Hard carbon (HC) is an attractive anode for sodium-ion batteries (SIBs), but its practical application has been hindered by low reversible capacity and initial coulombic efficiency (ICE). In this study, we propose a CO2-assisted carbonization strategy based on a tunable phenolic resin as the precursor. The carbonization process can be governed by a two-step process, CO2-induced pore opening followed by carbon skeletal reorganization, promoting the formation of well-controlled closed micropores and improved surface chemistry. Structural and electrochemical characterization studies further demonstrate that such modification greatly enhances sodium storage performance. The optimized HC anode exhibited a high initial capacity of 305.8 mAh g−1 and an ICE of 95.6% at 30 mA g−1. These values are much higher than those for the traditional control (230.9 mAh g−1, 86.16%). After 500 cycles at 1 A g−1, it also retained 90.02% of its capacity. This work provides an efficient and controllable route for designing high-performance SIB anodes and offering new application potential of phenolic resin-based carbons in sustainable electrochemical energy storage.
硬碳（HC）是一种极具吸引力的钠离子电池负极材料，但其可逆容量低、初始库仑效率（ICE）低，阻碍了其实际应用。在这项研究中，我们提出了一种基于可调酚醛树脂作为前驱体的二氧化碳辅助碳化策略。炭化过程可分为两步过程，即co2诱导孔隙打开，然后碳骨架重组，促进了封闭微孔的形成，并改善了表面化学性质。结构和电化学表征研究进一步表明，这种修饰大大提高了钠的存储性能。优化后的HC阳极具有305.8 mAh g−1的高初始容量，在30 mA g−1时的ICE为95.6%。这些值远高于传统对照（230.9 mAh g−1,86.16%）。在1 A g−1下循环500次后，它还保留了90.02%的容量。本研究为高性能SIB阳极的设计提供了一条有效、可控的途径，并为酚醛树脂基碳在可持续电化学储能方面的应用提供了新的潜力。
{"title":"Engineering the pore structure in phenolic resin-derived hard carbon via CO2-assisted carbonization for enhanced sodium storage","authors":"Wei Wang, Binyuan Zhang, Hairu Wang, Rui Ma, Lili Ai, Mengjiao Xu, Changyu Leng, Qingtao Ma, Dianzeng Jia, Nannan Guo, Luxiang Wang","doi":"10.1039/d5qi02184g","DOIUrl":"https://doi.org/10.1039/d5qi02184g","url":null,"abstract":"Hard carbon (HC) is an attractive anode for sodium-ion batteries (SIBs), but its practical application has been hindered by low reversible capacity and initial coulombic efficiency (ICE). In this study, we propose a CO<small><sub>2</sub></small>-assisted carbonization strategy based on a tunable phenolic resin as the precursor. The carbonization process can be governed by a two-step process, CO<small><sub>2</sub></small>-induced pore opening followed by carbon skeletal reorganization, promoting the formation of well-controlled closed micropores and improved surface chemistry. Structural and electrochemical characterization studies further demonstrate that such modification greatly enhances sodium storage performance. The optimized HC anode exhibited a high initial capacity of 305.8 mAh g<small><sup>−1</sup></small> and an ICE of 95.6% at 30 mA g<small><sup>−1</sup></small>. These values are much higher than those for the traditional control (230.9 mAh g<small><sup>−1</sup></small>, 86.16%). After 500 cycles at 1 A g<small><sup>−1</sup></small>, it also retained 90.02% of its capacity. This work provides an efficient and controllable route for designing high-performance SIB anodes and offering new application potential of phenolic resin-based carbons in sustainable electrochemical energy storage.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"87 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034160","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 Tian, Shiyu Wang, Min Wang, Nana Zheng, Jing Xie, Jindou Hu, Zhenjiang Lu, Yali Cao
The design of an efficient and corrosion-resistant bifunctional electrocatalyst through coupling the urea oxidation reaction (UOR) and the hydrogen evolution reaction (HER) in seawater for large-scale hydrogen generation still poses challenges. Herein, Pt/Ni(OH)2/NF was successfully synthesised via spontaneous galvanic displacement to improve the overall urea water/seawater splitting performance. Pt/Ni(OH)2/NF showed significantly reduced overpotentials/potentials of 8.5/243 mV and 1.32/1.44 V to achieve a current density of 20/500 mA cm−2 during the HER and the UOR, which are lower compared to those of commercial Pt/C/NF (41 mV@20 mA cm−2) and RuO2/NF (1.34 V@20 mA cm−2). Furthermore, the electrolytic cell voltage of the as-prepared electrode in the alkaline seawater–urea electrolyte was significantly reduced to 1.55 V in comparison with the voltage in commercial Pt/C and RuO2 systems (1.63 V) at a current density of 100 mA cm−2. The amorphous Ni(OH)2 facilitates the adsorption and activation of water, generating a unique Cl− shielding effect, and the Pt nanoparticles promote the formation and desorption of H2, which synergistically improve the performance and endurance of Pt/Ni(OH)2. Ultraviolet photoelectron spectroscopy (UPS) showed that Pt/Ni(OH)2/NF shows a diminished work function, making it easier for electrons to escape and promoting the activation of water molecules. In situ Raman spectroscopy testifies that NiOOH serves as the crucial intermediate in the UOR process over Pt/Ni(OH)2/NF. This work provides an important reference for efficient hydrogen production in seawater by coupling the thermodynamically more advantageous small molecule oxidation reaction with the HER.
