Oxidative desulfurization (ODS) is an effective technology to eliminate sulfur compounds from fuels. Zr-based MOFs are frequently employed as ODS catalyst support. In this paper, a Zr-based MOF (NNU-28) catalyst was synthesized by a hydrothermal method, and three hydrophobic catalysts (OTES-NNU-28, DTS-NNU-28, HDTMS-NNU-28) were synthesized by surface modification with organosilanes of different alkane chains. Then the hydrophobic OTES-NNU-28, DTS-NNU-28, and HDTMS-NNU-28 were used as ODS catalysts directly without the loading of active components. The catalysts before and after hydrophobic modification were characterized by FT-IR, XPS, XRD, FE-SEM, TEM, Contact angle test, UV–Vis DRS, Mott-Schottky and N2 adsorption–desorption. Under appropriate reaction circumstances, OTES-NNU-28 can completely remove DBT in 50 min and has a good removal efficiency for BT, 4,6-DMDBT, and DBT. The removal efficiency for DBT could reach 85% after 12 cycles. We found that the electronic structure of NNU-28 is more favorable for charge migration due to its anthracene-based ligand structure with a narrow band gap and higher electron density than other typical Zr-based MOFs, and the surface hydrophobicity modification greatly improves the ODS reaction rate and the stability of the catalyst, which also verifies that the degree of hydrophobicity modification needs to be in an appropriate range. Finally, the oxidation mechanism of the catalyst in the ODS process was examined.
{"title":"Hydrophobic surface modification of Zr-based metal–organic frameworks with silane for oxidative desulfurization","authors":"Gexian Li, Linyu You, Jilong Cheng, Zekai Liu, Jinbiao Wu, Linfeng Zhang, Huadong Wu, Jia Guo","doi":"10.1016/j.fuel.2025.135333","DOIUrl":"10.1016/j.fuel.2025.135333","url":null,"abstract":"<div><div>Oxidative desulfurization (ODS) is an effective technology to eliminate sulfur compounds from fuels. Zr-based MOFs are frequently employed as ODS catalyst support. In this paper, a Zr-based MOF (NNU-28) catalyst was synthesized by a hydrothermal method, and three hydrophobic catalysts (OTES-NNU-28, DTS-NNU-28, HDTMS-NNU-28) were synthesized by surface modification with organosilanes of different alkane chains. Then the hydrophobic OTES-NNU-28, DTS-NNU-28, and HDTMS-NNU-28 were used as ODS catalysts directly without the loading of active components. The catalysts before and after hydrophobic modification were characterized by FT-IR, XPS, XRD, FE-SEM, TEM, Contact angle test, UV–Vis DRS, Mott-Schottky and N<sub>2</sub> adsorption–desorption. Under appropriate reaction circumstances, OTES-NNU-28 can completely remove DBT in 50 min and has a good removal efficiency for BT, 4,6-DMDBT, and DBT. The removal efficiency for DBT could reach 85% after 12 cycles. We found that the electronic structure of NNU-28 is more favorable for charge migration due to its anthracene-based ligand structure with a narrow band gap and higher electron density than other typical Zr-based MOFs, and the surface hydrophobicity modification greatly improves the ODS reaction rate and the stability of the catalyst, which also verifies that the degree of hydrophobicity modification needs to be in an appropriate range. Finally, the oxidation mechanism of the catalyst in the ODS process was examined.</div></div>","PeriodicalId":325,"journal":{"name":"Fuel","volume":"397 ","pages":"Article 135333"},"PeriodicalIF":6.7,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858745","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-23DOI: 10.1016/j.fuel.2025.135440
A. Ballatore, L.M.T. Somers, J.A. van Oijen
Within the context of a global de-carbonization, hydrogen plays a significant role in the transition to low-carbon activities. In particular, the Argon Power Cycle (APC) is an engine concept that circulates argon in a closed-loop configuration, burning only hydrogen and oxygen and thus rendering a zero-emissions system. The work at hand aims to provide a first step towards accurate and affordable modelling of such an engine in the high-pressure direct-injection (HPDI-H2) configuration. Using the large-eddy simulation (LES) technique, coupled with a novel tabulated chemistry approach (HR-FGM), several injections of hydrogen at high pressure in an argon–oxygen atmosphere are simulated. More in detail, parametric studies on relevant engine parameters (injection pressure, nozzle diameter, ambient pressure, ambient temperature and ambient oxygen level) are carried out and analysed in terms of ignition delay, flame dynamics and heat release rate. The corresponding results represent valuable insights into the APC combustion process and its modelling. In particular, it is found that: (a) the ignition delay is strongly sensitive to the ambient temperature, but not to the other investigated parameters, (b) the total heat release increases with the injection pressure and the nozzle diameter (and, to a lesser extent, with the ambient oxygen concentration), but the instantaneous fraction of fuel that is converted into heat decreases with increasing nozzle diameter and decreasing injection pressure, (c) OH concentration might not be a good indicator of the mass burning rate in auto-igniting hydrogen flames.
