Constructing fullerene-like metal-organic nanocage integrating novel architectures and unique functions remains a formidable challenge. Herein, an unprecedented high-nuclearity fullerene-like heteropolyoxometalate cluster, {Na32[(V V O2)30(Mo VI O4)12(PhPO3)48(CH3COO)12](CO3)2}•5MeCN (Mo24V30P48, MeCN=acetonitrile) was successfully synthesized via a one-pot method. This anionic cluster can be described as a pseudo-cubic cage are assembled from 12 {Mo₂V₂P₄} quadrilaterals and 6 {VO₆} octahedra. Sodium ions are employed as templates to fill the cage. The entire structure displays a distinct four-shell {Mo₂₄}@{V₃₀P₄₈}@{Na₂₄}@{Na₈} arrangement. Since all the {Mo2} units and Na⁺ ions are located on the {V₃₀P₄₈} cage, this structure can also be simplified as a fullerene-like heterometallic cage composed of 12 {Mo₂V₂P₄} hexagons, 8 {NaV₃P₃} hexagons, and 24 {NaV₂P₃} pentagons. Additionally, Mo24V30P48 exhibits high solution stability, as confirmed by ESI-MS, PXRD and SEM, which makes it a highly efficient and stable catalyst for phenolic oxidation reactions.
构建集新型结构和独特功能于一体的类富勒烯金属有机纳米笼仍然是一个艰巨的挑战。在此基础上，通过一锅法成功合成了前所未有的高核类富勒烯异多金属氧酸盐簇{Na32[(V V O2)30(Mo VI O4)12(PhPO3)48(CH3COO)12](CO3)2}•5MeCN （Mo24V30P48, MeCN=乙腈）。该阴离子簇由12个{Mo₂V₂P₄}四边形和6个{VO₆}八面体组合而成的伪立方笼。钠离子作为模板填充笼。整个结构呈现出独特的四壳式{Mo₂₄}@{V₃₀P₄₈}@{Na₂₄}@{Na₈}排列。由于所有的{Mo2}单位和Na⁺离子都位于{V₃₀P₄₈}笼上，因此这种结构也可以简化为由12个{Mo₂V₂P₄}六边形、8个{NaV₃P₃}六边形和24个{NaV₂P₃}五边形组成的类富勒烯异型金属笼。此外，通过ESI-MS、PXRD和SEM分析，Mo24V30P48具有较高的溶液稳定性，是一种高效、稳定的酚类氧化反应催化剂。
{"title":"Self-assembly of a high-nuclearity fullerene-like heteropolyoxometalate cage","authors":"Shuangxue Wu, Chun-Yi Sun, Xinlong Wang, Kui-Zhan Shao, Chao Qin, Zhong-Min Su","doi":"10.1039/d5qi02549d","DOIUrl":"https://doi.org/10.1039/d5qi02549d","url":null,"abstract":"Constructing fullerene-like metal-organic nanocage integrating novel architectures and unique functions remains a formidable challenge. Herein, an unprecedented high-nuclearity fullerene-like heteropolyoxometalate cluster, {Na32[(V V O2)30(Mo VI O4)12(PhPO3)48(CH3COO)12](CO3)2}•5MeCN (Mo24V30P48, MeCN=acetonitrile) was successfully synthesized via a one-pot method. This anionic cluster can be described as a pseudo-cubic cage are assembled from 12 {Mo₂V₂P₄} quadrilaterals and 6 {VO₆} octahedra. Sodium ions are employed as templates to fill the cage. The entire structure displays a distinct four-shell {Mo₂₄}@{V₃₀P₄₈}@{Na₂₄}@{Na₈} arrangement. Since all the {Mo2} units and Na⁺ ions are located on the {V₃₀P₄₈} cage, this structure can also be simplified as a fullerene-like heterometallic cage composed of 12 {Mo₂V₂P₄} hexagons, 8 {NaV₃P₃} hexagons, and 24 {NaV₂P₃} pentagons. Additionally, Mo24V30P48 exhibits high solution stability, as confirmed by ESI-MS, PXRD and SEM, which makes it a highly efficient and stable catalyst for phenolic oxidation reactions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146001236","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 direct epoxidation of propylene using H2 and O2 has emerged as a promising alternative to conventional industrial processes, offering superior atom economy, environmental compatibility, and process economics. This work demonstrates a facile design strategy to enhance Au-Ti synergy in Au/TS-1 catalysts through precise control of TPAOH/Si ratios during zeolite synthesis. Systematic reduction of TS-1 crystallite dimensions to 220 nm was achieved through TPAOH/Si ratio optimization, simultaneously producing micro-mesoporous hierarchical architectures while preserving crystallinity. The engineered Au/TS-1 catalyst prepared via deposition-precipitation method exhibited exceptional propylene oxide selectivity (>95%) with stable activity, which is attributed to optimized electronic coupling between Au nanoparticles and framework Ti species. Spectroscopic analyses (XPS/UV-vis) revealed strengthened Au-Ti electronic interactions through positive binding energy shifts (Au 4f7/2: +0.4 eV; Ti 2p1/2: +0.9 eV), correlating with enhanced propylene activation. The catalytic efficiency was further governed by synergistic effects between accessible Ti-surrounded Au sites and surface silanol density. In-situ FT-IR kinetic analysis identified two distinct reaction phases: initial rate-limiting propylene chemisorption (0-20 min) followed by steady-state operation (25-55 min), with acetone and acetaldehyde identified as primary byproducts. This mechanistic understanding of structure-activity relationships advances fundamental principles for designing high-performance epoxidation catalysts while accelerating industrial implementation of sustainable propylene oxide production routes.