通过耦合海水中尿素氧化反应（UOR）和析氢反应（HER），设计一种高效、耐腐蚀的双功能电催化剂用于大规模制氢仍然是一个挑战。本文通过自发电驱成功合成了Pt/Ni(OH)2/NF，提高了尿素水/海水的整体裂解性能。在HER和UOR过程中，Pt/Ni(OH)2/NF显著降低了过电位/电位，分别为8.4 /243 mV和1.32/1.44 V，电流密度为20/500 mA cm - 2，低于商用Pt/C/NF （41 mV@20 mA cm - 2）和RuO2/NF （1.34 V@20 mA cm - 2）。此外，制备的电极在碱性海水-尿素电解质中的电解池电压明显降低到1.55 V，而在100 mA cm−2的电流密度下，商用Pt/C和RuO2体系的电压为1.63 V。无定形Ni(OH)2有利于水的吸附和活化，产生独特的Cl -屏蔽效应，Pt纳米颗粒促进H2的形成和解吸，协同提高Pt/Ni(OH)2的性能和续航能力。紫外光电子能谱（UPS）显示Pt/Ni(OH)2/NF的功函数减小，使电子更容易逸出，促进了水分子的活化。原位拉曼光谱证明NiOOH在Pt/Ni(OH)2/NF的UOR过程中起着关键的中间体作用。本研究为将热力学上更有利的小分子氧化反应与HER耦合在海水中高效产氢提供了重要参考。
{"title":"Pt nanoparticles loaded onto ultrathin Ni(OH)2 nanosheets for enhanced seawater–urea electro-oxidation and hydrogen evolution at an industrial-grade current density","authors":"Jie Tian, Shiyu Wang, Min Wang, Nana Zheng, Jing Xie, Jindou Hu, Zhenjiang Lu, Yali Cao","doi":"10.1039/d5qi02174j","DOIUrl":"https://doi.org/10.1039/d5qi02174j","url":null,"abstract":"The design of an efficient and corrosion-resistant bifunctional electrocatalyst through coupling the urea oxidation reaction (UOR) and the hydrogen evolution reaction (HER) in seawater for large-scale hydrogen generation still poses challenges. Herein, Pt/Ni(OH)<small><sub>2</sub></small>/NF was successfully synthesised <em>via</em> spontaneous galvanic displacement to improve the overall urea water/seawater splitting performance. Pt/Ni(OH)<small><sub>2</sub></small>/NF showed significantly reduced overpotentials/potentials of 8.5/243 mV and 1.32/1.44 V to achieve a current density of 20/500 mA cm<small><sup>−2</sup></small> during the HER and the UOR, which are lower compared to those of commercial Pt/C/NF (41 mV@20 mA cm<small><sup>−2</sup></small>) and RuO<small><sub>2</sub></small>/NF (1.34 V@20 mA cm<small><sup>−2</sup></small>). Furthermore, the electrolytic cell voltage of the as-prepared electrode in the alkaline seawater–urea electrolyte was significantly reduced to 1.55 V in comparison with the voltage in commercial Pt/C and RuO<small><sub>2</sub></small> systems (1.63 V) at a current density of 100 mA cm<small><sup>−2</sup></small>. The amorphous Ni(OH)<small><sub>2</sub></small> facilitates the adsorption and activation of water, generating a unique Cl<small><sup>−</sup></small> shielding effect, and the Pt nanoparticles promote the formation and desorption of H<small><sub>2</sub></small>, which synergistically improve the performance and endurance of Pt/Ni(OH)<small><sub>2</sub></small>. Ultraviolet photoelectron spectroscopy (UPS) showed that Pt/Ni(OH)<small><sub>2</sub></small>/NF shows a diminished work function, making it easier for electrons to escape and promoting the activation of water molecules. <em>In situ</em> Raman spectroscopy testifies that NiOOH serves as the crucial intermediate in the UOR process over Pt/Ni(OH)<small><sub>2</sub></small>/NF. This work provides an important reference for efficient hydrogen production in seawater by coupling the thermodynamically more advantageous small molecule oxidation reaction with the HER.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"179 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021960","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}
The removal of radionuclides from radioactive waste generated during nuclear fuel fabrication or post-irradiation remains a significant obstacle to the widespread adoption of nuclear power, driven by the waste's complex composition, high radiotoxicity, and the presence of numerous interfering elements. Metal –organic frameworks (MOFs) are promising candidates for radionuclide separation due to their high surface area, excellent pore structure, and tunable surface functional groups. The present review highlights the recent progress in the application of UiO-66-based MOFs for the remediation of radionuclides, concentrating on the adsorption of essential radionuclides such as U, Th, Tc, Pd, Sr, and Cs from aqueous solutions, which are crucial for the management of liquid radioactive waste. Additionally, the removal of I2 in gaseous and aqueous solutions using different UiO-66-based adsorbents is provided. The review commences with a succinct introduction to nuclear energy and UiO-66-based MOFs. The following sections systematically examine various UiO-66 variants, including the unmodified material, its composites, and derivatives produced through post-synthetic modification (PSM). Special emphasis is placed on structural alterations, along with a comprehensive assessment of their radionuclide sequestration capabilities and a detailed explanation of the interaction mechanisms between these MOF-based materials and various radionuclides. The discussion wraps up with specifying potential research avenues, highlighting the rational design of advanced UiO-66 variants, such as magnetic composites, to enhance separation and targeted functionalization with selective moieties, aiming for improved selectivity toward radionuclides even in complex matrices. Additionally, the creation of sustainable, scalable, and environmentally friendly synthesis methods is underscored as essential for replacing hazardous solvents and facilitating industrial-scale production, emphasizing the necessity for ongoing research to translate these materials into practical applications. Ultimately, these collaborative research initiatives are crucial for bridging the divide between fundamental advancements in material design and real-world applications, thus enabling the deployment of robust, recyclable, and highly selective UiO-66 derived adsorbents in large-scale systems for the remediation of nuclear wastewater and contaminated industrial effluents.