{"title":"A parametric study of high-pressure direct injections of hydrogen in an argon–oxygen environment by using large-eddy simulation and tabulated chemistry","authors":"A. Ballatore, L.M.T. Somers, J.A. van Oijen","doi":"10.1016/j.fuel.2025.135440","DOIUrl":"10.1016/j.fuel.2025.135440","url":null,"abstract":"<div><div>Within the context of a global de-carbonization, hydrogen plays a significant role in the transition to low-carbon activities. In particular, the Argon Power Cycle (APC) is an engine concept that circulates argon in a closed-loop configuration, burning only hydrogen and oxygen and thus rendering a zero-emissions system. The work at hand aims to provide a first step towards accurate and affordable modelling of such an engine in the high-pressure direct-injection (HPDI-H<sub>2</sub>) configuration. Using the large-eddy simulation (LES) technique, coupled with a novel tabulated chemistry approach (HR-FGM), several injections of hydrogen at high pressure in an argon–oxygen atmosphere are simulated. More in detail, parametric studies on relevant engine parameters (injection pressure, nozzle diameter, ambient pressure, ambient temperature and ambient oxygen level) are carried out and analysed in terms of ignition delay, flame dynamics and heat release rate. The corresponding results represent valuable insights into the APC combustion process and its modelling. In particular, it is found that: (a) the ignition delay is strongly sensitive to the ambient temperature, but not to the other investigated parameters, (b) the total heat release increases with the injection pressure and the nozzle diameter (and, to a lesser extent, with the ambient oxygen concentration), but the instantaneous fraction of fuel that is converted into heat decreases with increasing nozzle diameter and decreasing injection pressure, (c) OH concentration might not be a good indicator of the mass burning rate in auto-igniting hydrogen flames.</div></div>","PeriodicalId":325,"journal":{"name":"Fuel","volume":"397 ","pages":"Article 135440"},"PeriodicalIF":6.7,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143864982","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-23DOI: 10.1016/j.fuel.2025.135461
Xiao Luo, Peng Zhao, Xuemin Xu
CaO-based looping (CaL) process has attracted substantial attention as another available CO2 capture alternative. However, CaO-based sorbents are afflicted by severe capacity degradation over repeated carbonation/regeneration cycles. Currently, various modification approaches have been used to improve the anti-sintering property. However, these strategies are frequently associated with complex synthetic processing and expensive chemical agents, offsetting the cost gains of natural CaO resources. Herein, we developed a simple and cost-effective method to prepare self-stabilizing CaO-based sorbents via directly upcycling the CTMS only through hydration and calcination proceedings, without any additional chemical agents. Under mild conditions, CTMS-H-C exhibits an initial CO2 uptake of 0.37 gCO2 gspecimen−1. After 10 carbonation/regeneration cycles, its capacity decline rate is 29.73 %, which is much lower than that of calcined limestone (75.13 %) and commercial CaO (67.87 %), highlighting the superior cyclic stability of CTMS-H-C. Moreover, the sorption kinetic analysis reveals that the degeneration of the sorption rate is correlated with the structural deterioration caused by thermal sintering of the sorbent after multiple cycles, especially at the kinetically-controlled state. By density functional theory calculations and TG/DTG characterizations, we provide a new perspective of the enhancement mechanism of MgO on cyclic CO2 capture capability of CaO-based sorbents. The findings suggest that the incorporation of MgO can weaken the binding interaction of CO2 with CaO, which is conducive to accelerating the desorption of CO2, thereby avoiding sintering triggered by Ostwald ripening. Overall, the work not only provides a cost-effective route to CaO-based sorbent synthesis, but also offers a sustainable waste management method for magnesium smelting via vacuum carbothermal reduction by transforming CTMS to CaO-based sorbent.
