Energy & Fuels最新文献

{"title":"Enhanced Oxygen Evolution Reaction Performance of ZnO Nanorods on Activated Carbon Cloth","authors":"Chandra Prakash,&nbsp;Ula Suliman,&nbsp;Sadegh Pour-Ali,&nbsp;Ambesh Dixit*,&nbsp;Jing Liu* and Shiva Mohajernia*,&nbsp;","doi":"10.1021/acs.energyfuels.4c0618410.1021/acs.energyfuels.4c06184","DOIUrl":"https://doi.org/10.1021/acs.energyfuels.4c06184https://doi.org/10.1021/acs.energyfuels.4c06184","url":null,"abstract":"<p >The employment of an abundant and cost-effective electrocatalyst for water splitting gained significant attention, as there is a need for a substitute for precious metals in the production of affordable H₂ as a promising energy carrier. This study addresses the need for cost-effective, high-activity, and binder-free oxygen evolution reaction (OER) electrocatalysts by investigating ZnO nanorods (ZnO NRs) integrated with electrochemically activated carbon cloth (ECAT@CC). Various characterization techniques, including XRD, XPS, and FE-SEM, confirmed the formation of ZnO NRs on ECAT@CC during conventional hydrothermal synthesis in an aqueous solution containing (CH₃COO)₂Zn·2H₂O and C₆H₁₂N₄ at 95 °C. The electrochemical performance was evaluated using linear sweep voltammetry, chronopotentiometry, and electrochemical impedance spectroscopy in alkaline conditions. The ZnO NRs/ECAT@CC annealed for 3 h at 450 °C exhibited superior OER activity, with an overpotential of 1.58 V vs RHE at a current density of 10 mA/cm², and improved charge transfer resistance of 65.89 Ω·cm², significantly lower than that of pristine and ECAT@CC samples. During the stability test, the robustness of the ZnO NRs/ECAT@CC-3h sample was demonstrated over the prolonged operation. This research highlights ZnO NRs/ECAT@CC-3h as a promising, binder-free, and self-supported OER electrocatalyst, which can contribute to more efficient and sustainable processes in electrochemical water splitting.</p>","PeriodicalId":35,"journal":{"name":"Energy & Fuels","volume":"39 12","pages":"5897–5906 5897–5906"},"PeriodicalIF":5.2,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703858","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Advances in Developing Inorganic Calcium Solid-State Electrolytes: A Minireview","authors":"Xiaofeng Wu,&nbsp;Anik Brinckerhoff,&nbsp;Julie Nguyen,&nbsp;Marshall Pasternak and Hong Fang*,&nbsp;","doi":"10.1021/acs.energyfuels.5c0027310.1021/acs.energyfuels.5c00273","DOIUrl":"https://doi.org/10.1021/acs.energyfuels.5c00273https://doi.org/10.1021/acs.energyfuels.5c00273","url":null,"abstract":"<p >The technology of lithium-ion batteries is reaching its limit of energy density and cost reduction in usage for electrochemical energy storage. As a promising long-term sustainable alternative to lithium-based technology, Ca-ion batteries (CIBs) coupled with metal anodes are increasingly gaining scientific attention. Ca solid-state electrolytes (SSEs) are key components for the development of CIBs. In this minireview, we summarize and discuss the most recent advances of inorganic Ca ionic conductors as potential SSE candidates. We focus on their SSE-relevant properties, including the Ca-ion conductivity, electrochemical stability, and ionic diffusion mechanisms, with the key challenges and future perspectives elucidated.</p>","PeriodicalId":35,"journal":{"name":"Energy & Fuels","volume":"39 12","pages":"5691–5698 5691–5698"},"PeriodicalIF":5.2,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703869","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Designing Spherical Sucrose-Derived Hard Carbon Materials with Abundant Closed Pores via Amino-Aldehyde Condensation","authors":"Yanmei Zhao,&nbsp;Yafang Zhao,&nbsp;Jun Zheng,&nbsp;Yueying Lin,&nbsp;Chuanfang Liu,&nbsp;Jiafan Zheng,&nbsp;Chengyu Zhang,&nbsp;Kai Zhang* and Zhongrong Shen*,&nbsp;","doi":"10.1021/acs.energyfuels.5c0008810.1021/acs.energyfuels.5c00088","DOIUrl":"https://doi.org/10.1021/acs.energyfuels.5c00088https://doi.org/10.1021/acs.energyfuels.5c00088","url":null,"abstract":"<p >Hydrothermal carbonization of sucrose is a conventional method for preparing hard carbon (HC) microsphere precursors; the construction of closed pores plays a crucial role in enhancing the platform capacity of sugar-based HC materials. This work