使用H2和O2直接环氧化丙烯已成为传统工业工艺的一种有前途的替代方法，具有优越的原子经济性，环境相容性和工艺经济性。这项工作证明了一种简单的设计策略，通过精确控制沸石合成过程中TPAOH/Si的比例来增强Au/TS-1催化剂中Au- ti的协同作用。通过优化TPAOH/Si比，系统地将TS-1晶体尺寸减小到220 nm，同时产生微介孔分层结构，同时保持结晶度。通过沉积-沉淀法制备的工程Au/TS-1催化剂具有优异的环氧丙烷选择性（>95%）和稳定的活性，这归因于Au纳米颗粒与框架Ti之间的优化电子耦合。光谱分析（XPS/UV-vis）显示通过正结合能位移（Au 4f7/2: +0.4 eV; Ti 2p1/2: +0.9 eV）增强了Au-Ti电子相互作用，这与丙烯活化增强有关。催化效率进一步受到可接近的钛包围金位点和表面硅醇密度之间的协同效应的支配。原位FT-IR动力学分析确定了两个不同的反应阶段：初始限速丙烯化学吸附（0-20分钟），然后是稳态操作（25-55分钟），丙酮和乙醛被确定为主要副产物。这种结构-活性关系的机制理解推进了设计高性能环氧化催化剂的基本原则，同时加速了可持续环氧丙烷生产路线的工业实施。
{"title":"Propene epoxidation over low-cost Au/TS-1 catalyst: modulation of synergetic effect between Ti and Au sites","authors":"Yupeng Tian, Yujia Liu, Chenyang Zhao, Mingzhi Li, Xinmei Liu, Bing Sun, Wei Xu","doi":"10.1039/d5qi02258d","DOIUrl":"https://doi.org/10.1039/d5qi02258d","url":null,"abstract":"The direct epoxidation of propylene using H2 and O2 has emerged as a promising alternative to conventional industrial processes, offering superior atom economy, environmental compatibility, and process economics. This work demonstrates a facile design strategy to enhance Au-Ti synergy in Au/TS-1 catalysts through precise control of TPAOH/Si ratios during zeolite synthesis. Systematic reduction of TS-1 crystallite dimensions to 220 nm was achieved through TPAOH/Si ratio optimization, simultaneously producing micro-mesoporous hierarchical architectures while preserving crystallinity. The engineered Au/TS-1 catalyst prepared via deposition-precipitation method exhibited exceptional propylene oxide selectivity (>95%) with stable activity, which is attributed to optimized electronic coupling between Au nanoparticles and framework Ti species. Spectroscopic analyses (XPS/UV-vis) revealed strengthened Au-Ti electronic interactions through positive binding energy shifts (Au 4f7/2: +0.4 eV; Ti 2p1/2: +0.9 eV), correlating with enhanced propylene activation. The catalytic efficiency was further governed by synergistic effects between accessible Ti-surrounded Au sites and surface silanol density. In-situ FT-IR kinetic analysis identified two distinct reaction phases: initial rate-limiting propylene chemisorption (0-20 min) followed by steady-state operation (25-55 min), with acetone and acetaldehyde identified as primary byproducts. This mechanistic understanding of structure-activity relationships advances fundamental principles for designing high-performance epoxidation catalysts while accelerating industrial implementation of sustainable propylene oxide production routes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995930","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}
Yuta Takeuchi, Minoru Yamada, Itaru Tsuchiya, Yoshiki Ozawa, Masaaki Abe, Akiko Hori
Dumbbell-shaped Zn(II) paddlewheel dimers bearing π-extended triphenylamine-ethynylpyridine ligands were synthesized to investigate how fluorination and axial π-extension influence structural flexibility and luminescence responsiveness. Singlecrystal X-ray diffraction revealed that the benzoate and pentafluorobenzoate derivatives retain the Zn2(μ-carboxylate)4 core but differ in carboxylate planarity, intermolecular contacts, and overall molecular distortion. These subtle structural variations strongly affect their excited-state landscapes. The fluorinated complex exhibits an additional intramolecular charge-transfer absorption band and enhanced electronic anisotropy, leading to pronounced changes in the solid-state emission. Both complexes display reversible mechanochromic luminescence associated with partial amorphization and recrystallization, while the fluorinated derivative undergoes a larger red shift and higher quantum yield after grinding. Highpressure photoluminescence measurements on single crystals revealed continuous and nearly reversible emission shifts.The fluorinated complex shows a substantial 83 nm shift (ΔE = 0.36 eV) and a full multicolor progression from green to orange-red up to 3.6 GPa, whereas the non-fluorinated analogue displays only modest changes. These behaviors demonstrate that fluorination increases structural flexibility and enhances the pressure adaptability of the Zn2 core. The results establish a design strategy in which a d10 metal scaffold is combined with electronically tunable π-extended axial ligands to achieve multicolor, reversible, and stimuli-responsive luminescence in simple molecular assemblies.
