Inorganic Chemistry Frontiers最新文献

{"title":"Mechanistic Insights into MnOx-Cocatalyzed Piezophotocatalytic Dye Degradation over S-Scheme MnOx/BiFeO3 Heterojunctions","authors":"Yuxing Chu, Yekang Zheng, Jiating Xu, Ruoyu Dong, Feng Zhu, Kaiqi Wang, Ying Wu, Yiming He","doi":"10.1039/d5qi01226k","DOIUrl":"https://doi.org/10.1039/d5qi01226k","url":null,"abstract":"MnOx is commonly used as an oxidative cocatalyst to promote charge carrier separation, yet, its underlying mechanism remains incompletely understood. In this study, MnOx nanoparticles were deposited onto the surface of BiFeO3 nanosheets via a photodeposition method, and their promoting effects in piezocatalytic and piezo-photocatalytic reactions were systematically investigated. The synthesized MnOx/BiFeO3 composites exhibited enhanced catalytic performance in RhB degradation. In the piezocatalytic system, the optimized MnOx/BiFeO3 catalyst achieved a degradation rate constant of 0.78 h⁻¹, approximately 4.6 times that of pure BiFeO3. Under simultaneous ultrasonic vibration and light irradiation, the rate constant further increased to 1.4 h⁻¹, representing 1.8 times and 1.4 times the rates observed under individual piezocatalytic and photocatalytic conditions, respectively. Comprehensive characterization techniques were employed to elucidate the mechanism behind the enhanced performance. The results reveal that MnOx modification induces interfacial stress, enhancing the piezoelectric response of BiFeO3. Moreover, an S-scheme heterojunction is formed at the MnOx/BiFeO3 interface, wherein holes in the valence band of BiFeO3 recombine with electrons from MnOx, effectively promoting charge separation and transport while preserving the strong redox capability of both charge carriers. The synergistic piezo-photocatalytic effect of MnOx/BiFeO3 is attributed to the global piezoelectric potential of BiFeO3, which extends the spatial range of interfacial charge separation within the S-scheme heterojunction. Additionally, the high-density photogenerated electron-hole pairs produced under light irradiation effectively supplement the intrinsic charge carriers. This study not only clarifies the potential mechanism by which MnOx functions as a hole-trapping cocatalyst, but also highlights the unique advantages of S-scheme heterojunctions in the field of piezo-photocatalysis, offering valuable insights for the design of efficient piezocatalytic materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"11 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533747","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structural optimization of VO₂/NH₄V₄O₁₀ cathode materials for high-performance wide-temperature zinc-ion batteries","authors":"Ming Zhao, Xiang Wu, Yoshio Bando","doi":"10.1039/d5qi01098e","DOIUrl":"https://doi.org/10.1039/d5qi01098e","url":null,"abstract":"Ammonium vanadate is considered as one of the most desirable cathodes for aqueous zinc ion batteries due to its favorable theoretical capacity and open crystal structure. Nevertheless, their further development is still limited by the poor structural stability, low electrical conductivity and compatibility of the electrolytes. In this work, we propose a regulation strategy through the pre-introduction of Ce ions. The incorporation of Ce ions increases the interlayer spacing of the host material, which improves the electrical conductivity and accelerates the ion transfer efficiency. The assembled Zn//0.05Ce-VO/NHVO cells deliver an initial capacity of 547.8 mAh g-1 at 0.2 A g-1. And they still keep a capacity of 331 mAh g-1 at 5 A g-1 after 4000 times cycling. Moreover, the system operates well over a wide temperature range (-20-40 oC). It keeps 92% and 87% capacity retention rate after 1500 cycles at the temperatures of -20 oC and 0 oC, respectively.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"19 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533749","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Aqueous-Triggered Self-Destructive Persistent Luminescent Nanoparticles for Dynamic Hierarchical Security Encoding","authors":"Yiqing Chen, Zhishan Chen, Xingzhong Chen, Ziqing Mao, Hongqiang Zhu, Jingrui Guo, Jialong Xu, Ziyi Lin, Shaoan Zhang, Yang Li","doi":"10.1039/d5qi01219h","DOIUrl":"https://doi.org/10.1039/d5qi01219h","url":null,"abstract":"Persistent luminescence has emerged as a robust platform for anti-counterfeiting applications due to its exceptional spatial-temporal decoding capability. Yet, conventional strategies often suffer from uniform emission patterns and predictable replication, compromising their security. Herein, we present “Snap-PLNPs”—near-infrared emitting CaS: Tm persistent luminescent nanoparticles engineered to undergo aqueous-triggered self-destruction via a hydrolysis mechanism. In contrast to traditional photophysical approaches, this chemically initiated degradation irreversibly terminates the luminescence, ensuring that security information can be decoded only once. Moreover, by incorporating an additional SiO₂ shell, we introduce a programmable delay in the hydrolysis process, thereby modulating the duration of the emission and adding a temporal regulation layer. This dual control—combining instantaneous chemical deactivation with time-resolved modulation—establishes a dynamic hierarchical security encoding framework. When embedded into laser-engraved logos, these CaS: Tm@SiO₂ hybrids enable a novel triple-layer anti-counterfeiting strategy that integrates spatial, temporal, and chemical dimensions. Our results underscore the potential of Snap-PLNPs as a next-generation platform for robust and adaptive security technologies.