Achieving high-performance electronic structure engineering in multi-component photocatalysts that enable effective cooperation and synergy in photoinduced charge transfer and surface reaction kinetics remains a major challenge for the sustainable conversion of solar energy into hydrogen. Herein, well-defined ZnIn2S4 nanosheets modified with metallic 1T-phase WS2 and Ni2P dual cocatalysts with superior photoactivity and stability were fabricated by two-step ultrasonic self-assembly processes. A series of photoelectrochemical characterizations revealed that the metallic phase 1T-WS2 with excellent conductivity can effectively lower the charge transport resistance and enhance electron transfer efficiency, while Ni2P with abundant active sites can efficiently promote the surface H2-production reaction dynamics in this dual cocatalyst system. Moreover, the synergistic effects of the 1T-WS2 and Ni2P dual cocatalysts can boost the oxidation efficiency of the sacrificial regents (lactic acid) by elevating the valence band levels of ZnIn2S4, which in turn promotes photocarriers separation. As a result, the optimized tandem Ni2P/1T-WS2/ZnIn2S4 ternary heterojunction with a cascade electron transfer pathway achieved the highest hydrogen generation rate of 16.87 mmol g-1 h-1, roughly 3.45, 1.56 and 1.38 times greater than bare ZnIn2S4, binary 1T-WS2/ZnIn2S4 and Ni2P/ZnIn2S4, respectively. This work would inspire the design of other highly efficient, cost-effective and multifunctional dual cocatalysts for efficient and sustainable solar-to-fuel conversion.
{"title":"Electronic structure engineering and cascade electron transfer channel in Ni2P/1T-WS2/ZnIn2S4 ternary heterojunction for enhanced photocatalytic hydrogen evolution: Construction, kinetics, and mechanistic insights","authors":"Hua Lv, Zhiyun Suo, Fubiao Zhang, Baoliang Wan, Chayuan Zhou, Xinyan Xing, Gongke Wang, Yuehua Chen, Yumin Liu","doi":"10.1039/d4qi03266g","DOIUrl":"https://doi.org/10.1039/d4qi03266g","url":null,"abstract":"Achieving high-performance electronic structure engineering in multi-component photocatalysts that enable effective cooperation and synergy in photoinduced charge transfer and surface reaction kinetics remains a major challenge for the sustainable conversion of solar energy into hydrogen. Herein, well-defined ZnIn2S4 nanosheets modified with metallic 1T-phase WS2 and Ni2P dual cocatalysts with superior photoactivity and stability were fabricated by two-step ultrasonic self-assembly processes. A series of photoelectrochemical characterizations revealed that the metallic phase 1T-WS2 with excellent conductivity can effectively lower the charge transport resistance and enhance electron transfer efficiency, while Ni2P with abundant active sites can efficiently promote the surface H2-production reaction dynamics in this dual cocatalyst system. Moreover, the synergistic effects of the 1T-WS2 and Ni2P dual cocatalysts can boost the oxidation efficiency of the sacrificial regents (lactic acid) by elevating the valence band levels of ZnIn2S4, which in turn promotes photocarriers separation. As a result, the optimized tandem Ni2P/1T-WS2/ZnIn2S4 ternary heterojunction with a cascade electron transfer pathway achieved the highest hydrogen generation rate of 16.87 mmol g-1 h-1, roughly 3.45, 1.56 and 1.38 times greater than bare ZnIn2S4, binary 1T-WS2/ZnIn2S4 and Ni2P/ZnIn2S4, respectively. This work would inspire the design of other highly efficient, cost-effective and multifunctional dual cocatalysts for efficient and sustainable solar-to-fuel conversion.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703322","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}
Yurong Wu, Ziyun Zhang, Jiangshan Huo, Runguo Zheng, Zhishuang Song, Zhiyuan Wang, Yanguo Liu, Dan Wang
P2-type layered oxides emerge as promising cathode candidate materials for potassium ion batteries. Nevertheless, unsatisfying cyclic stability hinders its practical application, chiefly arising from the deleterious phase transition and the Jahn-Teller distortion of Mn3+. Herein, an anion-doped strategy by incorporating F- into the P2-K0.6Zn0.1Ti0.05Al0.05Mn0.8O2 (KTMO) cathode materials is proposed. Raman testing was employed to investigate the material’s local chemical environment. The results denoted a slight shift to higher wavenumbers in the Eg and A1g peaks, which was ascribed to the shortening of the average TM-O bond length triggered by the addition of F. Ex-situ XRD analysis revealed that the material K0.6Zn0.1Ti0.05Al0.05Mn0.8O1.93F0.07 effectively suppresses the undesirable phase transformation. Moreover, the maximum variation in the lattice parameter c is only 2.2% during potassium insertion/extraction, which fully demonstrates the outstanding performance of this material in terms of structural stability. The strategy brings about excellent cyclic stability with a reversible capacity of 131.8 mAh g-1 and capacity retention of 76.8% after 100 cycles at 4.0 V. Therse findings offer novel insights for the design of cathode materials possessing optimal structures and enhanced performance in potassium-ion batteries.