{"title":"Multicolor and reversible stimuli-responsive luminescence of dumbbell-shaped Zn(II) complexes with extended triphenylamine-attached ethynylpyridine terminals","authors":"Yuta Takeuchi, Minoru Yamada, Itaru Tsuchiya, Yoshiki Ozawa, Masaaki Abe, Akiko Hori","doi":"10.1039/d5qi02451j","DOIUrl":"https://doi.org/10.1039/d5qi02451j","url":null,"abstract":"Dumbbell-shaped Zn(II) paddlewheel dimers bearing π-extended triphenylamine-ethynylpyridine ligands were synthesized to investigate how fluorination and axial π-extension influence structural flexibility and luminescence responsiveness. Singlecrystal X-ray diffraction revealed that the benzoate and pentafluorobenzoate derivatives retain the Zn2(μ-carboxylate)4 core but differ in carboxylate planarity, intermolecular contacts, and overall molecular distortion. These subtle structural variations strongly affect their excited-state landscapes. The fluorinated complex exhibits an additional intramolecular charge-transfer absorption band and enhanced electronic anisotropy, leading to pronounced changes in the solid-state emission. Both complexes display reversible mechanochromic luminescence associated with partial amorphization and recrystallization, while the fluorinated derivative undergoes a larger red shift and higher quantum yield after grinding. Highpressure photoluminescence measurements on single crystals revealed continuous and nearly reversible emission shifts.The fluorinated complex shows a substantial 83 nm shift (ΔE = 0.36 eV) and a full multicolor progression from green to orange-red up to 3.6 GPa, whereas the non-fluorinated analogue displays only modest changes. These behaviors demonstrate that fluorination increases structural flexibility and enhances the pressure adaptability of the Zn2 core. The results establish a design strategy in which a d10 metal scaffold is combined with electronically tunable π-extended axial ligands to achieve multicolor, reversible, and stimuli-responsive luminescence in simple molecular assemblies.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"70 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021967","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 systematic nucleophilic functionalisation of the cationic pentaphosphole ligand complex [Cp*Fe(η4-P5Me)][OTf] (A) with sterically demanding CpR derivatives is reported. This newly developed protocol turned out to be a highly reliable method for the synthesis of end-deck cyclo-P5 ligand complexes bearing bulky CpR substituents. By the reaction of A with anionic CpR salts, complexes of the type [Cp*Fe(η4-P5MeCpR)] (Cp* = η5-C5Me5; CpR = Cp´ (1), Cp´´ (2), Cp´´´ (3), CpMe (4); Cp´ = η5-C5H4tBu, Cp´´ = η5-1,3-tBu2C5H3, Cp´´´ = η5-1,3,4-tBu3C5H2, CpMe = η5-C5Me4H) are obtained. All products feature a selective 1,1´-disubstitution at the cyclo-P5 ligand. Further reactivity studies of these complexes with FeBr2 enabled the formation of novel, sterically demanding ferrocene derivatives [{Cp*Fe(η4-P5Me(h5-Cp´´))}2Fe] (5) and [Cp*Fe(η4-P5Me(η5-Cp´´))FeCp´´] (6), featuring three different Fe atoms in a ferrocene-like environment. Oxidation of 5 yielded the dicationic complex [{Cp*Fe(η4-P5Me(η5-Cp´´))}2Fe][FAl]2 (7). EPR, zero-field 57Fe Mössbauer, as well as DFT investigations on 7, showed a symmetric distribution of the positive charges on the outer Fe atoms.
