Wen-Jing Zhang , Yan-Cheng Hu , Yan-Hong Tan , Jia Li , Ning Li , Jing-Pei Cao
{"title":"Catalytic production of high-energy-density spiro polycyclic jet fuel with biomass derivatives","authors":"Wen-Jing Zhang , Yan-Cheng Hu , Yan-Hong Tan , Jia Li , Ning Li , Jing-Pei Cao","doi":"10.1016/j.jechem.2024.10.024","DOIUrl":"10.1016/j.jechem.2024.10.024","url":null,"abstract":"<div><div>High-energy-density (HED) fuel (e.g. widely used JP-10 and RJ-4), featuring compact 3D polycyclic structure with high strain, is of critical importance for volume-limited military aircraft, since their high density and combustion heat can provide more propulsion energy. To reduce the reliance on petroleum source, it is highly desirable to develop renewable alternatives for the production of strained polycyclic HED fuel, but which remains a big challenge because of the inaccessibility caused by the high strain. We herein demonstrate a three-step catalytic route towards highly strained C<sub>17</sub> and C<sub>18</sub> spirofuel with biomass feedstocks. The process includes catalytic aldol condensation of renewable cyclohexanone/cyclopentanone with benzaldehyde, catalytic spiro Diels-Alder (D-A) reaction of aldol adduct with isoprene, and catalytic hydrodeoxygenation. The key spiro D-A reaction is enabled by the catalysis of heterogeneous Lewis acidic ionic liquid. The chloroaluminate IL, formed by benign urea and AlCl<sub>3</sub>, exhibits good catalytic performance and reusability for this step. An eventual hydrodeoxygenation (HDO) over Pd/C and H-Y produces strained tricyclic spirofuel with density >0.93 g/mL, combustion heat >41 MJ/L and freezing point < −40 °C, which are better than the properties of tactical fuel RJ-4. Therefore, it is anticipated that the as-prepared renewable fuels have the potential to replace traditional petroleum-derived HED fuels.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"101 ","pages":"Pages 760-768"},"PeriodicalIF":13.1,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142664085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ziyi Cao , Haoteng Sun , Yi Zhang , Lixia Yuan , Yaqi Liao , Haijin Ji , Shuaipeng Hao , Zhen Li , Long Qie , Yunhui Huang
{"title":"Metallized polymer current collector as “stress acceptor” for stable micron-sized silicon anodes","authors":"Ziyi Cao , Haoteng Sun , Yi Zhang , Lixia Yuan , Yaqi Liao , Haijin Ji , Shuaipeng Hao , Zhen Li , Long Qie , Yunhui Huang","doi":"10.1016/j.jechem.2024.09.071","DOIUrl":"10.1016/j.jechem.2024.09.071","url":null,"abstract":"<div><div>Micron-sized silicon (μSi) is a promising anode material for next-generation lithium-ion batteries due to its high specific capacity, low cost, and abundant reserves. However, the volume expansion that occurs during cycling leads to the accumulation of undesirable stresses, resulting in pulverization of silicon microparticles and shortened lifespan of the batteries. Herein, a composite film of Cu-PET-Cu is proposed as the current collector (CC) for μSi anodes to replace the conventional Cu CC. Cu-PET-Cu CC is prepared by depositing Cu on both sides of a polyethylene terephthalate (PET) film. The PET layer promises good ductility of the film, permitting the Cu-PET-Cu CC to accommodate the volumetric changes of silicon microparticles and facilitates the stress release through ductile deformation. As a result, the μSi electrode with Cu-PET-Cu CC retains a high specific capacity of 2181 mA h g<sup>−1</sup>, whereas the μSi electrode with Cu CC (μSi/Cu) exhibits a specific capacity of 1285 mA h g<sup>−1</sup> after 80 cycles. The stress relieving effect of Cu-PET-Cu was demonstrated by in-situ fiber optic stress monitoring and multi-physics simulations. This work proposes an effective stress relief strategy at the electrode level for the practical implementation of μSi anodes.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"101 ","pages":"Pages 786-794"},"PeriodicalIF":13.1,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142664011","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dewen Wang , Yuting Chen , Bohan Yao , Tian Meng , Yanchao Xu , Dongxu Jiao , Zhicai Xing , Xiurong Yang