{"title":"Carbothermal magnesium slag-derived self-stabilizing CaO-based sorbent for CO2 capture and its novel sintering-resistance mechanism","authors":"Xiao Luo, Peng Zhao, Xuemin Xu","doi":"10.1016/j.fuel.2025.135461","DOIUrl":"10.1016/j.fuel.2025.135461","url":null,"abstract":"<div><div>CaO-based looping (CaL) process has attracted substantial attention as another available CO<sub>2</sub> capture alternative. However, CaO-based sorbents are afflicted by severe capacity degradation over repeated carbonation/regeneration cycles. Currently, various modification approaches have been used to improve the anti-sintering property. However, these strategies are frequently associated with complex synthetic processing and expensive chemical agents, offsetting the cost gains of natural CaO resources. Herein, we developed a simple and cost-effective method to prepare self-stabilizing CaO-based sorbents via directly upcycling the CTMS only through hydration and calcination proceedings, without any additional chemical agents. Under mild conditions, CTMS-H-C exhibits an initial CO<sub>2</sub> uptake of 0.37 g<sub>CO2</sub> g<sub>specimen</sub><sup>−1</sup>. After 10 carbonation/regeneration cycles, its capacity decline rate is 29.73 %, which is much lower than that of calcined limestone (75.13 %) and commercial CaO (67.87 %), highlighting the superior cyclic stability of CTMS-H-C. Moreover, the sorption kinetic analysis reveals that the degeneration of the sorption rate is correlated with the structural deterioration caused by thermal sintering of the sorbent after multiple cycles, especially at the kinetically-controlled state. By density functional theory calculations and TG/DTG characterizations, we provide a new perspective of the enhancement mechanism of MgO on cyclic CO<sub>2</sub> capture capability of CaO-based sorbents. The findings suggest that the incorporation of MgO can weaken the binding interaction of CO<sub>2</sub> with CaO, which is conducive to accelerating the desorption of CO<sub>2</sub>, thereby avoiding sintering triggered by Ostwald ripening. Overall, the work not only provides a cost-effective route to CaO-based sorbent synthesis, but also offers a sustainable waste management method for magnesium smelting via vacuum carbothermal reduction by transforming CTMS to CaO-based sorbent.</div></div>","PeriodicalId":325,"journal":{"name":"Fuel","volume":"397 ","pages":"Article 135461"},"PeriodicalIF":6.7,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143864988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-23DOI: 10.1016/j.fuel.2025.135449
Pavol Suly, Barbora Hanulikova, Abdulkadir Bozarslan, Milan Masar, Michal Urbanek, Eva Domincova Bergerova, Michal Machovsky, Ivo Kuritka
Dual asymmetric centrifuge high-speed shear mixing is introduced as a versatile and rapid dry method for physically impregnating solid adsorbents with amine compounds. Unlike wet impregnation, which is the most reported method in literature, the dry process enables impregnating the supporting material by both low (pentaethylenehexamine) and high molecular weight amines (branched polyethyleneimine, Mw ∼ 800 g.mol−1) without using any solvent. High-speed shear mixing yields materials with CO2 adsorption/desorption abilities (simulating direct air capture and flue gas, which includes cycling) comparable to those prepared by wet impregnation, while significantly reducing the preparation time and energy consumption and decreasing the use of toxic substances. Thus, the preparation procedure for CO2 adsorbents can be successfully transformed into a clean, energy-efficient, and solvent-free process that supports sustainable development and mitigates climate change, and also be simultaneously applied to any other class I adsorbents.