{"title":"Cationic Polypnictogen Complexes as Building Blocks for Novel Ferrocenes","authors":"Maximilian Widmann, Zihan Zhang, Anja Rehse, Gabor Balazs, Alexey Timoshkin, Karsten Meyer, Rainer R.F. Winter, Manfred Scheer","doi":"10.1039/d5qi02477c","DOIUrl":"https://doi.org/10.1039/d5qi02477c","url":null,"abstract":"The systematic nucleophilic functionalisation of the cationic pentaphosphole ligand complex [Cp*Fe(η<small><sup>4</sup></small>-P<small><sub>5</sub></small>Me)][OTf] (<strong>A</strong>) with sterically demanding Cp<small><sup>R</sup></small> derivatives is reported. This newly developed protocol turned out to be a highly reliable method for the synthesis of end-deck <em>cyclo</em>-P<small><sub>5</sub></small> ligand complexes bearing bulky Cp<small><sup>R</sup></small> substituents. By the reaction of <strong>A</strong> with anionic Cp<small><sup>R</sup></small> salts, complexes of the type [Cp*Fe(η<small><sup>4</sup></small>-P<small><sub>5</sub></small>MeCp<small><sup>R</sup></small>)] (Cp* = η<small><sup>5</sup></small>-C<small><sub>5</sub></small>Me<small><sub>5</sub></small>; Cp<small><sup>R</sup></small> = Cp´ (<strong>1</strong>), Cp´´ (<strong>2</strong>), Cp´´´ (<strong>3</strong>), Cp<small><sup>Me</sup></small> (<strong>4</strong>); Cp´ = η<small><sup>5</sup></small>-C<small><sub>5</sub></small>H<small><sub>4</sub></small><small><sup>t</sup></small>Bu, Cp´´ = η<small><sup>5</sup></small>-1,3-<small><sup>t</sup></small>Bu<small><sub>2</sub></small>C<small><sub>5</sub></small>H<small><sub>3</sub></small>, Cp´´´ = η<small><sup>5</sup></small>-1,3,4-<small><sup>t</sup></small>Bu<small><sub>3</sub></small>C<small><sub>5</sub></small>H<small><sub>2</sub></small>, Cp<small><sup>Me</sup></small> = η<small><sup>5</sup></small>-C<small><sub>5</sub></small>Me<small><sub>4</sub></small>H) are obtained. All products feature a selective 1,1´-disubstitution at the <em>cyclo</em>-P<small><sub>5</sub></small> ligand. Further reactivity studies of these complexes with FeBr<small><sub>2</sub></small> enabled the formation of novel, sterically demanding ferrocene derivatives [{Cp*Fe(η<small><sup>4</sup></small>-P<small><sub>5</sub></small>Me(h<small><sup>5</sup></small>-Cp´´))}<small><sub>2</sub></small>Fe] (<strong>5</strong>) and [Cp*Fe(η<small><sup>4</sup></small>-P<small><sub>5</sub></small>Me(η<small><sup>5</sup></small>-Cp´´))FeCp´´] (<strong>6</strong>), featuring three different Fe atoms in a ferrocene-like environment. Oxidation of <strong>5</strong> yielded the dicationic complex [{Cp*Fe(η<small><sup>4</sup></small>-P<small><sub>5</sub></small>Me(η<small><sup>5</sup></small>-Cp´´))}<small><sub>2</sub></small>Fe][FAl]<small><sub>2</sub></small> (<strong>7</strong>). EPR, zero-field <small><sup>57</sup></small>Fe Mössbauer, as well as DFT investigations on <strong>7</strong>, showed a symmetric distribution of the positive charges on the outer Fe atoms.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"52 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146022013","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}
Achieving multilevel conduction in a cost-effective transition metal complex of a redox-active ligand will be an efficient way of designing a molecular memristor. This paper presents a rare example of a tris-azo anion radical ligand wrapped singlet five-coordinate low-spin Co(II) complex, [(L)˙⁻Co(II)]PF6, [1]PF6, that showed solution-processible resistive switching memory with synaptic functionality. The single-crystal X-ray structure, variable-temperature magnetic studies, and DFT calculations of [1]PF₆ showed that it has one electron reduced ligand, [L]˙⁻ which is antiferromagnetically coupled with the low-spin Co(II) center resulting in an s = 0 ground state. The [1]PF₆ showed multiple reversible and quasi-reversible redox events, insisting to explored as a molecular memristor. The indium tin oxide/[1]PF6/Ag memristor demonstrated excellent switching property with a large ON/OFF ratio (>103), endurance (>500 cycles), retention time (>104 s), and stability at an elevated temperature (100 °C). Moreover, on applying pulsed electrical stimuli, the memristor exhibits potentiation and depression behavior, a key feature for synaptic plasticity. The device was SET at cathodic potential, and thus, the facile ligand-based reductions in [1]PF6 played a decisive role in the device.