{"title":"Advancements in UiO-66-based adsorbents: a critical review of their role in radionuclide sequestration","authors":"Nitin Gumber, Rajesh V. Pai","doi":"10.1039/d5qi02253c","DOIUrl":"https://doi.org/10.1039/d5qi02253c","url":null,"abstract":"The removal of radionuclides from radioactive waste generated during nuclear fuel fabrication or post-irradiation remains a significant obstacle to the widespread adoption of nuclear power, driven by the waste's complex composition, high radiotoxicity, and the presence of numerous interfering elements. Metal –organic frameworks (MOFs) are promising candidates for radionuclide separation due to their high surface area, excellent pore structure, and tunable surface functional groups. The present review highlights the recent progress in the application of UiO-66-based MOFs for the remediation of radionuclides, concentrating on the adsorption of essential radionuclides such as U, Th, Tc, Pd, Sr, and Cs from aqueous solutions, which are crucial for the management of liquid radioactive waste. Additionally, the removal of I<small><sub>2</sub></small> in gaseous and aqueous solutions using different UiO-66-based adsorbents is provided. The review commences with a succinct introduction to nuclear energy and UiO-66-based MOFs. The following sections systematically examine various UiO-66 variants, including the unmodified material, its composites, and derivatives produced through post-synthetic modification (PSM). Special emphasis is placed on structural alterations, along with a comprehensive assessment of their radionuclide sequestration capabilities and a detailed explanation of the interaction mechanisms between these MOF-based materials and various radionuclides. The discussion wraps up with specifying potential research avenues, highlighting the rational design of advanced UiO-66 variants, such as magnetic composites, to enhance separation and targeted functionalization with selective moieties, aiming for improved selectivity toward radionuclides even in complex matrices. Additionally, the creation of sustainable, scalable, and environmentally friendly synthesis methods is underscored as essential for replacing hazardous solvents and facilitating industrial-scale production, emphasizing the necessity for ongoing research to translate these materials into practical applications. Ultimately, these collaborative research initiatives are crucial for bridging the divide between fundamental advancements in material design and real-world applications, thus enabling the deployment of robust, recyclable, and highly selective UiO-66 derived adsorbents in large-scale systems for the remediation of nuclear wastewater and contaminated industrial effluents.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"17 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021963","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}
Nonlinear optical (NLO) crystals can expand the wavelength of coherent light by frequency conversion, and thus have significant applications in modern lasers, semiconductor manufacturing and lithography. However, the targeted synthesis of high-performance NLO crystals remains an ongoing challenge. Herein, two stable strong NLO crystals, (A2I)[PbI(OOC(CH2)2COO)] (A = Rb, K), have been rationally obtained through a convenient mixed solvothermal method. The highly distorted [PbI2O4] polyhedra which owns large hyperpolarizability and polarizability anisotropy adopt an oriented arrangement that enables favourable superposition of their microscopic second-order susceptibilities. Remarkably, (A2I)[PbI(OOC(CH2)2COO)] (A = Rb, K) not only exhibit strong phase-matching SHG response (7.3 and 5.8 × KDP) and large birefringence (0.205 and 0.245 @ 1064 nm), but also present high thermal stability up to 250 oC in air and good crystal growth habit. Based on theoretical calculations and structural analysis, their strong SHG response are predominantly originated from the distorted [PbI2O4] polyhedron. This study provides an efficient approach for the future discovery of new high-performance NLO crystals.