P2- 型层状氧化物是很有前途的钾离子电池阴极候选材料。然而，令人不满意的循环稳定性阻碍了它的实际应用，主要原因是有害的相变和 Mn3+ 的 Jahn-Teller 畸变。本文提出了一种阴离子掺杂策略，即在 P2-K0.6Zn0.1Ti0.05Al0.05Mn0.8O2 (KTMO) 阴极材料中加入 F-。拉曼测试用于研究材料的局部化学环境。原位 XRD 分析表明，K0.6Zn0.1Ti0.05Al0.05Mn0.8O1.93F0.07 材料有效地抑制了不良相变。此外，在钾插入/提取过程中，晶格参数 c 的最大变化仅为 2.2%，这充分证明了该材料在结构稳定性方面的出色表现。该策略带来了出色的循环稳定性，在 4.0 V 下循环 100 次后，可逆容量为 131.8 mAh g-1，容量保持率为 76.8%。这些发现为设计具有最佳结构和更高性能的钾离子电池阴极材料提供了新的见解。
{"title":"Anionic F Doping-Induced Engineering of P2-Type Layered Cathode Materials for High-Performance Potassium-Ion Batteries","authors":"Yurong Wu, Ziyun Zhang, Jiangshan Huo, Runguo Zheng, Zhishuang Song, Zhiyuan Wang, Yanguo Liu, Dan Wang","doi":"10.1039/d5qi00385g","DOIUrl":"https://doi.org/10.1039/d5qi00385g","url":null,"abstract":"P2-type layered oxides emerge as promising cathode candidate materials for potassium ion batteries. Nevertheless, unsatisfying cyclic stability hinders its practical application, chiefly arising from the deleterious phase transition and the Jahn-Teller distortion of Mn3+. Herein, an anion-doped strategy by incorporating F- into the P2-K0.6Zn0.1Ti0.05Al0.05Mn0.8O2 (KTMO) cathode materials is proposed. Raman testing was employed to investigate the material’s local chemical environment. The results denoted a slight shift to higher wavenumbers in the Eg and A1g peaks, which was ascribed to the shortening of the average TM-O bond length triggered by the addition of F. Ex-situ XRD analysis revealed that the material K0.6Zn0.1Ti0.05Al0.05Mn0.8O1.93F0.07 effectively suppresses the undesirable phase transformation. Moreover, the maximum variation in the lattice parameter c is only 2.2% during potassium insertion/extraction, which fully demonstrates the outstanding performance of this material in terms of structural stability. The strategy brings about excellent cyclic stability with a reversible capacity of 131.8 mAh g-1 and capacity retention of 76.8% after 100 cycles at 4.0 V. Therse findings offer novel insights for the design of cathode materials possessing optimal structures and enhanced performance in potassium-ion batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"183 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703329","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}
Miguel A. Sierra, Alejandro Torres, Sergio Aguado, Alba Collado, Elena Sáez, MAR GOMEZ GALLEGO
Mimics of [FeFe] hydrogenases having two [(-adt)Fe2(CO)6] moieties linked through 1,2,3-triazole rings with polyethylene glycol (PEG) chains [(-OCH2CH2O-)4 (7) and (-OCH2CH2O-)5 (8)] are able to coordinate to alkali ions (Na+, K+) by means of the O-PEG atoms and the triazole-N3 positions. Electrocatalytic studies in trifluoroacetic acid (TFA) demonstrate that their catalytic performance is affected by the presence of Na+ and K+ salts. The addition of NaPF6 decreases the electrocatalytic activity of 7 and 8 (about 50% reduction of the TOF values). As in TFA 7 and 8 could be protonated in both, the triazole and the adt-amino groups, the reduction in the TOF values suggests that the NaPF6 inhibits the contribution of the triazolium species to the electrocatalytic process, likely due to the involvement of the triazole-N3 positions in Na+ binding. However, the addition of KPF6 either does not change (7) or increases the TOF values (8). 1H NMR titration experiments demonstrate that, despite the presence of K+ ions in the media, the triazolium salts are formed. Therefore, the TOF values should reflect the contribution of species protonated in both, the triazole and the adt-amino groups, to the HER process.