{"title":"High-speed shear mixing: Versatile strategy towards the sustainable design of amine-supported CO2 adsorbents","authors":"Pavol Suly, Barbora Hanulikova, Abdulkadir Bozarslan, Milan Masar, Michal Urbanek, Eva Domincova Bergerova, Michal Machovsky, Ivo Kuritka","doi":"10.1016/j.fuel.2025.135449","DOIUrl":"10.1016/j.fuel.2025.135449","url":null,"abstract":"<div><div>Dual asymmetric centrifuge high-speed shear mixing is introduced as a versatile and rapid dry method for physically impregnating solid adsorbents with amine compounds. Unlike wet impregnation, which is the most reported method in literature, the dry process enables impregnating the supporting material by both low (pentaethylenehexamine) and high molecular weight amines (branched polyethyleneimine, <em>M<sub>w</sub></em> ∼ 800 g.mol<sup>−1</sup>) without using any solvent. High-speed shear mixing yields materials with CO<sub>2</sub> adsorption/desorption abilities (simulating direct air capture and flue gas, which includes cycling) comparable to those prepared by wet impregnation, while significantly reducing the preparation time and energy consumption and decreasing the use of toxic substances. Thus, the preparation procedure for CO<sub>2</sub> adsorbents can be successfully transformed into a clean, energy-efficient, and solvent-free process that supports sustainable development and mitigates climate change, and also be simultaneously applied to any other class I adsorbents.</div></div>","PeriodicalId":325,"journal":{"name":"Fuel","volume":"397 ","pages":"Article 135449"},"PeriodicalIF":6.7,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143865083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-22DOI: 10.1016/j.fuel.2025.135435
Zhendong Yao , Wenqing Li , Xuepeng Liu , Jianbo Chen , Chao Li , Yican Chu , Jinlong Cui , Leichao Meng , Yongfu Cui , Meiqiang Fan
Hydrolytic hydrogen production materials, particularly MgH2, have garnered extensive attention for their high hydrogen storage capacity and environmental benefits. Highly active MgH2 has better hydrolysis properties, but is also more prone to oxidative deactivation during storage, which has a great impact on its practical application. To address this contradiction between hydrolysis activity and storage stability, we developed a polymer coated cream-type MgH2. The novel designed MgH2 cream maintains air stability while enabling controllable hydrolysis upon mixing with polyethylene glycol, achieving a final hydrogen yield of 1440 mL/g, with only an 8.2% reduction after 12 h of air exposure. Furthermore, the MgH2 cream simplifies storage, enhances safety, and supports diverse applications, which provides a practical and innovative pathway for advancing hydrolytic hydrogen production technologies.
{"title":"Spear and shield in the design of cream-type MgH2 for hydrolytic hydrogen production","authors":"Zhendong Yao , Wenqing Li , Xuepeng Liu , Jianbo Chen , Chao Li , Yican Chu , Jinlong Cui , Leichao Meng , Yongfu Cui , Meiqiang Fan","doi":"10.1016/j.fuel.2025.135435","DOIUrl":"10.1016/j.fuel.2025.135435","url":null,"abstract":"<div><div>Hydrolytic hydrogen production materials, particularly MgH<sub>2</sub>, have garnered extensive attention for their high hydrogen storage capacity and environmental benefits. Highly active MgH<sub>2</sub> has better hydrolysis properties, but is also more prone to oxidative deactivation during storage, which has a great impact on its practical application. To address this contradiction between hydrolysis activity and storage stability, we developed a polymer coated cream-type MgH<sub>2</sub>. The novel designed MgH<sub>2</sub> cream maintains air stability while enabling controllable hydrolysis upon mixing with polyethylene glycol, achieving a final hydrogen yield of 1440 mL/g, with only an 8.2% reduction after 12 h of air exposure. Furthermore, the MgH<sub>2</sub> cream simplifies storage, enhances safety, and supports diverse applications, which provides a practical and innovative pathway for advancing hydrolytic hydrogen production technologies.</div></div>","PeriodicalId":325,"journal":{"name":"Fuel","volume":"397 ","pages":"Article 135435"},"PeriodicalIF":6.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858742","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-22DOI: 10.1016/j.fuel.2025.135400
Yin Yu , Jun Jiang , Xiu-Min Liu , Qi-Ying Xia , Xue-Hai Ju
Ammonia borane (AB) is known for its high hydrogen storage density. This study aims to investigate the effects of CO2 atmosphere and electric field (EF) on the mechanism of hydrogen production from AB pyrolysis. The variations of the main products, chemical bonds and the detailed decomposition pathways of AB were obtained from the reactive force field molecular dynamics (ReaxFF-MD) simulations. First, under no EF, the H2 yield in S3 system (AB/CO2 molar ratio of 2.89) is higher than that of other systems. Comparing different EF conditions, it is found that S3 system has the highest yield of H2 and H2O when the EF frequency (νEF) is 0.005 fs−1. The high-frequency EF increases the reaction rate while reducing the formation of the by-product NH3. The initial decomposition of AB is dominated by the cleavage of BH and NH bonds, as well as more intermolecular H transfer. The high-frequency EF significantly enhanced the activation of AB and promoted the pyrolysis dehydrogenation of AB·NH3BH3 → H2 + NH2BH2 is the dominant pathway. When the value of νEF exceeds 0.001 fs−1, the proportion of this pathway gradually decreases with increasing νEF. The main reaction pathway of CO2 is hydrogenation to generate CO2H fragments. The apparent activation energy of S3 system in the presence of optimal CO2 ratio and EF is 53.9 kJ/mol, which is lower than 80.0 kJ/mol of S1 (without CO2 and EF) and 68.6 kJ/mol of S3 (with CO2 but without EF). The coupling effect of CO2 and high-frequency alternating EF significantly reduces the reaction energy barrier of AB pyrolysis dehydrogenation. By leveraging the combined effects of CO2 and EF, both the yield and quality of H2 are improved. This approach not only achieves efficient hydrogen conversion but also contributes to carbon neutrality.