{"title":"Microdynamic modulation through Pt–O–Ni proton and electron “superhighway” for pH-universal hydrogen evolution","authors":"Dewen Wang , Yuting Chen , Bohan Yao , Tian Meng , Yanchao Xu , Dongxu Jiao , Zhicai Xing , Xiurong Yang","doi":"10.1016/j.jechem.2024.10.020","DOIUrl":"10.1016/j.jechem.2024.10.020","url":null,"abstract":"<div><div>Optimizing the microdynamics in alkaline and neutral conditions is a significant but challenging task in developing pH-universal hydrogen evolution (HER) electrocatalysts. Herein, a unique Pt–O–Ni bridge has been constructed to alter the coordination and electronic environment between Pt nanoparticles (Pt<sub>n</sub>) and nickel metaphosphate (NPO) substrate (Pt-NPO). Sufficient electron transfer from NPO to Pt<sub>n</sub> to maintain an electron-rich environment and a low valence state of Pt<sub>n</sub>. Furthermore, H* is produced from the H<sub>2</sub>O dissociation on Ni site and then spillover toward Pt sites to bind into H<sub>2</sub>, which makes up for the insufficient H<sub>2</sub>O dissociation ability of Pt in Volmer step. Pt-NPO exhibits long-term stability and only need the overpotentials of 22.3, 33.0 and 30.5 mV to attain 10 mA cm<sup>−2</sup> in alkaline, neutral and acidic media, respectively. The anion-exchange membrane (AEM) water electrolyzer catalyzed by Pt-NPO shows high water electrolysis performance that a cell voltage of 1.73 V is needed to obtain the current density of 500 mA cm<sup>−2</sup> in 1 M KOH at 80 °C, at the same time maintains good stability for 350 h. The regulation strategy proposed in this work is helpful for the design and synthesis of highly efficient pH-universal HER electrocatalysts.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"101 ","pages":"Pages 808-815"},"PeriodicalIF":13.1,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142664012","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yanchen Liu , Yang Lu , Zongliang Zhang , Bin Xu , Fangbo He , Yang Liu , Yongle Chen , Kun Zhang , Fangyang Liu
{"title":"High-areal-capacity and long-life sulfide-based all-solid-state lithium battery achieved by regulating surface-to-bulk oxygen activity","authors":"Yanchen Liu , Yang Lu , Zongliang Zhang , Bin Xu , Fangbo He , Yang Liu , Yongle Chen , Kun Zhang , Fangyang Liu","doi":"10.1016/j.jechem.2024.10.022","DOIUrl":"10.1016/j.jechem.2024.10.022","url":null,"abstract":"<div><div>Sulfide-based all-solid-state lithium batteries (ASSLBs) with nickel-rich oxide cathodes are emerging as primary contenders for the next generation rechargeable batteries, owing to their superior safety and energy density. However, the all-solid-state batteries with nickel-rich oxide cathodes suffer from performance degradation due to the reactions between the highly reactive surface oxygen of the cathode and the electrolyte, as well as the instability of the bulk oxygen structure in the cathode. Herein, we propose a synergistic modification design scheme to adjust the oxygen activity from surface to bulk. The LiBO<sub>2</sub> coating inhibits the reactivity of surface lattice oxygen ions. Meanwhile, Zr doping in the bulk phase forms strong Zr–O covalent bonds that stabilize the bulk lattice oxygen structure. The synergistic effect of these modifications prevents the release of oxygen, thus avoiding the degradation of the cathode/SE interface. Additionally, the regulation of surface-to-bulk oxygen activity establishes a highly stable interface, thereby enhancing the lithium ion diffusion kinetics and mechanical stability of the cathode. Consequently, cathodes modified with this synergistic strategy exhibit outstanding performance in sulfide-based ASSLBs, including an ultra-long cycle life of 100,000 cycles, ultra-high rate capability at 45C, and 85% high active material content in the composite cathode. Additionally, ASSLB exhibits stable cycling under high loading conditions of 82.82 mg cm<sup>−2</sup>, achieving an areal capacity of 17.90 mA h cm<sup>−2</sup>. These encouraging results pave the way for practical applications of ASSLBs in fast charging, long cycle life, and high energy density in the future.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"101 ","pages":"Pages 795-807"},"PeriodicalIF":13.1,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142664013","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jie Xu , Acheng Zhu , Zhangyu Zheng , Yiming Qi , Yuwen Cheng , Yongjie Cao , Bo Peng , Lianbo Ma , Yonggang Wang