{"title":"Exploring Protonation Sites with Cation-Responsive Polyethylene glycol (PEG) Tethers in [FeFe]-Hydrogenase Mimics","authors":"Miguel A. Sierra, Alejandro Torres, Sergio Aguado, Alba Collado, Elena Sáez, MAR GOMEZ GALLEGO","doi":"10.1039/d5qi00170f","DOIUrl":"https://doi.org/10.1039/d5qi00170f","url":null,"abstract":"Mimics of [FeFe] hydrogenases having two [(-adt)Fe2(CO)6] moieties linked through 1,2,3-triazole rings with polyethylene glycol (PEG) chains [(-OCH2CH2O-)4 (7) and (-OCH2CH2O-)5 (8)] are able to coordinate to alkali ions (Na+, K+) by means of the O-PEG atoms and the triazole-N3 positions. Electrocatalytic studies in trifluoroacetic acid (TFA) demonstrate that their catalytic performance is affected by the presence of Na+ and K+ salts. The addition of NaPF6 decreases the electrocatalytic activity of 7 and 8 (about 50% reduction of the TOF values). As in TFA 7 and 8 could be protonated in both, the triazole and the adt-amino groups, the reduction in the TOF values suggests that the NaPF6 inhibits the contribution of the triazolium species to the electrocatalytic process, likely due to the involvement of the triazole-N3 positions in Na+ binding. However, the addition of KPF6 either does not change (7) or increases the TOF values (8). 1H NMR titration experiments demonstrate that, despite the presence of K+ ions in the media, the triazolium salts are formed. Therefore, the TOF values should reflect the contribution of species protonated in both, the triazole and the adt-amino groups, to the HER process.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"215 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703325","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}
Lithium (Li)-metal anode holds great promise for high-energy-density battery applications. However, the issue of uncontrollable Li dendrite growth, which is associated with large volume expansion during cycling, remains a significant hurdle. It is well known that the uniform Li+ flux, rich lithiophilic nucleation sites, and low local current density are of significant importance for inducing even Li deposition. Herein, a three-dimensional (3D) composite host was constructed by decorating an ultrafine Pt-nanoparticle layer on a carbon fiber framework (CF@Pt) via sputtering. CF with a high graphitic degree was in situ transformed into a lithiophilic LiC6 phase upon charging, endowing self-lithiophilicity with a low Li nucleation energy barrier. A reversible “dual-phase” Li storage behavior (lithiation and metallization) was spontaneously realized in this 3D host with low local current density. Highly dispersed Pt heterogeneous nano-seeds further served as the lithiophilicity and Li nucleation boosters, consequently leading to even Li+ flux distribution and boosting the dense and smooth Li nucleation/growth. Additionally, the as-obtained CF@Pt host shows remarkably improved electrochemical performances in half-cells, symmetrical cells and full-cells.