proposes a strategy of a cohydrothermal method with sucrose and organic amine molecules to regulate the content of closed pores. Amine molecules undergo an amine-aldehyde condensation reaction with furfural intermediates during the hydrothermal process of sucrose, participating in the formation of carbon precursors. During the carbonization process, the presence of amine molecules accelerates the pyrolysis of the precursor and alters the microstructure of the HC microsphere precursor. This ultimately leads to the construction of closed pore structures during subsequent carbonization, thereby significantly enhancing the platform capacity. Research finds that different amine molecules affect the sodium ion storage behavior of the HC anode materials. Specifically, aniline-involved sucrose-derived HC (HCBS) and benzylamine-involved sucrose-derived HC (HCBIS) deliver large closed-pore volume of 0.072 m³ g^–1 and 0.095 m³ g^–1, respectively, much higher than sucrose-derived HC (HCS) of 0.024 m³ g^–1. HCBS exhibits a remarkable reversible capacity of 382 mA h g^–1 at a current density of 0.020 A g^–1. Ex situ Raman tests demonstrate that the plateau capacity of HCBS (277 mA h g^–1) results from both sodium ion intercalation and closed pore filling; conversely, the plateau capacity of HCBIS is primarily attributed to closed-pore filling. This work proposes a novel design concept to create abundant closed pores HC from sucrose, contributing to the rational design of the pore structure of sugar-based HC.</p>","PeriodicalId":35,"journal":{"name":"Energy & Fuels","volume":"39 12","pages":"5974–5985 5974–5985"},"PeriodicalIF":5.2,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703865","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Machine Learning-Guided Optimization of Bimetallic Oxide Nanostructures for Enhanced OER Electrocatalytic Activity","authors":"Ammara Fatima,&nbsp;Muhammad Asad,&nbsp;Ghada Eid,&nbsp;Farhan Zafar,&nbsp;Merfat M. Alsabban,&nbsp;Mehar Muhammad Hamza Maqbool,&nbsp;Naeem Akhtar*,&nbsp;Muhammad Ali Khan*,&nbsp;Cong Yu* and Mohamed M. El-Toony,&nbsp;","doi":"10.1021/acs.energyfuels.4c0541710.1021/acs.energyfuels.4c05417","DOIUrl":"https://doi.org/10.1021/acs.energyfuels.4c05417https://doi.org/10.1021/acs.energyfuels.4c05417","url":null,"abstract":"<p >Transition metals are increasingly replacing noble-metal-based OER electrocatalysts due to their low cost and availability. However, they often face challenges of low electrocatalytic activity and stability. To address these limitations, bimetallic or composite materials have been extensively developed, leveraging synergistic effects to enhance catalytic efficiency. Unfortunately, optimizing these systems remains challenging, as the individual contributions of each component to the overall electrocatalytic performance are not yet fully understood, and limited attention has been given to this issue. To address this issue, herein we employed machine learning (ML) algorithms to optimize and identify the most influential component governing OER electrocatalytic efficacy. We synthesized a bimetallic OER catalyst by coating electrospun nanofibers of polyaniline (PA) and cellulose acetate (CA) on nickel foam (NF), followed by drop-casting of CuO-NiO (CNO) onto the nanofiber surface. ML was applied to optimize and construct the best-fit combination of the designed bimetallic OER catalyst. Results reveal that ML-optimized CNO/CA-PA@NF shows high electrocatalytic activity, showing a low overpotential of 326 mV at 10 mA cm^–2, Tafel slope of 52 mV dec^–1, and an onset potential of 1.48 V vs RHE. Additionally, it shows high stability, which could be ascribed to cohesive interfacial interactions between CNO and CA-PA nanofibers. To the best of our knowledge, this is the first report to highlight the transformative role of ML optimization in advancing bimetallic transition-metal-based electrocatalysts, thus paving the way for durable and efficient OER systems for sustainable energy applications.