{"title":"A tris-azo anion radical ligand wrapped multiple redox singlet Co(II) complex for efficient molecular memristor towards neuromorphic computing","authors":"Swati Rani, Priya Kaith, Swayang Priya Mahanta, Muskan Muskan, Nisha Yadav, Avtar Changotra, Subhankar Bedanta, Siriyara Jagannatha Prathapa, Ashok Bera, Subhas Samanta","doi":"10.1039/d5qi01965f","DOIUrl":"https://doi.org/10.1039/d5qi01965f","url":null,"abstract":"Achieving multilevel conduction in a cost-effective transition metal complex of a redox-active ligand will be an efficient way of designing a molecular memristor. This paper presents a rare example of a tris-azo anion radical ligand wrapped singlet five-coordinate low-spin Co(II) complex, [(<strong>L</strong>)˙⁻Co(II)]PF<small><sub>6</sub></small>, [<strong>1</strong>]PF<small><sub>6</sub></small>, that showed solution-processible resistive switching memory with synaptic functionality. The single-crystal X-ray structure, variable-temperature magnetic studies, and DFT calculations of [<strong>1</strong>]PF₆ showed that it has one electron reduced ligand, [<strong>L</strong>]˙⁻ which is antiferromagnetically coupled with the low-spin Co(II) center resulting in an s = 0 ground state. The [<strong>1</strong>]PF₆ showed multiple reversible and quasi-reversible redox events, insisting to explored as a molecular memristor. The indium tin oxide/[<strong>1</strong>]PF<small><sub>6</sub></small>/Ag memristor demonstrated excellent switching property with a large ON/OFF ratio (>10<small><sup>3</sup></small>), endurance (>500 cycles), retention time (>10<small><sup>4</sup></small> s), and stability at an elevated temperature (100 °C). Moreover, on applying pulsed electrical stimuli, the memristor exhibits potentiation and depression behavior, a key feature for synaptic plasticity. The device was SET at cathodic potential, and thus, the facile ligand-based reductions in [<strong>1</strong>]PF<small><sub>6</sub></small> played a decisive role in the device.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"31 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995928","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}
Jun Wu, Gang Pan, Ming Jin, Jiahao Bai, Tailong Shi, Yong Li
The catalytic reductive amination of biomass-derived carbonyl compounds into value-added primary amines has attracted significant attention in renewable biomass upgrading. Herein, highly dispersed Ru clusters embedded nitrogen-doped hollow carbon spheres (Ru@NHCS) catalysts were constructed, which achieved a 100% furfurylamine (FUA) yield, and exhibited the superior initial reaction rate of 3745.7 mmol gRu-1 h-1 and turnover frequency of 378.58 h-1 in the reductive amination of biomass-derived furfural. Systematic structure characterization indicated that the presence of abundant N species promoted the uniform dispersion of Ru clusters and induced the electronic metal-support interaction (EMSI) between Ru and NHCS support, thus leading to the formation of bifunctional Ru0 and Ruδ+ active sites. Structure-activity relationship study demonstrated that the synergistic catalysis of Ru0 and Ruδ+ active sites effectively promoted the adsorption and activation of H2 and NH3 molecules, and accelerated the hydrogenation of imine and the aminolysis of Schiff base intermediates, thereby achieving the highly selective synthesis of FUA under mild reaction conditions. Moreover, the Ru@NHCS catalyst exhibited excellent catalytic stability in the five consecutive cycles, and showed broad substrate applicability for sustainable primary amine synthesis. This work not only unveils rational design strategies for developing efficient, stable metal catalysts to achieve highly selective synthesis of value-added primary amines but also provides essential theoretical guidance for efficient biomass conversion.
{"title":"Highly dispersed Ru clusters embedded nitrogen-doped hollow carbon spheres with tunable electronic property for efficient catalytic reductive amination of biomass-derived furfural","authors":"Jun Wu, Gang Pan, Ming Jin, Jiahao Bai, Tailong Shi, Yong Li","doi":"10.1039/d5qi02342d","DOIUrl":"https://doi.org/10.1039/d5qi02342d","url":null,"abstract":"The catalytic reductive amination of biomass-derived carbonyl compounds into value-added primary amines has attracted significant attention in renewable biomass upgrading. Herein, highly dispersed Ru clusters embedded nitrogen-doped hollow carbon spheres (Ru@NHCS) catalysts were constructed, which achieved a 100% furfurylamine (FUA) yield, and exhibited the superior initial reaction rate of 3745.7 mmol gRu-1 h-1 and turnover frequency of 378.58 h-1 in the reductive amination of biomass-derived furfural. Systematic structure characterization indicated that the presence of abundant N species promoted the uniform dispersion of Ru clusters and induced the electronic metal-support interaction (EMSI) between Ru and NHCS support, thus leading to the formation of bifunctional Ru0 and Ruδ+ active sites. Structure-activity relationship study demonstrated that the synergistic catalysis of Ru0 and Ruδ+ active sites effectively promoted the adsorption and activation of H2 and NH3 molecules, and accelerated the hydrogenation of imine and the aminolysis of Schiff base intermediates, thereby achieving the highly selective synthesis of FUA under mild reaction conditions. Moreover, the Ru@NHCS catalyst exhibited excellent catalytic stability in the five consecutive cycles, and showed broad substrate applicability for sustainable primary amine synthesis. This work not only unveils rational design strategies for developing efficient, stable metal catalysts to achieve highly selective synthesis of value-added primary amines but also provides essential theoretical guidance for efficient biomass conversion.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"26 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995927","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}