{"title":"Stable Lead Succinate-Iodides with Strong Second-Harmonic Generation Response and Large Birefringence","authors":"Yulu Wu, Jialin Zeng, Ruibiao Fu, Wenjing Yang, Zilong Geng, Senfu Lei, Yiting Luo, Xiaofan Tong, Zuju Ma","doi":"10.1039/d5qi02471d","DOIUrl":"https://doi.org/10.1039/d5qi02471d","url":null,"abstract":"Nonlinear optical (NLO) crystals can expand the wavelength of coherent light by frequency conversion, and thus have significant applications in modern lasers, semiconductor manufacturing and lithography. However, the targeted synthesis of high-performance NLO crystals remains an ongoing challenge. Herein, two stable strong NLO crystals, (A2I)[PbI(OOC(CH2)2COO)] (A = Rb, K), have been rationally obtained through a convenient mixed solvothermal method. The highly distorted [PbI2O4] polyhedra which owns large hyperpolarizability and polarizability anisotropy adopt an oriented arrangement that enables favourable superposition of their microscopic second-order susceptibilities. Remarkably, (A2I)[PbI(OOC(CH2)2COO)] (A = Rb, K) not only exhibit strong phase-matching SHG response (7.3 and 5.8 × KDP) and large birefringence (0.205 and 0.245 @ 1064 nm), but also present high thermal stability up to 250 oC in air and good crystal growth habit. Based on theoretical calculations and structural analysis, their strong SHG response are predominantly originated from the distorted [PbI2O4] polyhedron. This study provides an efficient approach for the future discovery of new high-performance NLO crystals.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"142 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005744","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}
Xiaolong Leng, Nunna Guru Prakash, Yumei Li, Lei Zhu, Gang Xu, Wei Xiong, Changping Li, Shuang Li, Yini Chen, Tae Jo Ko
Lithium metal batteries (LMBs) suffer from severe safety risks and limited cycle life, largely attributed to the uncontrolled growth of Li dendrites. In this work, we propose a facile modification approach to construct high-performance LMBs. A heat-treated electrospun PAN/PVDF membrane was further functionalized with graphene oxide (GO) and SiO2 (HPPSG), which together ensured dendrite-free Li deposition and enhanced electrochemical stability. The thermal treatment significantly reinforced the mechanical robustness of the nanofiber scaffold, while GO, with abundant lithiophilic sites, guided uniform nucleation of Li. Meanwhile, SiO2 promoted Li-ion transport, improved electrolyte affinity, and chemically consumed dendrites during cycling. Benefiting from this synergistic design, the HPPSG composite separator enabled long-term reversible plating/stripping behavior, delivering an initial capacity of 159 mAh g−1 at 0.2C and maintaining 109 mAh g−1 after 500 cycles at 2C (capacity retention 85.8%, decay rate 0.028%). Compared with commercial Celgard membranes, the proposed composite exhibited excellent thermal dimensional stability (intact up to 180 °C), high porosity (75%), superior electrolyte uptake (552%), and outstanding cycling stability, highlighting its potential for next-generation safe and durable LMBs.
锂金属电池（lmb）存在严重的安全风险和有限的循环寿命，很大程度上归因于锂枝晶的不可控生长。在这项工作中，我们提出了一种简单的修改方法来构建高性能的lmb。用氧化石墨烯（GO）和二氧化硅（HPPSG）进一步功能化了经过热处理的电纺丝PAN/PVDF膜，共同确保了无枝晶的锂沉积，增强了电化学稳定性。热处理显著增强了纳米纤维支架的机械稳健性，而氧化石墨烯具有丰富的亲锂位点，引导了锂的均匀成核。同时，SiO2促进了锂离子的传输，提高了电解质的亲和力，并在循环过程中化学消耗了枝晶。得益于这种协同设计，HPPSG复合隔膜实现了长期可逆的电镀/剥离行为，在0.2C下提供159 mAh g- 1的初始容量，在2C下循环500次后保持109 mAh g- 1（容量保持率85.8%，衰减率0.028%）。与商用Celgard膜相比，该复合材料具有优异的热尺寸稳定性（高达180°C）、高孔隙率（75%）、优异的电解质吸收率（552%）和出色的循环稳定性，突出了其作为下一代安全耐用的lmb的潜力。
{"title":"Graphene oxide/SiO2 functionalized heat-treated electrospun membranes for dendrite-free and durable lithium metal batteries","authors":"Xiaolong Leng, Nunna Guru Prakash, Yumei Li, Lei Zhu, Gang Xu, Wei Xiong, Changping Li, Shuang Li, Yini Chen, Tae Jo Ko","doi":"10.1039/d5qi02194d","DOIUrl":"https://doi.org/10.1039/d5qi02194d","url":null,"abstract":"Lithium metal batteries (LMBs) suffer from severe safety risks and limited cycle life, largely attributed to the uncontrolled growth of Li dendrites. In this work, we propose a facile modification approach to construct high-performance LMBs. A heat-treated electrospun PAN/PVDF membrane was further functionalized with graphene oxide (GO) and SiO<small><sub>2</sub></small> (HPPSG), which together ensured dendrite-free Li deposition and enhanced electrochemical stability. The thermal treatment significantly reinforced the mechanical robustness of the nanofiber scaffold, while GO, with abundant lithiophilic sites, guided uniform nucleation of Li. Meanwhile, SiO<small><sub>2</sub></small> promoted Li-ion transport, improved electrolyte affinity, and chemically consumed dendrites during cycling. Benefiting from this synergistic design, the HPPSG composite separator enabled long-term reversible plating/stripping behavior, delivering an initial capacity of 159 mAh g<small><sup>−1</sup></small> at 0.2C and maintaining 109 mAh g<small><sup>−1</sup></small> after 500 cycles at 2C (capacity retention 85.8%, decay rate 0.028%). Compared with commercial Celgard membranes, the proposed composite exhibited excellent thermal dimensional stability (intact up to 180 °C), high porosity (75%), superior electrolyte uptake (552%), and outstanding cycling stability, highlighting its potential for next-generation safe and durable LMBs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"86 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005675","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}