{"title":"Heterogeneous seeds boosting the self-lithiophilic host with dual-phase lithium storage for a stable lithium-metal anode","authors":"Zhicui Song, Jing Xue, Chaohui Wei, Donghuang Wang, Yingchun Ding, Aijun Zhou, Jingze Li","doi":"10.1039/d5qi00286a","DOIUrl":"https://doi.org/10.1039/d5qi00286a","url":null,"abstract":"Lithium (Li)-metal anode holds great promise for high-energy-density battery applications. However, the issue of uncontrollable Li dendrite growth, which is associated with large volume expansion during cycling, remains a significant hurdle. It is well known that the uniform Li<small><sup>+</sup></small> flux, rich lithiophilic nucleation sites, and low local current density are of significant importance for inducing even Li deposition. Herein, a three-dimensional (3D) composite host was constructed by decorating an ultrafine Pt-nanoparticle layer on a carbon fiber framework (CF@Pt) <em>via</em> sputtering. CF with a high graphitic degree was <em>in situ</em> transformed into a lithiophilic LiC<small><sub>6</sub></small> phase upon charging, endowing self-lithiophilicity with a low Li nucleation energy barrier. A reversible “dual-phase” Li storage behavior (lithiation and metallization) was spontaneously realized in this 3D host with low local current density. Highly dispersed Pt heterogeneous nano-seeds further served as the lithiophilicity and Li nucleation boosters, consequently leading to even Li<small><sup>+</sup></small> flux distribution and boosting the dense and smooth Li nucleation/growth. Additionally, the as-obtained CF@Pt host shows remarkably improved electrochemical performances in half-cells, symmetrical cells and full-cells.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"183 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695479","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}
Xiaofei Yang, Qianqian Deng, Shanting Liu, De Bin Fu, Ming-Xing Zhang, Jun Zhu, Shenghua Liu
Since the concept of aromaticity was first introduced in transition metal complexes, metals have become a crucial component for modulating aromaticity, leading to a variety of structural frameworks. Initial studies successfully achieved aromatic pentalene dianions through metal-ion coordination, and recent advancements in bridgehead metallapentalenes have demonstrated the transformation of antiaromaticity into aromaticity. This research introduces an efficient [2+2+1] cycloaddition strategy with a dual-path cooperative mechanism for constructing the first structurally defined non-aromatic wingtip metallapentalene, including wingtip osmapentalene and its methoxy and hydroxy derivatives. Osmapentalenes display versatile reactivity, allowing for multi-site functionalization via nucleophilic and electrophilic substitutions. Furthermore, the hydroxy derivative easily undergoes a ring-opening reaction with methanol to form osmafuran. The lowest-energy absorption of wingtip osmapentalene falls within the visible range, with adjustable optical and electrochemical properties based on substituents and π-conjugation modifications.
