TIAN , Xingang LI
γ-valerolactone (GVL) is a platform chemical derived from lignocellulose, which can be used as fuel additives, green solvent and feeding for the production of other high-value chemicals. Its efficient synthesis is of great significance for the development and utilization of biomass downstream products. Herein, with CuZnAl hydrotalcite as the precursor, a series of Cu-based catalysts with different Cu grain sizes were prepared by changing the aging temperature and used in the solvent-free gas-phase hydrogenation of ethyl levulinate (EL) to produce GVL. The Cu-based catalysts were systematically characterized by various techniques such as N2 sorption, XRD, SEM, TEM, H2-TPR, NH3-TPD, and in situ XPS, while the effect of Cu grain size on the performance of Cu-based catalyst in the EL hydrogenation was investigated. The results indicate that the electron cloud density of Cu as well as the Cu0/(Cu0+Cu+) ratio increase with a decrease of the Cu grain size; in addition, the Cu-based catalyst prepared by aging at a low temperature displays a large surface area and abundant acid sites. The synergistic effect of Cu0 sites and acid sites endows the Cu-based catalyst with superior performance in the EL hydrogenation to GVL. In particular, for the EL gas-phase hydrogenation under mild conditions (atmospheric pressure, 140 ℃, 0.3 h−1), the Cu-based catalyst prepared by aging at 30 ℃ achieves an EL conversion of 99.9% and a selectivity of 99.5% to GVL, with no significant deactivation observed in 240 h. The insight shown in this work should be meaningful for the large-scale production of GVL.
{"title":"Influence of Cu grain size on the performance of Cu-based catalyst in the gas-phase hydrogenation of ethyl levulinate","authors":"Hongxing WANG , Lifeng CUI , Jie ZHANG , Shuhao WU , Shuai ZHANG , Ye TIAN , Xingang LI","doi":"10.1016/S1872-5813(25)60541-X","DOIUrl":"10.1016/S1872-5813(25)60541-X","url":null,"abstract":"<div><div>γ-valerolactone (GVL) is a platform chemical derived from lignocellulose, which can be used as fuel additives, green solvent and feeding for the production of other high-value chemicals. Its efficient synthesis is of great significance for the development and utilization of biomass downstream products. Herein, with CuZnAl hydrotalcite as the precursor, a series of Cu-based catalysts with different Cu grain sizes were prepared by changing the aging temperature and used in the solvent-free gas-phase hydrogenation of ethyl levulinate (EL) to produce GVL. The Cu-based catalysts were systematically characterized by various techniques such as N<sub>2</sub> sorption, XRD, SEM, TEM, H<sub>2</sub>-TPR, NH<sub>3</sub>-TPD, and <em>in situ</em> XPS, while the effect of Cu grain size on the performance of Cu-based catalyst in the EL hydrogenation was investigated. The results indicate that the electron cloud density of Cu as well as the Cu<sup>0</sup>/(Cu<sup>0</sup>+Cu<sup>+</sup>) ratio increase with a decrease of the Cu grain size; in addition, the Cu-based catalyst prepared by aging at a low temperature displays a large surface area and abundant acid sites. The synergistic effect of Cu<sup>0</sup> sites and acid sites endows the Cu-based catalyst with superior performance in the EL hydrogenation to GVL. In particular, for the EL gas-phase hydrogenation under mild conditions (atmospheric pressure, 140 ℃, 0.3 h<sup>−1</sup>), the Cu-based catalyst prepared by aging at 30 ℃ achieves an EL conversion of 99.9% and a selectivity of 99.5% to GVL, with no significant deactivation observed in 240 h. The insight shown in this work should be meaningful for the large-scale production of GVL.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 8","pages":"Pages 1223-1232"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144886498","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(24)60531-1
Ruitao LI , Kun GONG , Yuanyuan DAI , Qiang NIU , Tiejun LIN , Liangshu ZHONG
CeO2 based semiconductor are widely used in solar-driven photothermal catalytic dry reforming of methane (DRM) reaction, but still suffer from low activity and low light utilization efficiency. This study developed graphite-CeO2 interfaces to enhance solar-driven photothermal catalytic DRM. Compared with carbon nanotubes-modified CeO2 (CeO2-CNT), graphite-modified CeO2 (CeO2-GRA) constructed graphite-CeO2 interfaces with distortion in CeO2, leading to the formation abundant oxygen vacancies. These graphite-CeO2 interfaces with oxygen vacancies enhanced optical absorption and promoted the generation and separation of photogenerated carriers. The high endothermic capacity of graphite elevated the catalyst surface temperature from 592.1−691.3 ℃, boosting light-to-thermal conversion. The synergy between photogenerated carriers and localized heat enabled Ni/CeO2-GRA to achieve a CO production rate of 9985.6 mmol/(g·h) (vs7192.4 mmol/(g·h) for Ni/ CeO2) and a light-to-fuel efficiency of 21.8% (vs13.8% for Ni/ CeO2). This work provides insights for designing graphite-semiconductor interfaces to advance photothermal catalytic efficiency.
{"title":"Constructing graphite-CeO2 interfaces to enhance the photothermal activity for solar-driven dry reforming of methane","authors":"Ruitao LI , Kun GONG , Yuanyuan DAI , Qiang NIU , Tiejun LIN , Liangshu ZHONG","doi":"10.1016/S1872-5813(24)60531-1","DOIUrl":"10.1016/S1872-5813(24)60531-1","url":null,"abstract":"<div><div>CeO<sub>2</sub> based semiconductor are widely used in solar-driven photothermal catalytic dry reforming of methane (DRM) reaction, but still suffer from low activity and low light utilization efficiency. This study developed graphite-CeO<sub>2</sub> interfaces to enhance solar-driven photothermal catalytic DRM. Compared with carbon nanotubes-modified CeO<sub>2</sub> (CeO<sub>2</sub>-CNT), graphite-modified CeO<sub>2</sub> (CeO<sub>2</sub>-GRA) constructed graphite-CeO<sub>2</sub> interfaces with distortion in CeO<sub>2</sub>, leading to the formation abundant oxygen vacancies. These graphite-CeO<sub>2</sub> interfaces with oxygen vacancies enhanced optical absorption and promoted the generation and separation of photogenerated carriers. The high endothermic capacity of graphite elevated the catalyst surface temperature from 592.1−691.3 ℃, boosting light-to-thermal conversion. The synergy between photogenerated carriers and localized heat enabled Ni/CeO<sub>2</sub>-GRA to achieve a CO production rate of 9985.6 mmol/(g·h) (<em>vs</em>7192.4 mmol/(g·h) for Ni/ CeO<sub>2</sub>) and a light-to-fuel efficiency of 21.8% (<em>vs</em>13.8% for Ni/ CeO<sub>2</sub>). This work provides insights for designing graphite-semiconductor interfaces to advance photothermal catalytic efficiency.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 8","pages":"Pages 1137-1147"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144886581","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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