Zhihao Wang, Wenqiang Li, Zibo Chen, HuiHui Jin, Yunfa Si, Xiaodong Ji, Lun Li, Cheng Chen, Daping He
The widespread application of proton exchange membrane fuel cells (PEMFCs) faces difficulties due to sluggish kinetics in the oxygen reduction reaction (ORR), the high expense, and the limited durability of platinum (Pt)-based catalysts. This work introduces a highly efficient electrocatalyst that involves the attachment of ordered PtCo intermetallic nanoparticles (NPs) to a three-dimensional defective graphene support, which is co-doped with nitrogen and fluorine (PtCo/N,F-DGC). The support was synthesized via an innovative molten salt-assisted method that enables simultaneous heteroatom doping and porous structure formation. The resulting catalyst demonstrates exceptional performance in ORR with a mass activity (MA) of 1.02 A mgPt−1, which signifies a 10.2-fold improvement over conventional Pt/C, and it retains impressive stability, exhibiting merely a 2 mV loss in half-wave potential after 30k accelerated cycles. Calculations based on density functional theory (DFT) indicate that co-doping with N and F effectively decreases the Pt d-band center, which optimizes the adsorption of oxygen intermediates and lowers the energy barrier for the reaction. Membrane electrode assembly (MEA) tests confirm its remarkable performance in fuel cells, offering a practical method for creating advanced low-Pt electrocatalysts that demonstrate improved activity and durability.
质子交换膜燃料电池（pemfc）的广泛应用面临着氧还原反应（ORR）动力学缓慢、成本高、铂基催化剂耐久性有限等问题。本研究介绍了一种高效的电催化剂，它将有序的PtCo金属间纳米颗粒（NPs）附着在三维缺陷石墨烯载体上，石墨烯载体共掺杂氮和氟（PtCo/N,F-DGC）。该支架是通过一种创新的熔盐辅助方法合成的，可以同时掺杂杂原子和形成多孔结构。所得催化剂在ORR中表现出优异的性能，质量活性（MA）为1.02 a mgPt−1，比传统Pt/C提高了10.2倍，并且保持了令人印象深刻的稳定性，在30k加速循环后，半波电位仅损失2 mV。基于密度泛函理论（DFT）的计算表明，N和F的共掺杂有效地降低了Pt d带中心，从而优化了氧中间体的吸附，降低了反应的能垒。膜电极组件（MEA）测试证实了其在燃料电池中的卓越性能，为制造先进的低铂电催化剂提供了一种实用的方法，该方法具有更高的活性和耐用性。
{"title":"Synergistic modulation of electronic structure in PtCo intermetallic electrocatalysts via N,F-co-doped graphene for robust oxygen reduction reaction","authors":"Zhihao Wang, Wenqiang Li, Zibo Chen, HuiHui Jin, Yunfa Si, Xiaodong Ji, Lun Li, Cheng Chen, Daping He","doi":"10.1039/d5qi02327k","DOIUrl":"https://doi.org/10.1039/d5qi02327k","url":null,"abstract":"The widespread application of proton exchange membrane fuel cells (PEMFCs) faces difficulties due to sluggish kinetics in the oxygen reduction reaction (ORR), the high expense, and the limited durability of platinum (Pt)-based catalysts. This work introduces a highly efficient electrocatalyst that involves the attachment of ordered PtCo intermetallic nanoparticles (NPs) to a three-dimensional defective graphene support, which is co-doped with nitrogen and fluorine (PtCo/N,F-DGC). The support was synthesized <em>via</em> an innovative molten salt-assisted method that enables simultaneous heteroatom doping and porous structure formation. The resulting catalyst demonstrates exceptional performance in ORR with a mass activity (MA) of 1.02 A mg<small><sub>Pt</sub></small><small><sup>−1</sup></small>, which signifies a 10.2-fold improvement over conventional Pt/C, and it retains impressive stability, exhibiting merely a 2 mV loss in half-wave potential after 30k accelerated cycles. Calculations based on density functional theory (DFT) indicate that co-doping with N and F effectively decreases the Pt d-band center, which optimizes the adsorption of oxygen intermediates and lowers the energy barrier for the reaction. Membrane electrode assembly (MEA) tests confirm its remarkable performance in fuel cells, offering a practical method for creating advanced low-Pt electrocatalysts that demonstrate improved activity and durability.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"45 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005676","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}
Hang Yu, Jianmei Jia, Tao Yang, Kai Chen, Shan Jin, lin xiong, Manzhou Zhu
Precise structural regulation of metal nanoclusters is critical for optimizing their catalytic performance. In this work, a core-shell copper-hydride nanocluster [Cu45(C6H11S)24(P(PhF)3)4H19]2+ was successfully synthesized via a one-pot method. Single-crystal X-ray diffraction (SCXRD), electrospray ionization mass spectrometry (ESI-MS), and X-ray photoelectron spectroscopy (XPS) were employed to characterize the nanocluster, confirming its structure consists of a Cu11@Cu15 core encapsulated by a cage-like Cu19((C6H11S)24(P(PhF)3)4) shell, with all Cu atoms in the +1-oxidation state. Density functional theory (DFT) calculations clarified the positions of hydride atoms, electronic structure, and optical absorption properties of the nanocluster. Catalytic tests demonstrated that [Cu45(C6H11S)24(P(PhF)3)4H19]2+ exhibited excellent activity in the hydroboration of terminal alkynes, achieving a maximum product yield of 98.3% under optimized conditions. It also showed good compatibility with substrates bearing electron-withdrawing groups or electron-donating groups. This study bridges precise atomic-level design and catalytic application of copper nanoclusters, providing both experimental and theoretical insights for their future development in homogeneous catalysis.