</p>","PeriodicalId":35,"journal":{"name":"Energy & Fuels","volume":"39 12","pages":"5877–5885 5877–5885"},"PeriodicalIF":5.2,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703838","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of CaCO3 on the Phase Evolution in Simultaneous Removal of SO2 and NO2 by Calcium Hydroxide","authors":"Bin Zhou,&nbsp;Xinqing Zou,&nbsp;Guoqiang Gao,&nbsp;Jianguo Hong,&nbsp;Tiehua Cao,&nbsp;Shuhua Geng*,&nbsp;Yuwen Zhang* and Xionggang Lu,&nbsp;","doi":"10.1021/acs.energyfuels.4c0631810.1021/acs.energyfuels.4c06318","DOIUrl":"https://doi.org/10.1021/acs.energyfuels.4c06318https://doi.org/10.1021/acs.energyfuels.4c06318","url":null,"abstract":"<p >This study mainly focuses on investigating the effect of in situ-generated CaCO₃ on simultaneous SO₂ and NO₂ removal, clarifying the competitive mechanism of CO₂, SO₂, and NO₂ with absorbent Ca(OH)₂ in the removal process. The experiments were carried out by the precarbonated absorbent, whose contents were mainly Ca(OH)₂ and CaCO₃. The results of the DFT calculation showed that the molecular adsorption energies of CO₂, NO₂, and SO₂ on the surface of Ca(OH)₂ were −3.42, −1.28, and −1.16 eV, respectively, and the adsorption order on the surface of Ca(OH)₂ was CO₂ &gt; NO₂ &gt; SO₂ under the sintering flue gas condition. The phase evolution was elucidated by morphology and composition analysis of the removal products. In the process of simultaneous removal of SO₂ and NO₂, CO₂ first reacted with absorbent Ca(OH)₂ to reach equilibrium. The generated CaCO₃ covered the surface of the absorbent, which weakens the activity of the absorbent. At the later stage of the removal process, the activity of Ca(OH)₂ decreased. The in situ-generated CaCO₃ participated in SO₂ and NO₂ removal reactions, while the removal effect was lower than that of Ca(OH)₂.</p>","PeriodicalId":35,"journal":{"name":"Energy & Fuels","volume":"39 12","pages":"5919–5928 5919–5928"},"PeriodicalIF":5.2,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703830","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Characterization of Light Hydrocarbons in Brazilian Pre-Salt Crude Oils: Applications in Reservoir Geochemistry","authors":"Dayane M. Coutinho*,&nbsp;Clarisse L. Torres,&nbsp;Vinícius B. Pereira,&nbsp;Raquel V. S. Silva,&nbsp;Mônica C. Santos,&nbsp;Daniel S. Dubois,&nbsp;Joelma P. Lopes,&nbsp;Gabriela Vanini,&nbsp;Francisco R. Aquino Neto and Débora A. Azevedo*,&nbsp;","doi":"10.1021/acs.energyfuels.4c0611210.1021/acs.energyfuels.4c06112","DOIUrl":"https://doi.org/10.1021/acs.energyfuels.4c06112https://doi.org/10.1021/acs.energyfuels.4c06112","url":null,"abstract":"<p >The analysis of crude oil, especially light hydrocarbons (LHs) fractions or ranges, remains a challenging task in reservoir geochemistry. The large number of isomers hinders chromatographic separation, highlighting the necessity and urgency of developing comprehensive and rapid assessment methods. Advanced analytical techniques are vital in providing practical answers for monitoring oil production from enhanced oil recovery. The present study employs a new approach for the detailed characterization of LHs (C₅–C₁₅) in crude oils using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS) with a 30 m column length in the first dimension (¹D) and multiple modulation periods in a single run with simple sample preparation. The work aimed to obtain a rapid analysis with adequate resolution and selectivity to apply to LHs monitoring and to understand the behavior of the oil under the influence of injection of water alternating gas (WAG) into a reservoir over time (time-lapse geochemistry study). Adjusting the temperature program associated with multiple modulation period parameters provided a considerably shorter overall runtime analysis. In a repeatability study, the ratios between saturated and aromatic hydrocarbons (LHs) showed 15% RSD, being important data for inferring the hydraulic communication process in wells. Seven presalt crude oils from the Brazilian Santos Basin were collected from the same well during a seven-year production period, and the WAG recovery process showed compositional variations in LHs per carbon atom distributions, mainly for aromatic, naphthenic, and <i>iso</i>-alkane classes. The individual saturated and aromatic hydrocarbon ratios revealed differences between the crude oils from the same well. The developed method achieved rapid LH assessment and has promise in enhancing oil field management.