{"title":"A Novel Metal-Wingtip Pentalene System: The Synthesis, Structure, and Reactivity of Non-Aromatic Wingtip Osmapentalenes","authors":"Xiaofei Yang, Qianqian Deng, Shanting Liu, De Bin Fu, Ming-Xing Zhang, Jun Zhu, Shenghua Liu","doi":"10.1039/d5qi00018a","DOIUrl":"https://doi.org/10.1039/d5qi00018a","url":null,"abstract":"Since the concept of aromaticity was first introduced in transition metal complexes, metals have become a crucial component for modulating aromaticity, leading to a variety of structural frameworks. Initial studies successfully achieved aromatic pentalene dianions through metal-ion coordination, and recent advancements in bridgehead metallapentalenes have demonstrated the transformation of antiaromaticity into aromaticity. This research introduces an efficient [2+2+1] cycloaddition strategy with a dual-path cooperative mechanism for constructing the first structurally defined non-aromatic wingtip metallapentalene, including wingtip osmapentalene and its methoxy and hydroxy derivatives. Osmapentalenes display versatile reactivity, allowing for multi-site functionalization via nucleophilic and electrophilic substitutions. Furthermore, the hydroxy derivative easily undergoes a ring-opening reaction with methanol to form osmafuran. The lowest-energy absorption of wingtip osmapentalene falls within the visible range, with adjustable optical and electrochemical properties based on substituents and π-conjugation modifications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"96 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695481","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}
Proteolysis targeting chimeras (PROTACs), which catalytically degrade disease-related proteins, can overcome the limitations of traditional small-molecule inhibitors and thus have revolutionized the field of targeted therapy. Building on this advancement, we present platinated PROTAC [PROTAC-Pt(IV)], a new class of “dual-action” prodrug that leverages the ubiquitin–proteasome system-mediated degradation capabilities of PROTAC and takes the advantages of Pt-based anticancer prodrugs. PROTAC-Pt(IV) exhibits exceptional cytotoxicity, with half-maximal inhibitory concentration values in the nanomolar range. It outperformed conventional inhibitor-based Pt(IV) prodrugs by up to three orders of magnitude by efficiently degrading the target protein BRD4 in a range of human cancer cells. PROTAC-Pt(IV) induces cancer cell death through mechanisms including augmented apoptosis, p21-mediated cell cycle arrest, and immune activation via PD-L1 downregulation. Compared with PROTAC alone, PROTAC-Pt(IV) more effectively suppressed the growth of tumor xenografts in a mouse model via its altered pharmacokinetic properties. Collectively, the development of PROTAC-Pt(IV) marks a revolution in dual-action Pt(IV) anticancer prodrugs and offers a promising avenue for enhanced and targeted cancer therapies.
{"title":"A platinated prodrug leveraging PROTAC technology for targeted protein degradation and enhanced antitumor efficacy","authors":"Jiaqian Xu, Shu Chen, Ka-Yan Ng, Xianfeng Chen, Wai Chung Fu, Guangyu Zhu","doi":"10.1039/d5qi00605h","DOIUrl":"https://doi.org/10.1039/d5qi00605h","url":null,"abstract":"Proteolysis targeting chimeras (PROTACs), which catalytically degrade disease-related proteins, can overcome the limitations of traditional small-molecule inhibitors and thus have revolutionized the field of targeted therapy. Building on this advancement, we present platinated PROTAC [PROTAC-Pt(IV)], a new class of “dual-action” prodrug that leverages the ubiquitin–proteasome system-mediated degradation capabilities of PROTAC and takes the advantages of Pt-based anticancer prodrugs. PROTAC-Pt(IV) exhibits exceptional cytotoxicity, with half-maximal inhibitory concentration values in the nanomolar range. It outperformed conventional inhibitor-based Pt(IV) prodrugs by up to three orders of magnitude by efficiently degrading the target protein BRD4 in a range of human cancer cells. PROTAC-Pt(IV) induces cancer cell death through mechanisms including augmented apoptosis, p21-mediated cell cycle arrest, and immune activation via PD-L1 downregulation. Compared with PROTAC alone, PROTAC-Pt(IV) more effectively suppressed the growth of tumor xenografts in a mouse model via its altered pharmacokinetic properties. Collectively, the development of PROTAC-Pt(IV) marks a revolution in dual-action Pt(IV) anticancer prodrugs and offers a promising avenue for enhanced and targeted cancer therapies.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"71 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695482","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}
Wenhui Yang, Chensi Zhan, Qiang Zhu, Lei Liu, Baiming Su, Haoxiang Yu, Liyuan Zhang, Lei Yan, Jie Shu
Sustainable and safe aqueous proton batteries (APBs) have attracted significant attention owing to the unique “Grotthuss mechanism”. Although organic small molecules with stable and adjustable framework are promising electrode materials, their easy-dissolution in electrolyte and unsatisfactory intrinsic conductivity cripple the broader application in APB devices. Herein, the 2,7-diammonio-4,5,9,10-tetraone (PTO-NH3+) with the stable intermolecular hydrogen-bond networks is designed via the in-situ electrochemical reduction strategy, while the optimized molecule structure endows low charge transport barriers, high chemical reactivity, and prominent charge affinity. The fast kinetics of proton coordination/de-coordination behavior in PTO-NH3+ electrode is corroborated by ex-situ characterization techniques and theoretical calculations. As a result, the robust four-step 4e- H+ coordination with PTO-NH3+ electrode achieves an excellent rate performance (214.3 mAh g-1 at 0.05 A g-1, 112.9 mAh g-1 at 40 A g-1), along with a long lifespan (10000 cycles). These findings shed light on the further avenue towards advanced proton batteries.