{"title":"Molecular dynamics simulations of hydrogen production from ammonia borane: Dual promotion by CO2 and alternating electric field","authors":"Yin Yu , Jun Jiang , Xiu-Min Liu , Qi-Ying Xia , Xue-Hai Ju","doi":"10.1016/j.fuel.2025.135400","DOIUrl":"10.1016/j.fuel.2025.135400","url":null,"abstract":"<div><div>Ammonia borane (AB) is known for its high hydrogen storage density. This study aims to investigate the effects of CO<sub>2</sub> atmosphere and electric field (EF) on the mechanism of hydrogen production from AB pyrolysis. The variations of the main products, chemical bonds and the detailed decomposition pathways of AB were obtained from the reactive force field molecular dynamics (ReaxFF-MD) simulations. First, under no EF, the H<sub>2</sub> yield in <strong>S3</strong> system (AB/CO<sub>2</sub> molar ratio of 2.89) is higher than that of other systems. Comparing different EF conditions, it is found that <strong>S3</strong> system has the highest yield of H<sub>2</sub> and H<sub>2</sub>O when the EF frequency (ν<sub>EF</sub>) is 0.005 fs<sup>−1</sup>. The high-frequency EF increases the reaction rate while reducing the formation of the by-product NH<sub>3</sub>. The initial decomposition of AB is dominated by the cleavage of B<img>H and N<img>H bonds, as well as more intermolecular H transfer. The high-frequency EF significantly enhanced the activation of AB and promoted the pyrolysis dehydrogenation of AB·NH<sub>3</sub>BH<sub>3</sub> → H<sub>2</sub> + NH<sub>2</sub>BH<sub>2</sub> is the dominant pathway. When the value of ν<sub>EF</sub> exceeds 0.001 fs<sup>−1</sup>, the proportion of this pathway gradually decreases with increasing ν<sub>EF</sub>. The main reaction pathway of CO<sub>2</sub> is hydrogenation to generate CO<sub>2</sub>H fragments. The apparent activation energy of <strong>S3</strong> system in the presence of optimal CO<sub>2</sub> ratio and EF is 53.9 kJ/mol, which is lower than 80.0 kJ/mol of <strong>S1</strong> (without CO<sub>2</sub> and EF) and 68.6 kJ/mol of <strong>S3</strong> (with CO<sub>2</sub> but without EF). The coupling effect of CO<sub>2</sub> and high-frequency alternating EF significantly reduces the reaction energy barrier of AB pyrolysis dehydrogenation. By leveraging the combined effects of CO<sub>2</sub> and EF, both the yield and quality of H<sub>2</sub> are improved. This approach not only achieves efficient hydrogen conversion but also contributes to carbon neutrality.</div></div>","PeriodicalId":325,"journal":{"name":"Fuel","volume":"397 ","pages":"Article 135400"},"PeriodicalIF":6.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143854779","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-22DOI: 10.1016/j.fuel.2025.135427
Ali Talebi, Ghasem Barati Darband
The hydrogen evolution reaction (HER) is an essential electrochemical process, integral to hydrogen production via water splitting, and a clean and sustainable energy source. The efficiency of HER is fundamentally dependent on the electrocatalyst’s performance, particularly for its intrinsic activity and long-term stability. In this study, nickel–manganese–phosphide (Ni-Mn-P) nanosheets were synthesized on nickel foam (NF) substrates through a one-step electrodeposition method using the galvanostatic technique at various current densities. The electrocatalytic behavior of these materials for HER was systematically evaluated using linear sweep voltammetry (LSV), cyclic voltammetry (CV), Tafel analysis, electrochemical impedance spectroscopy (EIS), dynamic specific resistance testing, and stability measurements. The results indicated that the sample synthesized at a current density of 1 A/cm2 exhibited superior electrocatalytic activity, achieving an overpotential of 79 mV vs. the reversible hydrogen electrode (RHE) to reach a current density of 10 mA.cm−2. Additionally, the optimized sample displayed the lowest Tafel slope and minimal charge transfer resistance (Rct), as confirmed by Tafel and EIS analyses. This study demonstrates an efficient electrochemical synthesis approach for producing highly active and stable electrocatalysts, significantly improving the efficiency of hydrogen generation.