{"title":"Building Li–S batteries with enhanced temperature adaptability via a redox-active COF-based barrier-trapping electrocatalyst","authors":"Jie Xu , Acheng Zhu , Zhangyu Zheng , Yiming Qi , Yuwen Cheng , Yongjie Cao , Bo Peng , Lianbo Ma , Yonggang Wang","doi":"10.1016/j.jechem.2024.10.019","DOIUrl":"10.1016/j.jechem.2024.10.019","url":null,"abstract":"<div><div>Covalent organic frameworks (COFs) are promising materials for mitigating polysulfide shuttling in lithium-sulfur (Li–S) batteries, but enhancing their ability to convert polysulfides across a wide temperature range remains a challenge. Herein, we introduce a redox-active COF (RaCOF) that functions as both a physical barrier and a kinetic enhancer to improve the temperature adaptability of Li–S batteries. The RaCOF constructed from redox-active anthraquinone units accelerates polysulfide conversion kinetics through reversible C=O/C-OLi transformations within a voltage range of 1.7 to 2.8 V (<em>vs.</em> Li<sup>+</sup>/Li), optimizing sulfur redox reactions in ether-based electrolytes. Unlike conventional COFs, RaCOF provides bidentate trapping of polysulfides, increasing binding energy and facilitating more effective polysulfide management. In-situ XRD and ToF-SIMS analyses confirm that RaCOF enhances polysulfide adsorption and promotes the transformation of lithium sulfide (Li<sub>2</sub>S), leading to better sulfur cathode reutilization. Consequently, RaCOF-modified Li–S batteries demonstrate low self-discharge (4.0% decay over a 7-day rest), excellent wide-temperature performance (stable from −10 to + 60 °C), and high-rate cycling stability (94% capacity retention over 500 cycles at 5.0 C). This work offers valuable insights for designing COF structures aimed at achieving temperature-adaptive performance in rechargeable batteries.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"101 ","pages":"Pages 702-712"},"PeriodicalIF":13.1,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142664017","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yicheng Lin , Shaohua Luo , Pengyu Li , Jun Cong , Wei Zhao , Lixiong Qian , Qi Sun , Shengxue Yan
{"title":"Introducing strong metal–oxygen bonds to suppress the Jahn-Teller effect and enhance the structural stability of Ni/Co-free Mn-based layered oxide cathodes for potassium-ion batteries","authors":"Yicheng Lin , Shaohua Luo , Pengyu Li , Jun Cong , Wei Zhao , Lixiong Qian , Qi Sun , Shengxue Yan","doi":"10.1016/j.jechem.2024.10.017","DOIUrl":"10.1016/j.jechem.2024.10.017","url":null,"abstract":"<div><div>Mn-based layered oxides (KMO) have emerged as one of the promising low-cost cathodes for potassium-ion batteries (PIBs). However, due to the multiple-phase transitions and the distortion in the MnO<sub>6</sub> structure induced by the Jahn-Teller (JT) effect associated with Mn-ion, the cathode exhibits poor structural stability. Herein, we propose a strategy to enhance structural stability by introducing robust metal–oxygen (M–O) bonds, which can realize the pinning effect to constrain the distortion in the transition metal (TM) layer. Concurrently, all the elements employed have exceptionally high crustal abundance. As a proof of concept, the designed K<sub>0.5</sub>Mn<sub>0.9</sub>Mg<sub>0.025</sub>Ti<sub>0.025</sub>Al<sub>0.05</sub>O<sub>2</sub> cathode exhibited a discharge capacity of approximately 100 mA h g<sup>−1</sup> at 20 mA g<sup>−1</sup> with 79% capacity retention over 50 cycles, and 73% capacity retention over 200 cycles at 200 mA g<sup>−1</sup>, showcased much better battery performance than the designed cathode with less robust M–O bonds. The properties of the formed M–O bonds were investigated using theoretical calculations. The enhanced dynamics, mitigated JT effect, and improved structural stability were elucidated through the in-situ X-ray diffractometer (XRD), in-situ electrochemical impedance spectroscopy (EIS) (and distribution of relaxation times (DRT) method), and ex-situ X-ray absorption fine structure (XAFS) tests. This study holds substantial reference value for the future design of cost-effective Mn-based layered cathodes for PIBs.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"101 ","pages":"Pages 713-722"},"PeriodicalIF":13.1,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142663938","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ruijuan Wang , Yixu Zhang , Zhi Li , Lei Wu , Jiarui Chen , Xiaolin Liu , Hui Hu , Hao Ding , Shuang Cao , Qiliang Wei , Xianyou Wang