{"title":"Proton Coordination Chemistry in Pyrene-based Anode for Ultralong-life Aqueous Proton Batteries","authors":"Wenhui Yang, Chensi Zhan, Qiang Zhu, Lei Liu, Baiming Su, Haoxiang Yu, Liyuan Zhang, Lei Yan, Jie Shu","doi":"10.1039/d5qi00269a","DOIUrl":"https://doi.org/10.1039/d5qi00269a","url":null,"abstract":"Sustainable and safe aqueous proton batteries (APBs) have attracted significant attention owing to the unique “Grotthuss mechanism”. Although organic small molecules with stable and adjustable framework are promising electrode materials, their easy-dissolution in electrolyte and unsatisfactory intrinsic conductivity cripple the broader application in APB devices. Herein, the 2,7-diammonio-4,5,9,10-tetraone (PTO-NH3+) with the stable intermolecular hydrogen-bond networks is designed via the in-situ electrochemical reduction strategy, while the optimized molecule structure endows low charge transport barriers, high chemical reactivity, and prominent charge affinity. The fast kinetics of proton coordination/de-coordination behavior in PTO-NH3+ electrode is corroborated by ex-situ characterization techniques and theoretical calculations. As a result, the robust four-step 4e- H+ coordination with PTO-NH3+ electrode achieves an excellent rate performance (214.3 mAh g-1 at 0.05 A g-1, 112.9 mAh g-1 at 40 A g-1), along with a long lifespan (10000 cycles). These findings shed light on the further avenue towards advanced proton batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695478","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}
Hyunjin Cho, Yujin Kim, Whi Dong Kim, Young-Shin Park, Ju Young Woo, Hyung-Kyu Lim, Doh C. Lee
InAs-based quantum dots (QDs) are promising heavy-metal-free semiconductors for infrared emission technologies, offering tunable bandgaps via quantum confinement and excellent charge-carrier transport properties. Building on these advantages, we report the synthesis of QDs tailored for emission in the near-infrared (NIR) and short-wave infrared (SWIR) regions, emphasizing the critical role of capping ligands in controlling surface facet populations and nanocrystal morphology. Specifically, we demonstrate that the choice of ligand plays a critical role in determining the morphology and surface characteristics of InAs QDs. Using dioctylamine as a ligand results in InAs QDs with a spherical or tetrapod morphology, where nonpolar (110) facets are predominantly exposed on the surface. In contrast, oleic acid as a ligand promotes the formation of tetrahedral-shaped QDs with polar (111) crystalline planes being more prominently exposed. Using a one-pot synthesis approach, we successfully synthesized InAs/InZnP/ZnSe/ZnS core-multi-shell structures that effectively minimize interfacial defects. QDs with dioctylamine-capped core exhibit significantly higher photoluminescence quantum yield (PLQY) compared to those with oleic acid-capped cores. We achieved a PLQY of 39% at 1260 nm and 7.3% at 1420 nm with QDs using dioctylamine, representing efficiency values among the best reported in both the NIR and SWIR regions. Transient absorption (TA) spectroscopy reveals that dioctylamine-capped QDs exhibit reduced ground-state bleaching differences across excitation wavelengths compared to oleic acid-capped QDs, indicating significantly reduced interfacial trap states. These findings highlight the importance of ligand-driven facet control in the context of minimizing interfacial defect formation.