{"title":"Ultra-fast one-step electrochemical synthesize of Ni-Mn-P as an active and stable electrocatalyst for green hydrogen production","authors":"Ali Talebi, Ghasem Barati Darband","doi":"10.1016/j.fuel.2025.135427","DOIUrl":"10.1016/j.fuel.2025.135427","url":null,"abstract":"<div><div>The hydrogen evolution reaction (HER) is an essential electrochemical process, integral to hydrogen production via water splitting, and a clean and sustainable energy source. The efficiency of HER is fundamentally dependent on the electrocatalyst’s performance, particularly for its intrinsic activity and long-term stability. In this study, nickel–manganese–phosphide (Ni-Mn-P) nanosheets were synthesized on nickel foam (NF) substrates through a one-step electrodeposition method using the galvanostatic technique at various current densities. The electrocatalytic behavior of these materials for HER was systematically evaluated using linear sweep voltammetry (LSV), cyclic voltammetry (CV), Tafel analysis, electrochemical impedance spectroscopy (EIS), dynamic specific resistance testing, and stability measurements. The results indicated that the sample synthesized at a current density of 1 A/cm2 exhibited superior electrocatalytic activity, achieving an overpotential of 79 mV vs. the reversible hydrogen electrode (RHE) to reach a current density of 10 mA.cm<sup>−2</sup>. Additionally, the optimized sample displayed the lowest Tafel slope and minimal charge transfer resistance (R<sub>ct</sub>), as confirmed by Tafel and EIS analyses. This study demonstrates an efficient electrochemical synthesis approach for producing highly active and stable electrocatalysts, significantly improving the efficiency of hydrogen generation.</div></div>","PeriodicalId":325,"journal":{"name":"Fuel","volume":"397 ","pages":"Article 135427"},"PeriodicalIF":6.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143854778","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This paper proposes an innovative double-layer reactor that decouples volatile-char interactions into distinct primary and secondary interactions, allowing for a systematic investigation of their respective effects on the pyrolysis behavior of poplar wood (PW) and the characteristics of the resulting products. Following primary interactions, a significant enhancement in bio-oil yield was observed, reaching 57.92 wt%, with anhydrosugars accounting for 13.27 % of the bio-oil composition. Concurrently, the non-condensable gas composition exhibited substantial concentrations of CO and CH4, constituting 29.05 % and 12.26 % of the gaseous products, respectively. Through controlled secondary interactions, the content of phenols and other aromatics in bio-oil ultimately reached 55.08 %. Simultaneously, the added activated carbon in interlayer demonstrated significant compositional modifications that the volatile content increased from 3.78 to 9.77 wt%, accompanied by a corresponding reduction in oxygen content to 5.73 wt%. The pore structure of activated carbon was also altered after secondary interactions. The innovative double-layer reactor enables precise control over pyrolysis product distribution and quality through its two-stage volatile-char interaction mechanism, establishing a technologically viable pathway for industrial-scale valorization of waste biomass.
{"title":"Volatile-char interactions during biomass pyrolysis: Effect of decoupled primary and secondary interactions on product control","authors":"Anjiang Gao, Hekuan Fu, Weiwei Wu, Shihao Lv, Wenran Gao, Nanfeng Zhu, Yong Huang, Félix Mérimé Bkangmo Kontchouo, Shu Zhang","doi":"10.1016/j.fuel.2025.135410","DOIUrl":"10.1016/j.fuel.2025.135410","url":null,"abstract":"<div><div>This paper proposes an innovative double-layer reactor that decouples volatile-char interactions into distinct primary and secondary interactions, allowing for a systematic investigation of their respective effects on the pyrolysis behavior of poplar wood (PW) and the characteristics of the resulting products. Following primary interactions, a significant enhancement in bio-oil yield was observed, reaching 57.92 wt%, with anhydrosugars accounting for 13.27 % of the bio-oil composition. Concurrently, the non-condensable gas composition exhibited substantial concentrations of CO and CH<sub>4</sub>, constituting 29.05 % and 12.26 % of the gaseous products, respectively. Through controlled secondary interactions, the content of phenols and other aromatics in bio-oil ultimately reached 55.08 %. Simultaneously, the added activated carbon in interlayer demonstrated significant compositional modifications that the volatile content increased from 3.78 to 9.77 wt%, accompanied by a corresponding reduction in oxygen content to 5.73 wt%. The pore structure of activated carbon was also altered after secondary interactions. The innovative double-layer reactor enables precise control over pyrolysis product distribution and quality through its two-stage volatile-char interaction mechanism, establishing a technologically viable pathway for industrial-scale valorization of waste biomass.</div></div>","PeriodicalId":325,"journal":{"name":"Fuel","volume":"397 ","pages":"Article 135410"},"PeriodicalIF":6.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858744","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-22DOI: 10.1016/j.fuel.2025.135454