{"title":"Improving structure stability of single-crystalline Ni-rich cathode at high voltage by element gradient doping and interfacial modification","authors":"Ruijuan Wang , Yixu Zhang , Zhi Li , Lei Wu , Jiarui Chen , Xiaolin Liu , Hui Hu , Hao Ding , Shuang Cao , Qiliang Wei , Xianyou Wang","doi":"10.1016/j.jechem.2024.10.015","DOIUrl":"10.1016/j.jechem.2024.10.015","url":null,"abstract":"<div><div>Single-crystalline Ni-rich cathodes can provide high energy density and capacity retention rates for lithium-ion batteries (LIBs). However, single-crystalline Ni-rich cathodes experience severe transition metal dissolution, irreversible phase transitions, and reduced structural stability during prolonged cycling at high voltage, which will significantly hinder their practical application. Herein, a Li<sub>4</sub>TeO<sub>5</sub> surface coating along with bulk Te-gradient doping strategy is proposed and developed to solve these issues for single-crystalline Ni-rich LiNi<sub>0.90</sub>Co<sub>0.05</sub>Mn<sub>0.05</sub>O<sub>2</sub> cathode (LTeO-1.0). It has been found that the bulk Te<sup>6+</sup> gradient doping can lead to the formation of robust Te–O bonds that effectively inhibit H2-H3 phase transformations and reinforce the lattice framework, and the in-situ Li<sub>4</sub>TeO<sub>5</sub> coating layer can act as a protective layer that suppresses the parasitic reactions and grain fragmentation. Besides, the modified material exhibits a higher Young’s modulus, which will be conducive to maintaining significant structural and electrochemical stability under high-voltage conditions. Especially, the LTeO-1.0 electrode shows the improved Li<sup>+</sup> diffusion kinetics and thermodynamic stability as well as high capacity retention of 95.83% and 82.12% after 200 cycles at the cut-off voltage of 4.3 and 4.5 V. Therefore, the efficacious dual-modification strategy will definitely contribute to enhancing the structural and electrochemical stability of single-crystalline Ni-rich cathodes and developing their application in LIBs.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"101 ","pages":"Pages 630-640"},"PeriodicalIF":13.1,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594084","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Duo Chen , Yuanhang Wang , Tengyu Yao , Hang Yang , Laifa Shen
{"title":"Unraveling the exceptional kinetics of Zn||organic batteries in hydrated deep eutectic solution","authors":"Duo Chen , Yuanhang Wang , Tengyu Yao , Hang Yang , Laifa Shen","doi":"10.1016/j.jechem.2024.10.016","DOIUrl":"10.1016/j.jechem.2024.10.016","url":null,"abstract":"<div><div>Intuitively, the solvation structure featuring stronger interacted sheath in deep eutectic solution (DES) electrolyte would result in sluggish interfacial charge transfer and intense polarization, which obstructs its practical application in emerging Zn based batteries. Unexpectedly, here we discover a Zn||organic battery with exceptional kinetics properties enabled by a hydrated DES electrolyte, which can render higher discharge capacity, smaller voltage polarization, and faster kinetics of charge transfer in comparison with conventional aqueous 3 M ZnCl<sub>2</sub> electrolyte, though its viscosity is two orders of magnitude higher than the latter. The improved kinetics of charge transfer and ion diffusion is demonstrated to originate from the local electron structure regulation of cathode in hydrated DES electrolyte. Furthermore, the DES electrolyte has also been shown to restrict parasitic reaction associated with active water by preferential urea-molecular adsorption on Zn surface and stronger water trapping in solvation structure, giving rise to long-term stable dendrite-free Zn plating/stripping. This work provides a new rationale for understanding electrochemical behaviors of organic cathodes in DES electrolyte, which is conducive to the development of high-performance Zn||organic batteries.