Oxygen vacancies (OVs) play a critical role in enhancing the catalytic performance of transition-metal oxides in advanced oxidation processes (AOPs). However, the effect of OVs on the activation of different persulfates, peroxymonosulfate (PMS) and peroxydisulfate (PDS), is still not well understood. Here, we employ ultrasonic defect engineering to adjust the OV content of α-MnO2 and systematically benchmark its activation of PMS and PDS. XPS, EPR, and electrochemical analyses revealed that the ultrasound-treated α-MnO2 exhibited a significantly increased proportion of Mn(III) and a markedly higher OV concentration, thereby creating densely populated redox-active sites for persulfate adsorption and electron transfer. Mechanistic investigations indicated that in the PMS system, the oxidation pathway was closely associated with OVs: at low OV densities, radical oxidation (SO4•⁻/•OH) predominates, whereas at high OV densities, a non-radical route dominated by singlet oxygen (1O2) prevails. In contrast, the oxidation pathway in the PDS system exhibited a weak correlation with OV content, implicating distinct adsorption/activation motifs for PMS versus PDS on α-MnO2. Radical scavenging experiments and identification of reactive oxygen species further validated these mechanistic differences. Collectively, this work establishes a clear structure-reactivity correlation and provides a defect-engineering blueprint for tailoring targeted reactive oxygen species in water purification applications.
{"title":"Comparative insights into the role of oxygen vacancies in α-MnO2 for activating peroxymonosulfate and peroxydisulfate","authors":"Qianwei Li, Daoqing Liu, Wei Yan, Hao LIu, Chunmao Chen","doi":"10.1039/d5qi02252e","DOIUrl":"https://doi.org/10.1039/d5qi02252e","url":null,"abstract":"Oxygen vacancies (OVs) play a critical role in enhancing the catalytic performance of transition-metal oxides in advanced oxidation processes (AOPs). However, the effect of OVs on the activation of different persulfates, peroxymonosulfate (PMS) and peroxydisulfate (PDS), is still not well understood. Here, we employ ultrasonic defect engineering to adjust the OV content of α-MnO2 and systematically benchmark its activation of PMS and PDS. XPS, EPR, and electrochemical analyses revealed that the ultrasound-treated α-MnO2 exhibited a significantly increased proportion of Mn(III) and a markedly higher OV concentration, thereby creating densely populated redox-active sites for persulfate adsorption and electron transfer. Mechanistic investigations indicated that in the PMS system, the oxidation pathway was closely associated with OVs: at low OV densities, radical oxidation (SO4•⁻/•OH) predominates, whereas at high OV densities, a non-radical route dominated by singlet oxygen (1O2) prevails. In contrast, the oxidation pathway in the PDS system exhibited a weak correlation with OV content, implicating distinct adsorption/activation motifs for PMS versus PDS on α-MnO2. Radical scavenging experiments and identification of reactive oxygen species further validated these mechanistic differences. Collectively, this work establishes a clear structure-reactivity correlation and provides a defect-engineering blueprint for tailoring targeted reactive oxygen species in water purification applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"46 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995929","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}
Zhuzhu Du, Conghao Yu, Lei Liu, Jinmeng Sun, Wei Ai
Starch-derived hard carbons suffer from volatile release and insufficient carbon-layer rearrangement during pyrolysis, leading to structural collapse, small graphite domains, and poor sodium storage performance. Here, we report a space-confined carbonization strategy enabled by the flame-retardant polymer p-phenylenediamine polyphosphate (PPD-PP), which coats starch and stabilizes its structure during pyrolysis. Nitrogen- and phosphorus-containing species released from PPD-PP catalyze polysaccharide dehydrogenation and aromatization, forming a protective carbon layer that preserves the granular morphology and directs the growth of long-range nanographite-like domains. The resulting quasi-spherical hard carbon (QSHC) integrates reduced defects and controlled microporosity with a mesoporous framework that facilitates rapid ion transport and enhances intrinsic conductivity. As a result, QSHC delivers a high capacity of 180 mAh g-1 at 1 A g-1, with plateau contributions of up to 70%. Full cells pairing QSHC with Na3V2(PO4)3F3@C cathodes achieve an energy density of 239 Wh kg-1 at a power output of 7.1 kW kg-1, while retaining 95% capacity after 120 cycles. This work demonstrates a simple and scalable route for engineering biomass-derived carbons and provides new insights into the rational design of high-rate hard carbon anodes for practical sodium-ion batteries.