{"title":"Ligand-Driven Facet Control of InAs-Based Quantum Dots for Enhanced Near- and Shortwave Infrared Emission","authors":"Hyunjin Cho, Yujin Kim, Whi Dong Kim, Young-Shin Park, Ju Young Woo, Hyung-Kyu Lim, Doh C. Lee","doi":"10.1039/d5qi00142k","DOIUrl":"https://doi.org/10.1039/d5qi00142k","url":null,"abstract":"InAs-based quantum dots (QDs) are promising heavy-metal-free semiconductors for infrared emission technologies, offering tunable bandgaps via quantum confinement and excellent charge-carrier transport properties. Building on these advantages, we report the synthesis of QDs tailored for emission in the near-infrared (NIR) and short-wave infrared (SWIR) regions, emphasizing the critical role of capping ligands in controlling surface facet populations and nanocrystal morphology. Specifically, we demonstrate that the choice of ligand plays a critical role in determining the morphology and surface characteristics of InAs QDs. Using dioctylamine as a ligand results in InAs QDs with a spherical or tetrapod morphology, where nonpolar (110) facets are predominantly exposed on the surface. In contrast, oleic acid as a ligand promotes the formation of tetrahedral-shaped QDs with polar (111) crystalline planes being more prominently exposed. Using a one-pot synthesis approach, we successfully synthesized InAs/InZnP/ZnSe/ZnS core-multi-shell structures that effectively minimize interfacial defects. QDs with dioctylamine-capped core exhibit significantly higher photoluminescence quantum yield (PLQY) compared to those with oleic acid-capped cores. We achieved a PLQY of 39% at 1260 nm and 7.3% at 1420 nm with QDs using dioctylamine, representing efficiency values among the best reported in both the NIR and SWIR regions. Transient absorption (TA) spectroscopy reveals that dioctylamine-capped QDs exhibit reduced ground-state bleaching differences across excitation wavelengths compared to oleic acid-capped QDs, indicating significantly reduced interfacial trap states. These findings highlight the importance of ligand-driven facet control in the context of minimizing interfacial defect formation.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"57 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703330","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}
Zhe Hong, Lei Miao, Jialin Tan, Yang Liu, Shujing Chen, Lihua Deng, Qun Yang, Xianlong Gao, Fangtao Huang, Zhirong Zhu
Platelike zeolites with short diffusion pathway are promising catalysts due to the mass transfer advantages. Herein, a platelike ZSM-5 with shortened b‑axis thicknesses (~90 nm) was synthesized using a urea-assisted crystallization strategy. We disclose the significant application of this platelike catalyst in the reaction of toluene alkylation with ethanol to produce para-ethyltoluene (p-ET). The reaction results demonstrate that this platelike ZSM-5 exhibits a higher toluene conversion (58.3%) and ET selectivity (88.7%) than that of conventional ZSM-5. The improvement should be primarily due to the shortened straight channels of platelike ZSM-5, which facilitate the mass transport and increase the accessibility of acid sites. Nevertheless, the shortened b-axis of platelike ZSM-5 seems to have no significant positive impact on para-selectivity for p-ET. Hence, we construct a Si-zoned external surface on the platelike ZSM-5 by means of the surface modification strategy to accurately passivate the surface acid sites, thereby inhibiting the isomerization reaction, and achieving higher selectivity for p-ET (> 95%) and good catalytic stability (>100 h) in the reaction of toluene alkylation with ethanol.