{"title":"Core-Shell [Cu45(C6H11S)24(P(PhF)3)4H19]2+ Nanocluster: Synthesis, Structure and Catalytic Hydroboration","authors":"Hang Yu, Jianmei Jia, Tao Yang, Kai Chen, Shan Jin, lin xiong, Manzhou Zhu","doi":"10.1039/d5qi02480c","DOIUrl":"https://doi.org/10.1039/d5qi02480c","url":null,"abstract":"Precise structural regulation of metal nanoclusters is critical for optimizing their catalytic performance. In this work, a core-shell copper-hydride nanocluster [Cu45(C6H11S)24(P(PhF)3)4H19]2+ was successfully synthesized via a one-pot method. Single-crystal X-ray diffraction (SCXRD), electrospray ionization mass spectrometry (ESI-MS), and X-ray photoelectron spectroscopy (XPS) were employed to characterize the nanocluster, confirming its structure consists of a Cu11@Cu15 core encapsulated by a cage-like Cu19((C6H11S)24(P(PhF)3)4) shell, with all Cu atoms in the +1-oxidation state. Density functional theory (DFT) calculations clarified the positions of hydride atoms, electronic structure, and optical absorption properties of the nanocluster. Catalytic tests demonstrated that [Cu45(C6H11S)24(P(PhF)3)4H19]2+ exhibited excellent activity in the hydroboration of terminal alkynes, achieving a maximum product yield of 98.3% under optimized conditions. It also showed good compatibility with substrates bearing electron-withdrawing groups or electron-donating groups. This study bridges precise atomic-level design and catalytic application of copper nanoclusters, providing both experimental and theoretical insights for their future development in homogeneous catalysis.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"11 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005678","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}
Silicon monoxide (SiO) is a promising high-capacity anode material for lithium-ion batteries (LIBs), yet its substantial volume expansion during lithiation/delithiation leads to mechanical stress, structural degradation, and rapid capacity fading, thereby limiting practical application. To overcome these challenges, we propose an in situ cross-linking strategy to construct a dual network binder that firmly anchors onto SiO particles through an ester-based covalent framework and dynamic hydrogen bonding, achieved by a one-step thermal reaction of tapioca starch (TA), fumaric acid (FA), and SiO. Multi-scale testing reveals that the branched TA structure provides abundant hydroxyl groups for strong covalent cross-linking, while the hydrogen bond network imparts self-healing capability and volume-change adaptability. Simultaneously, anchoring polar groups to the SiO surface enhances interfacial adhesion. This synergistic dual network architecture binder effectively dissipates stress and preserves electrode integrity, ensuring continuous Li+ transport. As a result, the TA–FA modified SiO anode delivers exceptional cycling stability, maintaining a high reversible capacity of 921.7 mAh g−1 after 300 cycles at 1 A g−1, far surpassing the sodium alginate (SA)/SiO (443.1 mAh g−1). This study utilizes natural polymer architectures to create a covalent-hydrogen bond dual network binder via an in situ route, offering a novel strategy for developing high-performance SiO anodes in practical LIBs.