淀粉类硬碳在热解过程中挥发性释放和碳层重排不足，导致结构坍塌，石墨畴小，储钠性能差。在这里，我们报告了一种由阻燃聚合物对苯二胺聚磷酸（PPD-PP）实现的空间限制碳化策略，该策略在热解过程中包裹淀粉并稳定其结构。PPD-PP释放的含氮和含磷物质催化多糖脱氢和芳构化，形成保护碳层，保持颗粒形态并指导远程纳米石墨样结构域的生长。由此产生的准球形硬碳（QSHC）结合了减少缺陷和控制微孔隙度的介孔框架，促进了离子的快速传输并提高了固有电导率。因此，QSHC在1 a g-1时提供180 mAh g-1的高容量，平台贡献高达70%。将QSHC与Na3V2(PO4)3F3@C阴极配对的全电池在7.1 kW kg-1的功率输出下获得239 Wh kg-1的能量密度，并且在120次循环后保持95%的容量。这项工作为工程生物质衍生碳提供了一条简单而可扩展的途径，并为实用钠离子电池的高速率硬碳阳极的合理设计提供了新的见解。
{"title":"Flame-retardant polymer-enabled space-confined carbonization toward quasi-spherical hard carbon for high-rate sodium storage","authors":"Zhuzhu Du, Conghao Yu, Lei Liu, Jinmeng Sun, Wei Ai","doi":"10.1039/d5qi02175h","DOIUrl":"https://doi.org/10.1039/d5qi02175h","url":null,"abstract":"Starch-derived hard carbons suffer from volatile release and insufficient carbon-layer rearrangement during pyrolysis, leading to structural collapse, small graphite domains, and poor sodium storage performance. Here, we report a space-confined carbonization strategy enabled by the flame-retardant polymer p-phenylenediamine polyphosphate (PPD-PP), which coats starch and stabilizes its structure during pyrolysis. Nitrogen- and phosphorus-containing species released from PPD-PP catalyze polysaccharide dehydrogenation and aromatization, forming a protective carbon layer that preserves the granular morphology and directs the growth of long-range nanographite-like domains. The resulting quasi-spherical hard carbon (QSHC) integrates reduced defects and controlled microporosity with a mesoporous framework that facilitates rapid ion transport and enhances intrinsic conductivity. As a result, QSHC delivers a high capacity of 180 mAh g-1 at 1 A g-1, with plateau contributions of up to 70%. Full cells pairing QSHC with Na3V2(PO4)3F3@C cathodes achieve an energy density of 239 Wh kg-1 at a power output of 7.1 kW kg-1, while retaining 95% capacity after 120 cycles. This work demonstrates a simple and scalable route for engineering biomass-derived carbons and provides new insights into the rational design of high-rate hard carbon anodes for practical sodium-ion batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993176","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 selective production of linear aldehydes from long-chain α-olefins using heterogeneous Rh catalysts faces a challenge, as non-selective sites in unconfined environments severely compromise regioselectivity. Herein, we report a strategy to achieve high regioselectivity and activity in 1-hexene hydroformylation by confining atomically dispersed Rh sites within the micropores of a silicalite-1 (S-1) zeolite, followed by the selective poisoning of external Rh sites. A series of Rh@S-1 catalysts with varying loadings were synthesized by an in situ hydrothermal method. Comprehensive characterization (XRD, XPS, STEM) confirmed the successful incorporation of Rh as atomically dispersed species within the MFI framework while preserving the zeolite’s textural properties. In the hydroformylation of 1-hexene, the unpoisoned catalyst exhibited high conversion (98.3%) but poor regioselectivity (n/i = 2.7). The introduction of bulky thiol poisons (DMBT and TPMT), which are size-excluded from the zeolite micropores, selectively passivated the external Rh sites. Consequently, the reaction was confined predominantly to the internal Rh sites, thereby dramatically boosting the n/i ratio to 59.9 and 9.3 for DMBT and TPMT poisoned catalysts, respectively, at a low 1-hexene concentration. The superior regioselectivity achieved with DMBT over TPMT is attributed to its more effective poisoning of pore-mouth Rh sites. However, it also introduced higher diffusion resistance, leading to lower conversion and higher apparent activation energy. Moreover, the catalysts demonstrated excellent recyclability. This work elucidates the decisive roles of confined internal versus unconfined external Rh sites in the atomically dispersed Rh@S-1 catalyst for 1-hexene hydroformylation. This finding provides a key design principle for developing efficient heterogeneous Rh catalysts for long-chain α-olefin hydroformylation.