Jiale Ren , Qianfei Ma , Xiaofeng Sun , Jinyuan Ma , Guorong Liu , Hua Yang
Photocatalytic reduction of CO2 into renewable fuels has been received as one of the most promising technologies to alleviate the problems of greenhouse effect and energy crisis; however, achieving the efficient conversion of CO2 selectively into a single product remains a significant challenge. In this study, we report that In3+-doping and oxygen vacancies co-engineer the active sites of the Bi2WO6 (BWO) photocatalyst to achieve efficient photoreduction of CO2 selectively into CO. Novel In3+-doped BWO hollow nanospheres with abundant oxygen vacancies have been hydrothermally prepared by using ethylene glycol (EG) as the solvent. Comprehensive experimental and theoretical studies demonstrate that the In3+ doping and oxygen vacancies synergistically lead to the formation of coordination-unsaturated Bi active sites, enhance the CO2 adsorption on the photocatalyst, promote the electron transfer from the photocatalyst to CO2, and lower the energy barriers of CO2 photoreduction; moreover, mixed defect states are introduced within the bandgap, which expand the light absorption range, promote the separation of photocarriers and prolong their lifetime. These factors collectively endow the photocatalyst with excellent CO2 photoreduction performance. The optimal In0.075BWO-EG results in the CO yield rate as high as 95.6 μmol g−1h−1 with 99.7 % selectivity, which is superior to that of other reported BWO-based photocatalysts. This research offers an important strategy and understanding for improving the CO2 photoreduction performance of photocatalysts.
{"title":"In3+-doping and oxygen vacancies co-engineering active sites of Bi2WO6 hollow nanospheres to achieve efficient photoreduction of CO2 to CO with nearly 100 % selectivity","authors":"Jiale Ren , Qianfei Ma , Xiaofeng Sun , Jinyuan Ma , Guorong Liu , Hua Yang","doi":"10.1016/j.fuel.2025.135454","DOIUrl":"10.1016/j.fuel.2025.135454","url":null,"abstract":"<div><div>Photocatalytic reduction of CO<sub>2</sub> into renewable fuels has been received as one of the most promising technologies to alleviate the problems of greenhouse effect and energy crisis; however, achieving the efficient conversion of CO<sub>2</sub> selectively into a single product remains a significant challenge. In this study, we report that In<sup>3+</sup>-doping and oxygen vacancies co-engineer the active sites of the Bi<sub>2</sub>WO<sub>6</sub> (BWO) photocatalyst to achieve efficient photoreduction of CO<sub>2</sub> selectively into CO. Novel In<sup>3+</sup>-doped BWO hollow nanospheres with abundant oxygen vacancies have been hydrothermally prepared by using ethylene glycol (EG) as the solvent. Comprehensive experimental and theoretical studies demonstrate that the In<sup>3+</sup> doping and oxygen vacancies synergistically lead to the formation of coordination-unsaturated Bi active sites, enhance the CO<sub>2</sub> adsorption on the photocatalyst, promote the electron transfer from the photocatalyst to CO<sub>2</sub>, and lower the energy barriers of CO<sub>2</sub> photoreduction; moreover, mixed defect states are introduced within the bandgap, which expand the light absorption range, promote the separation of photocarriers and prolong their lifetime. These factors collectively endow the photocatalyst with excellent CO<sub>2</sub> photoreduction performance. The optimal In<sub>0.075</sub>BWO-EG results in the CO yield rate as high as 95.6 μmol g<sup>−1</sup>h<sup>−1</sup> with 99.7 % selectivity, which is superior to that of other reported BWO-based photocatalysts. This research offers an important strategy and understanding for improving the CO<sub>2</sub> photoreduction performance of photocatalysts.</div></div>","PeriodicalId":325,"journal":{"name":"Fuel","volume":"397 ","pages":"Article 135454"},"PeriodicalIF":6.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143854781","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-22DOI: 10.1016/j.fuel.2025.135443
Bei Zhang , Huan He , Qian Zhang , Xiuxiang Tao , Fengjuan Lan , Han Zhao , Linyong Chen , Hengxing Ren , Yanfei Zhang , Hongguang Guo , Fang-Jing Liu , Asif Jamal , Muhammad Ishtiaq Ali , Rizwan Haider , P. Gopinathan , Michael Urynowicz , Zaixing Huang