一氧化硅（SiO）是一种很有前途的锂离子电池（LIBs）高容量负极材料，但其在锂化/去锂化过程中的大量体积膨胀导致机械应力、结构退化和容量快速衰减，从而限制了实际应用。为了克服这些挑战，我们提出了一种原位交联策略，通过木薯淀粉（TA）、富马酸（FA）和SiO的一步热反应，通过酯基共价框架和动态氢键，构建一种双网络粘合剂，牢固地锚定在SiO颗粒上。多尺度测试表明，支链TA结构为强共价交联提供了丰富的羟基，而氢键网络具有自愈能力和体积变化适应性。同时，在SiO表面锚定极性基团增强了界面附着力。这种协同的双网络结构粘合剂有效地消散应力并保持电极的完整性，确保连续的Li+传输。因此，TA-FA修饰的SiO阳极具有优异的循环稳定性，在1 a g−1下循环300次后保持921.7 mAh g−1的高可逆容量，远远超过海藻酸钠(SA)/SiO （443.1 mAh g−1）。本研究利用天然聚合物结构，通过原位路径创建共价键-氢键双网络粘合剂，为在实际lib中开发高性能SiO阳极提供了一种新策略。
{"title":"In situ construction of dual network binder synergistically enables the stability of SiO anodes","authors":"Siyi Jing, Weihua Wang, Yudai Huang, Wenyi Li, Haozhe Liu, Wei Wang, Xueyan Ma, Yingde Huang, Chengwei Fan, Letao Zhang, Zhouliang Tan","doi":"10.1039/d5qi02392k","DOIUrl":"https://doi.org/10.1039/d5qi02392k","url":null,"abstract":"Silicon monoxide (SiO) is a promising high-capacity anode material for lithium-ion batteries (LIBs), yet its substantial volume expansion during lithiation/delithiation leads to mechanical stress, structural degradation, and rapid capacity fading, thereby limiting practical application. To overcome these challenges, we propose an <em>in situ</em> cross-linking strategy to construct a dual network binder that firmly anchors onto SiO particles through an ester-based covalent framework and dynamic hydrogen bonding, achieved by a one-step thermal reaction of tapioca starch (TA), fumaric acid (FA), and SiO. Multi-scale testing reveals that the branched TA structure provides abundant hydroxyl groups for strong covalent cross-linking, while the hydrogen bond network imparts self-healing capability and volume-change adaptability. Simultaneously, anchoring polar groups to the SiO surface enhances interfacial adhesion. This synergistic dual network architecture binder effectively dissipates stress and preserves electrode integrity, ensuring continuous Li<small><sup>+</sup></small> transport. As a result, the TA–FA modified SiO anode delivers exceptional cycling stability, maintaining a high reversible capacity of 921.7 mAh g<small><sup>−1</sup></small> after 300 cycles at 1 A g<small><sup>−1</sup></small>, far surpassing the sodium alginate (SA)/SiO (443.1 mAh g<small><sup>−1</sup></small>). This study utilizes natural polymer architectures to create a covalent-hydrogen bond dual network binder <em>via</em> an <em>in situ</em> route, offering a novel strategy for developing high-performance SiO anodes in practical LIBs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021966","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}
Shuang Liu, Pan Xu, Junyao Pan, Sihui Li, Yuxin Yan, Rui Wu, Junhui Guo, Chang Liu, Wenfu Yan
In protonic acid-catalyzed methanol amination, achieving high selectivity toward methylamine (MMA) and dimethylamine (DMA) while suppressing dimethyl ether (DME) formation remains challenging. The catalytic performance of protonic zeolites in this reaction depends on Brønsted acidity, which is controlled by both the Si/Al ratio and the spatial distribution of framework Al. CHA zeolite is particularly attractive because of its unique pore architecture and tunable acidity. Here, we synthesized CHA zeolites with Si/Al ratios from 3.4 to 4.3 and systematically varied their Al distributions, without using organic structure-directing agents (OSDAs). The synthesis exploited the synergistic effect of alkali metal cations (Na + , Cs + ) and CHA seeds with different Al contents (SAPO-34, SSZ-13, and pure silica CHA). The Al content of the seed determined the Si/Al ratio of the final product, while the seed type controlled the Al distribution. At a fixed Si/Al ratio of 3.8, the sample synthesized with a SAPO-34 seed (CHA-S34-3.8) showed the best performance. At 350 °C and 0.813 h -1 , and at 400 °C and 4.3 h -1 , MMA + DMA yield reached 86.6% and 87.6%, respectively, with no detectable DME after stabilization. These values represent the highest reported performance for methanol amination. Characterization revealed that enrichment of Al pairs in the eight-membered rings, combined with optimal acid density and strength, accounts for the superior activity. This study provides mechanistic insight into the role of Al distribution and offers a strategy to design high-performance zeolite catalysts for methanol amination.