{"title":"Probing the Distinct Roles of Zeolite-Confined and External Rh Sites by Selective Poisoning in 1-Hexene Hydroformylation Regioselectivity","authors":"Rui Feng, Wei Wang, Tianbo Li, Feifei Yang, Xiaoyan Hu, Xinlong Yan, Lianming Zhao, Shijian Lu","doi":"10.1039/d5qi02438b","DOIUrl":"https://doi.org/10.1039/d5qi02438b","url":null,"abstract":"The selective production of linear aldehydes from long-chain α-olefins using heterogeneous Rh catalysts faces a challenge, as non-selective sites in unconfined environments severely compromise regioselectivity. Herein, we report a strategy to achieve high regioselectivity and activity in 1-hexene hydroformylation by confining atomically dispersed Rh sites within the micropores of a silicalite-1 (S-1) zeolite, followed by the selective poisoning of external Rh sites. A series of Rh@S-1 catalysts with varying loadings were synthesized by an in situ hydrothermal method. Comprehensive characterization (XRD, XPS, STEM) confirmed the successful incorporation of Rh as atomically dispersed species within the MFI framework while preserving the zeolite’s textural properties. In the hydroformylation of 1-hexene, the unpoisoned catalyst exhibited high conversion (98.3%) but poor regioselectivity (n/i = 2.7). The introduction of bulky thiol poisons (DMBT and TPMT), which are size-excluded from the zeolite micropores, selectively passivated the external Rh sites. Consequently, the reaction was confined predominantly to the internal Rh sites, thereby dramatically boosting the n/i ratio to 59.9 and 9.3 for DMBT and TPMT poisoned catalysts, respectively, at a low 1-hexene concentration. The superior regioselectivity achieved with DMBT over TPMT is attributed to its more effective poisoning of pore-mouth Rh sites. However, it also introduced higher diffusion resistance, leading to lower conversion and higher apparent activation energy. Moreover, the catalysts demonstrated excellent recyclability. This work elucidates the decisive roles of confined internal versus unconfined external Rh sites in the atomically dispersed Rh@S-1 catalyst for 1-hexene hydroformylation. This finding provides a key design principle for developing efficient heterogeneous Rh catalysts for long-chain α-olefin hydroformylation.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"85 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993168","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}
Mei Hu, Zhencheng Wu, Xin Su, Hongheng Chen, Qun Jing, Zhaohui Chen, Ming-Hsien Lee
Functional groups are crucial for achieving the balanced properties with a short cutoff edge, moderate birefringence, and strong second-harmonic generation (SHG). Herein, a targeted design strategy integrating small heteroatom-substituted tetrahedral and π-conjugated units was employed. This approach successfully yielded two functionally distinct crystals of C(NH2)3SO3NH2: a birefringent crystal (α-phase: P21/c) and a novel nonlinear optical (NLO) crystal (β-phase: Iba2). These compounds exhibit a short deep-ultraviolet (DUV) cutoff edge (below 190 nm) and suitable birefringence (0.068–0.074@546 nm). Additionally, β-C(NH2)3SO3NH2 possesses a strong SHG response (1.41 × KDP). Functional group analysis reveals that the [C(NH2)3] cation exhibits a dual functionality: its small heteroatom structure widens the band gap, while its π-conjugated framework enhances the birefringence and the SHG response, achieving an optimal balance. This study establishes a generalizable design framework for DUV optical crystals, offering a viable strategy to reconcile the trade-off between key properties.
{"title":"Strategically designed deep-ultraviolet optical crystals with balanced properties by small heteroatom substitution","authors":"Mei Hu, Zhencheng Wu, Xin Su, Hongheng Chen, Qun Jing, Zhaohui Chen, Ming-Hsien Lee","doi":"10.1039/d5qi02475g","DOIUrl":"https://doi.org/10.1039/d5qi02475g","url":null,"abstract":"Functional groups are crucial for achieving the balanced properties with a short cutoff edge, moderate birefringence, and strong second-harmonic generation (SHG). Herein, a targeted design strategy integrating small heteroatom-substituted tetrahedral and π-conjugated units was employed. This approach successfully yielded two functionally distinct crystals of C(NH<small><sub>2</sub></small>)<small><sub>3</sub></small>SO<small><sub>3</sub></small>NH<small><sub>2</sub></small>: a birefringent crystal (α-phase: <em>P</em>2<small><sub>1</sub></small>/<em>c</em>) and a novel nonlinear optical (NLO) crystal (β-phase: <em>Iba</em>2). These compounds exhibit a short deep-ultraviolet (DUV) cutoff edge (below 190 nm) and suitable birefringence (0.068–0.074@546 nm). Additionally, β-C(NH<small><sub>2</sub></small>)<small><sub>3</sub></small>SO<small><sub>3</sub></small>NH<small><sub>2</sub></small> possesses a strong SHG response (1.41 × KDP). Functional group analysis reveals that the [C(NH<small><sub>2</sub></small>)<small><sub>3</sub></small>] cation exhibits a dual functionality: its small heteroatom structure widens the band gap, while its π-conjugated framework enhances the birefringence and the SHG response, achieving an optimal balance. This study establishes a generalizable design framework for DUV optical crystals, offering a viable strategy to reconcile the trade-off between key properties.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"9 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993173","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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