Coal can be used to produce methane under anaerobic conditions through the action of microorganisms. A variety of environmental factors, including minerals, pH, and temperature, influence this process. The effect of a common carbonate mineral in coal, i.e., calcite, on the biogenic gas production was examined in this work. Biomimetic gas production was conducted by calcite amendments at various concentrations to an anaerobic fermentation system containing a high-volatile bituminous coal from Daliuta Coal Mine, Shaanxi, China. Changes in CH4 content, total volatile fatty acid (VFA) concentrations, coenzyme F420 activity, coal surface functional groups, and microbial community structure were analyzed. The results demonstrated that calcite addition promoted gas production, with the highest yield of 78.44 μmol CH4/g coal observed at a 4 % amendment. Calcite concentrations below 8 % effectively enhance the utilization of substrates such as acetic acid by methanogens, while 2 % and 4 % calcite addition significantly increased the activity of coenzyme F420. Functional groups on the coal surface, such as –OH, –NH- and –NH2, were utilized by microorganisms, which all contributed to methane generation. In terms of microbial communities, calcite addition increased the abundance of Firmicutes in the bacterial phylum and Halobacter in the archaeal phylum. At the genus level, Paraclostridium and Proteiniphilum were most abundant, suggesting their roles in the acid-producing stage and the subsequent conversion of fatty acids to methane. Based on these findings, we developed a regulatory model for methanogenic metabolism and microbial community dynamics, incorporating four regulatable points. In summary, the findings demonstrate that calcite addition at specific concentrations enhances the production of biogenic CBM through mechanisms involving microbial metabolism, community shifts, and substrate utilization.
{"title":"Effects of calcite on biogenic methane production and microbial community structure in coal","authors":"Bei Zhang , Huan He , Qian Zhang , Xiuxiang Tao , Fengjuan Lan , Han Zhao , Linyong Chen , Hengxing Ren , Yanfei Zhang , Hongguang Guo , Fang-Jing Liu , Asif Jamal , Muhammad Ishtiaq Ali , Rizwan Haider , P. Gopinathan , Michael Urynowicz , Zaixing Huang","doi":"10.1016/j.fuel.2025.135443","DOIUrl":"10.1016/j.fuel.2025.135443","url":null,"abstract":"<div><div>Coal can be used to produce methane under anaerobic conditions through the action of microorganisms. A variety of environmental factors, including minerals, pH, and temperature, influence this process. The effect of a common carbonate mineral in coal, i.e., calcite, on the biogenic gas production was examined in this work. Biomimetic gas production was conducted by calcite amendments at various concentrations to an anaerobic fermentation system containing a high-volatile bituminous coal from Daliuta Coal Mine, Shaanxi, China. Changes in CH<sub>4</sub> content, total volatile fatty acid (VFA) concentrations, coenzyme F<sub>420</sub> activity, coal surface functional groups, and microbial community structure were analyzed. The results demonstrated that calcite addition promoted gas production, with the highest yield of 78.44 μmol CH<sub>4</sub>/g coal observed at a 4 % amendment. Calcite concentrations below 8 % effectively enhance the utilization of substrates such as acetic acid by methanogens, while 2 % and 4 % calcite addition significantly increased the activity of coenzyme F<sub>420</sub>. Functional groups on the coal surface, such as –OH, –NH- and –NH<sub>2</sub>, were utilized by microorganisms, which all contributed to methane generation. In terms of microbial communities, calcite addition increased the abundance of Firmicutes in the bacterial phylum and Halobacter in the archaeal phylum. At the genus level, <em>Paraclostridium</em> and <em>Proteiniphilum</em> were most abundant, suggesting their roles in the acid-producing stage and the subsequent conversion of fatty acids to methane. Based on these findings, we developed a regulatory model for methanogenic metabolism and microbial community dynamics, incorporating four regulatable points. In summary, the findings demonstrate that calcite addition at specific concentrations enhances the production of biogenic CBM through mechanisms involving microbial metabolism, community shifts, and substrate utilization.</div></div>","PeriodicalId":325,"journal":{"name":"Fuel","volume":"397 ","pages":"Article 135443"},"PeriodicalIF":6.7,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143854780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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