在质子酸催化的甲醇胺化反应中，实现对甲胺（MMA）和二甲胺（DMA）的高选择性同时抑制二甲醚（DME）的生成仍然是一个挑战。质子沸石在该反应中的催化性能取决于Brønsted的酸度，而Brønsted的酸度受Si/Al比和骨架Al的空间分布控制。CHA沸石因其独特的孔隙结构和可调的酸度而特别具有吸引力。在此，我们合成了Si/Al比值为3.4 ~ 4.3的CHA沸石，并在不使用有机结构导向剂（OSDAs）的情况下系统地改变了它们的Al分布。利用碱金属阳离子（Na +、Cs +）和不同Al含量的CHA种子（SAPO-34、SSZ-13和纯二氧化硅CHA）的协同作用合成。种子的Al含量决定了最终产物的Si/Al比，而种子类型控制了Al的分布。在固定Si/Al比为3.8时，以SAPO-34种子（CHA-S34-3.8）合成的样品表现出最佳性能。在350℃、0.813 h -1和400℃、4.3 h -1条件下，MMA + DMA的产率分别达到86.6%和87.6%，稳定后没有检测到二甲醚。这些值代表了甲醇胺化的最高报告性能。表征表明，八元环上Al对的富集，加上最佳的酸密度和强度，是其具有优异活性的原因。本研究提供了对Al分布作用的机理见解，并为设计高性能的甲醇胺化沸石催化剂提供了策略。
{"title":"Al pairing in 8-membered rings drives superior methanol amination on CHA zeolites","authors":"Shuang Liu, Pan Xu, Junyao Pan, Sihui Li, Yuxin Yan, Rui Wu, Junhui Guo, Chang Liu, Wenfu Yan","doi":"10.1039/d5qi02464a","DOIUrl":"https://doi.org/10.1039/d5qi02464a","url":null,"abstract":"In protonic acid-catalyzed methanol amination, achieving high selectivity toward methylamine (MMA) and dimethylamine (DMA) while suppressing dimethyl ether (DME) formation remains challenging. The catalytic performance of protonic zeolites in this reaction depends on Brønsted acidity, which is controlled by both the Si/Al ratio and the spatial distribution of framework Al. CHA zeolite is particularly attractive because of its unique pore architecture and tunable acidity. Here, we synthesized CHA zeolites with Si/Al ratios from 3.4 to 4.3 and systematically varied their Al distributions, without using organic structure-directing agents (OSDAs). The synthesis exploited the synergistic effect of alkali metal cations (Na + , Cs + ) and CHA seeds with different Al contents (SAPO-34, SSZ-13, and pure silica CHA). The Al content of the seed determined the Si/Al ratio of the final product, while the seed type controlled the Al distribution. At a fixed Si/Al ratio of 3.8, the sample synthesized with a SAPO-34 seed (CHA-S34-3.8) showed the best performance. At 350 °C and 0.813 h -1 , and at 400 °C and 4.3 h -1 , MMA + DMA yield reached 86.6% and 87.6%, respectively, with no detectable DME after stabilization. These values represent the highest reported performance for methanol amination. Characterization revealed that enrichment of Al pairs in the eight-membered rings, combined with optimal acid density and strength, accounts for the superior activity. This study provides mechanistic insight into the role of Al distribution and offers a strategy to design high-performance zeolite catalysts for methanol amination.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"29 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995926","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}
Zero thermal expansion is of great significance for materials science and industrial technology. However, achieving this property remains highly challenging. Here, we introduced the concept of high-entropy to design a novel oxide, KMnSc0.25In0.25Lu0.25Yb0.25(MoO4)3 (KMHO), which displays zero thermal expansion (αV = 1.53 × 10−6 K−1) over 300 to 800 K. The underlying mechanism was elucidated through synchrotron X-ray diffraction and high-pressure Raman spectroscopy. KMHO crystallizes in the NZP-type structure, where the positive thermal expansion along the c-axis is associated with the weak bonding at the K+ site, while the negative thermal expansion within the ab-plane originates from polyhedral rotations. High-pressure Raman spectroscopy further confirmed the contribution of polyhedral rotations to the negative thermal expansion. Moreover, it also exhibits typical semiconducting behavior, with an ionic conductivity reaching a maximum value of 1.62 × 10−3 S cm−1 at 1023 K. This work not only reports a novel high-entropy oxide with zero thermal expansion but also expands the potential applications of high-entropy materials in semiconducting and ionic conducting systems.
{"title":"Zero thermal expansion in high-entropy molybdate","authors":"Xin Chen, Hao Li, Qingjie Wang, Kaiyue Zhao, Gongshen He, Yongqiang Qiao, Qilong Gao, Shogo Kawaguchi, Bingbing Fan, Rui Zhang, Jun Chen","doi":"10.1039/d5qi02346g","DOIUrl":"https://doi.org/10.1039/d5qi02346g","url":null,"abstract":"Zero thermal expansion is of great significance for materials science and industrial technology. However, achieving this property remains highly challenging. Here, we introduced the concept of high-entropy to design a novel oxide, KMnSc<small><sub>0.25</sub></small>In<small><sub>0.25</sub></small>Lu<small><sub>0.25</sub></small>Yb<small><sub>0.25</sub></small>(MoO<small><sub>4</sub></small>)<small><sub>3</sub></small> (KMHO), which displays zero thermal expansion (<em>α</em><small><sub>V</sub></small> = 1.53 × 10<small><sup>−6</sup></small> K<small><sup>−1</sup></small>) over 300 to 800 K. The underlying mechanism was elucidated through synchrotron X-ray diffraction and high-pressure Raman spectroscopy. KMHO crystallizes in the NZP-type structure, where the positive thermal expansion along the <em>c</em>-axis is associated with the weak bonding at the K<small><sup>+</sup></small> site, while the negative thermal expansion within the <em>ab</em>-plane originates from polyhedral rotations. High-pressure Raman spectroscopy further confirmed the contribution of polyhedral rotations to the negative thermal expansion. Moreover, it also exhibits typical semiconducting behavior, with an ionic conductivity reaching a maximum value of 1.62 × 10<small><sup>−3</sup></small> S cm<small><sup>−1</sup></small> at 1023 K. This work not only reports a novel high-entropy oxide with zero thermal expansion but also expands the potential applications of high-entropy materials in semiconducting and ionic conducting systems.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"37 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995925","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}
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