{"title":"Urea-induced platelike ZSM-5 zeolite with Si zoning for efficient alkylation of toluene with ethanol to para-ethyltoluene","authors":"Zhe Hong, Lei Miao, Jialin Tan, Yang Liu, Shujing Chen, Lihua Deng, Qun Yang, Xianlong Gao, Fangtao Huang, Zhirong Zhu","doi":"10.1039/d5qi00100e","DOIUrl":"https://doi.org/10.1039/d5qi00100e","url":null,"abstract":"Platelike zeolites with short diffusion pathway are promising catalysts due to the mass transfer advantages. Herein, a platelike ZSM-5 with shortened b‑axis thicknesses (~90 nm) was synthesized using a urea-assisted crystallization strategy. We disclose the significant application of this platelike catalyst in the reaction of toluene alkylation with ethanol to produce para-ethyltoluene (p-ET). The reaction results demonstrate that this platelike ZSM-5 exhibits a higher toluene conversion (58.3%) and ET selectivity (88.7%) than that of conventional ZSM-5. The improvement should be primarily due to the shortened straight channels of platelike ZSM-5, which facilitate the mass transport and increase the accessibility of acid sites. Nevertheless, the shortened b-axis of platelike ZSM-5 seems to have no significant positive impact on para-selectivity for p-ET. Hence, we construct a Si-zoned external surface on the platelike ZSM-5 by means of the surface modification strategy to accurately passivate the surface acid sites, thereby inhibiting the isomerization reaction, and achieving higher selectivity for p-ET (> 95%) and good catalytic stability (>100 h) in the reaction of toluene alkylation with ethanol.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"57 19 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695480","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}
Sheng Wan, Hanbo Wang, Yan Wang, Rui Wang, Dongyu Pei, Ziming Wang, Yumei Tian, Shi Zhan, kechang li, Haiyan Lu
Nickel-cobalt double hydroxide is gaining significant interest due to its high theoretical specific capacitance. However, its tendency to agglomerate and low electrical conductivity present major challenges for its application. This study employed a one-step hydrothermal method to integrate exfoliated few-layer MXene materials with NiCo-LDH, facilitating the uniform vertical growth of NiCo-LDH nanosheets on the surface of the MXene, effectively minimizing agglomeration. Additionally, the interfacial synergy between MXene and NiCo-LDH enhances the transfer of electrons from NiCo-LDH to MXene, resulting in an electron-rich MXene and an oxygen vacancy-rich NiCo-LDH. Together, these characteristics significantly improve the electrochemical performance of the material at high current densities, achieving 7776 Wh kg−1 and 66.96 Wh k g−1 at 15 A g−1. After cycling 40,000 times, it retains an impressive capacity retention rate of 89.5%. These findings demonstrate that MXene materials effectively tackle the main challenges associated with NiCo-LDH, opening new possibilities for their application in electrode materials.
{"title":"Interfacial synergistic regulation of MXene-composited nickel-cobalt double hydroxide for high-performance supercapacitors","authors":"Sheng Wan, Hanbo Wang, Yan Wang, Rui Wang, Dongyu Pei, Ziming Wang, Yumei Tian, Shi Zhan, kechang li, Haiyan Lu","doi":"10.1039/d4qi02825b","DOIUrl":"https://doi.org/10.1039/d4qi02825b","url":null,"abstract":"Nickel-cobalt double hydroxide is gaining significant interest due to its high theoretical specific capacitance. However, its tendency to agglomerate and low electrical conductivity present major challenges for its application. This study employed a one-step hydrothermal method to integrate exfoliated few-layer MXene materials with NiCo-LDH, facilitating the uniform vertical growth of NiCo-LDH nanosheets on the surface of the MXene, effectively minimizing agglomeration. Additionally, the interfacial synergy between MXene and NiCo-LDH enhances the transfer of electrons from NiCo-LDH to MXene, resulting in an electron-rich MXene and an oxygen vacancy-rich NiCo-LDH. Together, these characteristics significantly improve the electrochemical performance of the material at high current densities, achieving 7776 Wh kg−1 and 66.96 Wh k g−1 at 15 A g−1. After cycling 40,000 times, it retains an impressive capacity retention rate of 89.5%. These findings demonstrate that MXene materials effectively tackle the main challenges associated with NiCo-LDH, opening new possibilities for their application in electrode materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"34 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677736","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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