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"101 ","pages":"Pages 570-577"},"PeriodicalIF":13.1,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571544","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Realizing interfacial coupled electron/ion transport through reducing the interfacial oxygen density of carbon skeletons for high-performance lithium metal anodes","authors":"Yao-Lu Ye , Yan Zhou , Huan Ye , Fei-Fei Cao","doi":"10.1016/j.jechem.2024.09.063","DOIUrl":"10.1016/j.jechem.2024.09.063","url":null,"abstract":"<div><div>Lithium plating/stripping occurs at the anode/electrolyte interface which involves the flow of electrons from the current collector and the migration of lithium ions from the solid-electrolyte interphase (SEI). The dual continuous rapid transport of interfacial electron/ion is required for homogeneous Li deposition. Herein, we propose a strategy to improve the Li metal anode performance by rationally regulating the interfacial electron density and Li ion transport through the SEI film. This key technique involves decreasing the interfacial oxygen density of biomass-derived carbon host by regulating the arrangement of the celluloses precursor fibrils. The higher specific surface area and lower interfacial oxygen density decrease the local current density and ensure the formation of thin and even SEI film, which stabilized Li<sup>+</sup> transfer through the Li/electrolyte interface. Moreover, the improved graphitization and the interconnected conducting network enhance the surface electronegativity of carbon and enable uninterruptible electron conduction. The result is continuous and rapid coupled interfacial electron/ion transport at the anode/electrolyte reaction interface, which facilitates uniform Li deposition and improves Li anode performance. The Li/C anode shows a high initial Coulombic efficiency of 98% and a long-term lifespan of over 150 cycles at a practical low N/P (negative-to-positive) ratio of 1.44 in full cells.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"101 ","pages":"Pages 744-750"},"PeriodicalIF":13.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142664084","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cao Guo , Sanshuang Gao , Jun Li , Menglin Zhou , Abdukader Abdukayum , Qingquan Kong , Yingtang Zhou , Guangzhi Hu
{"title":"P-tuned FeN2 binuclear sites for boosted CO2 electro-reduction","authors":"Cao Guo , Sanshuang Gao , Jun Li , Menglin Zhou , Abdukader Abdukayum , Qingquan Kong , Yingtang Zhou , Guangzhi Hu","doi":"10.1016/j.jechem.2024.10.011","DOIUrl":"10.1016/j.jechem.2024.10.011","url":null,"abstract":"<div><div>The recycling of CO<sub>2</sub> through electrochemical processes offers a promising solution for alleviating the greenhouse effect; however, the activation of CO<sub>2</sub> and desorption of *CO in electrocatalytic CO<sub>2</sub> reduction (ECR) frequently encounter high energy barriers and competitive hydrogen evolution reactions (HERs), which are urgent problems that need to be addressed. In this study, a catalyst (P<sub>100</sub>–Fe–N/C) with homogeneous P–tuned FeN<sub>2</sub> binuclear sites (N<sub>2</sub>PFe-FePN<sub>2</sub>) was successfully synthesised, demonstrating satisfactory performance in the ECR to CO. P<sub>100</sub>–Fe–N/C attains a peak <em>FE<sub>CO</sub></em> of 98.01% and a normalized TOF of 664.7 h<sup>−1</sup> at −0.7 V<sub>RHE</sub>, surpassing the performance of the Fe binuclear catalyst without P and single-atoms catalysts. In the MEA cell, a <em>FE</em><sub>CO</sub> exceeding 90% can still be achieved. Density functional theory analysis indicates that the asymmetric coordination configuration induced by the incorporation of P facilitates a reduction in the system’s energy. The modulation of P results in the <em>d</em>-band centre of the catalyst being positioned closer to the Fermi level, which facilitates the interaction of the catalyst with CO<sub>2</sub>, allowing more electrons to be injected into the CO<sub>2</sub> molecule at the Fe binuclear sites and inhibiting the HER. The P–tuned FeN<sub>2</sub> binuclear sites effectively lower the *CO desorption barrier.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"101 ","pages":"Pages 816-824"},"PeriodicalIF":13.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142664014","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}