</p>","PeriodicalId":35,"journal":{"name":"Energy & Fuels","volume":"39 12","pages":"5789–5801 5789–5801"},"PeriodicalIF":5.2,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.energyfuels.4c06112","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703775","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Dual-Role Additive as a CO2 Hydrate Promoter and a Corrosion Inhibitor: Application in CO2 Capture, Transportation, and Sequestration","authors":"Varsha Choudhary,&nbsp;Aditi Tyagi,&nbsp;Shweta Negi,&nbsp;Prakashaiah B G*,&nbsp;Gaurav Pandey,&nbsp;Sanat Kumar and Asheesh Kumar*,&nbsp;","doi":"10.1021/acs.energyfuels.5c0038910.1021/acs.energyfuels.5c00389","DOIUrl":"https://doi.org/10.1021/acs.energyfuels.5c00389https://doi.org/10.1021/acs.energyfuels.5c00389","url":null,"abstract":"<p >Chemical additives are known to play a crucial role in the deployment of gas hydrate-based CO₂ capture, transportation, and sequestration (CCTS) technologies. In this study, we investigate the effectiveness of a new additive, 1,2,3-benzotriazole (BTA), in promoting CO₂ hydrate formation and inhibiting corrosion. We evaluated the kinetics of CO₂ hydrate formation using various concentrations of BTA, ranging from 0.1 to 1.0 wt %, under operating conditions of 3.2 ± 0.2 MPa pressure and approximately 274 ± 0.5 K temperature. Moreover, we examine the impact of the gas-to-liquid ratio on the CO₂ hydrate formation kinetics. The results indicate that BTA significantly enhances the hydrate formation kinetics and improves CO₂ storage capacity. Additionally, we conducted electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), and gravimetric analysis to assess the corrosion inhibition efficacy of BTA in 1 M HCl and CO₂-saturated saline water (3.5% NaCl) at various concentrations. Our findings demonstrate that BTA serves a dual function as a hydrate promoter and a corrosion inhibitor.</p>","PeriodicalId":35,"journal":{"name":"Energy & Fuels","volume":"39 12","pages":"5832–5844 5832–5844"},"PeriodicalIF":5.2,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703781","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Comprehensive Analysis of the Mutual Feedback Mechanisms between CO2 Geological Storage and Underground Coal Mining in the Ordos Basin","authors":"Keyao Lin,&nbsp;Tieya Jing,&nbsp;Ning Wei*,&nbsp;Quan Chen,&nbsp;Wentao Zhao,&nbsp;Juan Zhou,&nbsp;Muhammad Ali,&nbsp;Wendong Wang and Xiaochun Li,&nbsp;","doi":"10.1021/acs.energyfuels.4c0630910.1021/acs.energyfuels.4c06309","DOIUrl":"https://doi.org/10.1021/acs.energyfuels.4c06309https://doi.org/10.1021/acs.energyfuels.4c06309","url":null,"abstract":"<p >The Ordos Basin, a representative sedimentary basin in China, possesses abundant underground coal and saline aquifer resources, which often overlap spatially. Complex mutual feedback mechanisms arise when the CO₂ geological storage (CGS) and underground coal mining (UCM) operate simultaneously. While previous studies have focused on CGS or UCM individually, the mutual feedback mechanisms between these activities remain poorly understood. To address this gap, this study comprehensively analyzes the mutual feedback mechanisms between CGS and UCM in the Ordos Basin. Specifically, this paper explores the necessity of CGS and UCM and the technological challenges they face while conducting rock laboratory experiments and establishing a mutual feedback model to analyze these mechanisms comprehensively. The results show that the deformation of the coal seam caused by a single reservoir CGS is 1.76 mm, and the deformation of the top of the reservoir caused by UCM is 0.39 mm, with both deformations at the millimeter scale. The safety distance between CGS and UCM is determined to be 500 m horizontally and 1187.26 m vertically. Beyond this safety distance, joint CGS and UCM operations can mitigate the magnitude of stress and displacement associated with UCM operations alone. Based on the Huaneng Zhengning power plant CCUS aquifer storage project, this study provides theoretical and technical guidance for integrating carbon capture, utilization, and storage (CCUS) with underground multiresource applications. This work aligns with global climate and energy security goals by improving resource utilization, reducing carbon emissions, and promoting environmental sustainability.</p>","PeriodicalId":35,"journal":{"name":"Energy & Fuels","volume":"39 12","pages":"5802–5817 5802–5817"},"PeriodicalIF":5.2,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"SiO2 Particle Deposition on KCl Initial Deposit Layers","authors":"Jakob Meister,&nbsp;Peter Glarborg,&nbsp;Wei Wang and Hao Wu*,&nbsp;","doi":"10.1021/acs.energyfuels.4c0586010.1021/acs.energyfuels.4c05860","DOIUrl":"https://doi.org/10.1021/acs.energyfuels.4c05860https://doi.org/10.1021/acs.energyfuels.4c05860","url":null,"abstract":"<p >This study presents experiments investigating the influence of an initial layer on particle sticking probability, proving that an initial layer can initiate and enhance the sticking probability of incoming particles. The findings reveal that the deposition of SiO₂ particles is influenced by both the deposit probe temperature (350 and 500 °C) and the morphology of the KCl initial layer. The KCl initial layer is composed of two types of morphology─a fine powdery layer made of submicron particles and a coarse layer made of crystal-like dendrites. The formation of the coarse layer is promoted by a longer KCl exposure time and a higher probe temperature. For thin initial layers with a large powdery fraction, higher probe temperatures during SiO₂ deposition result in a larger amount of deposit, highlighting the significant role of probe temperature in this phase. Additionally, the probe temperature during the KCl initial layer formation affects the deposition behavior, with higher temperatures reducing the deposit mass. Conversely, for thicker initial layers with a higher fraction of crystal-like dendrites, the probe temperature during the KCl initial layer generation becomes more critical, with higher temperatures leading to decreased SiO₂ deposits. The complexity of the deposition process, even in a simple two-component system, is attributed to multiple relevant phenomena, including the softening and melting of the initial layer, sintering, and the energy dissipation potential of the different structures in an initial layer.</p>","PeriodicalId":35,"journal":{"name":"Energy & Fuels","volume":"39 12","pages":"5938–5946 5938–5946"},"PeriodicalIF":5.2,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703782","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"One-Step Synthesis of Nitrogen-Doped α-MoC Supported on SBA-15 with Enhanced Catalytic Activity for the Reverse Water–Gas Shift Reaction","authors":"Jie Zhao*,&nbsp;Xiaolong Zhang,&nbsp;Ruru Sun,&nbsp;Tao Zhang,&nbsp;Ruixue Bao and Chuanyi Wang,&nbsp;","doi":"10.1021/acs.energyfuels.4c0585010.1021/acs.energyfuels.4c05850","DOIUrl":"https://doi.org/10.1021/acs.energyfuels.4c05850https://doi.org/10.1021/acs.energyfuels.4c05850","url":null,"abstract":"<p >The reverse water–gas shift reaction (RWGS) has been regarded as an essential route for CO₂ utilization, and molybdenum carbides show promise as efficient RWGS catalysts. Herein, we investigate the evolution of MoO₃ to α-MoC in a mixture of CH₄/NH₃/H₂ (5/1/15 by volume) and how the nitrogen dopant modulates the catalytic activity of α-MoC for the RWGS reaction. It is found that the MoO₃ evolution in the mixture follows a path: MoO₃ → MoO₂ → MoO_<i>z</i>N_<i>y</i>C_<i>x</i> → MoN_<i>y</i>C_<i>x</i> → N-doped α-MoC. The moderate nitrogen-doped content favors the α-MoC activity due to enhanced CO desorption. As a result, the optimized N-doped α-MoC synthesized at 680 °C exhibited 39% CO₂ conversion with 98.5% CO selectivity at 400 °C, 24,000 mL g^–1 h^–1 space velocity, and 0.1 MPa, which is close to the equilibrium conversion (40.3%). <i>In situ</i> Fourier transform infrared (FTIR) spectroscopy reveals that the adsorbed formic acid, carboxyl, and formate species were identified as intermediates of the RWGS reaction. The enhanced CO desorption makes the conversion of the intermediates to CO smoother and the activity more stable at lower reaction temperatures. This work develops a simple method for the preparation of cubic α-MoC and the role of N doping in the RWGS reaction.</p>","PeriodicalId":35,"journal":{"name":"Energy & Fuels","volume":"39 12","pages":"5778–5788 5778–5788"},"PeriodicalIF":5.2,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703742","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}