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"3 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533745","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synergistic activating effects of a strong Lewis acid (metal ion) and a strong BrØnsted acid enable KMnO4 to oxidize CH4 at room temperature","authors":"Huatian Shi, Miaomiao Zhou, Chi Keung Mak, Kai Chung Lau, Tai-Chu Lau","doi":"10.1039/d5qi01117e","DOIUrl":"https://doi.org/10.1039/d5qi01117e","url":null,"abstract":"The search for reagents that can oxidize methane (CH<small>₄</small>) under mild conditions has long been a challenge for chemists. In this work, we report the synergistic effects of a strong Lewis acid Sc(OTf)<small>₃</small> and a strong Bronsted acid CF<small>₃</small>CO<small>₂</small>H (TFA) to activate KMnO<small>₄</small> towards the oxidation of CH<small>₄</small> at room temperature. KMnO<small>₄</small> in the presence of 0.5-2 mol equiv. of Sc(OTf)<small>₃</small> in TFA/TFAA (1: 4 by vol., TFAA = trifluoroacetic anhydride) is able to oxidize CH<small>₄</small> (30 atm) at 22 °C to produce methyl trifluoroacetate (CF<small>₃</small>CO<small>₂</small>CH<small>₃</small>) in 17±2 % yield (based on KMnO<small>₄</small>). The yield is increased to 34% when the temperature is raised to 40 °C. No product is observed using Sc(OTf)<small>₃</small> alone, and only 2% of methyl trifluoroacetate is produced using TFA alone. A kinetic isotope effect of 2.2 is found using a mixture of CH<small>₄</small> and CD<small>₄</small> as substrate. The use of BrCCl<small>₃</small> as a radical trap results in the formation of BrCH<small>₃</small>, indicating that CH<small>₃</small>• radical is an intermediate in CH<small>₄</small> oxidation. These results suggest the Sc(OTf)<small>₃</small> and TFA form an active intermediate with MnO<small>₄</small>−, which undergoes hydrogen-atom abstraction (HAT) from CH<small>₄</small> to give CH<small>₃</small>•, which is further oxidized to CH<small>₃</small>OH. CH<small>₃</small>OH is prevented from further oxidation by trapping with TFAA to produce CF<small>₃</small>CO<small>₂</small>CH<small>₃</small>. DFT calculations show that Sc(OTf)<small>₂</small><small>⁺</small> and CF<small>₃</small>CO<small>₂</small>H combine together with MnO<small>₄</small>− to produce an active intermediate that undergoes HAT with CH<small>₄</small> with a low barrier of 12.5 kcal mol−<small>¹</small>.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"36 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144547015","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mixed Addenda Polyoxometalates by Cooperative Self-Assembly and Modulation of their Optoelectronic Properties","authors":"Ganga Singh, Ruchika Choudhary, Debaprasad Mandal","doi":"10.1039/d5qi00961h","DOIUrl":"https://doi.org/10.1039/d5qi00961h","url":null,"abstract":"Orbital engineering through the cooperative effect of different transition metals (TMs) is powerful and versatile approach for modulating the chemistry of polyoxometalates (POMs), either by introducing novel POM structures or designing POM-hybrids for more effective catalytic applications. Here, we present a cooperative mixed-metal strategy for the synthesis of mixed-addenda (Mo/W) sandwich POMs with varying compositions, denoted by the general formula [(TM<small>_i</small>)<small>₂</small>(TM<small>_e</small>)<small>₂</small>(H<small>₂</small>O)<small>₂</small>(XMo<small>_x</small>W<small>_9-x</small>O<small>₃₄</small>)<small>₂</small>]<small>^n-</small> (TM<small>_e</small>(II)=Fe/Co/Ni/Zn and TM<small>_i</small>(III)=Mn/Fe, X=Zn/Co/Fe). Using this cooperative mix-metal strategy, overall, we report 24 new POMs, including 8 mixed-addenda, 12 W-based sandwich POMs, and 4 POM-based 1-D coordination frameworks. Structural analyses reveal that Mo-addenda incorporation into the POM framework, alongside W (Mo/W), is strongly influenced by the variation of transition metal composition at sandwich core, their oxidation states, and pH of the reaction media. Electrospray ionization mass spectrometry (ESI-MS) and energy dispersive X-ray analysis (EDAX) analysis confirm detailed POM compositions, while UV-vis spectra and complementary density functional theory (DFT) analysis provide insights into orbital engineering via distinctive charge transfer processes. Theoretical and electrochemical studies demonstrate that electron transfer modulation occurs through both mixed-addenda incorporation and mixed-metal substitution at the sandwich position. This is further elucidated by enhanced oxygen evolution (OER) activity, where the cooperative mixed-metal and mixed-addenda POMs exhibit significantly improved performance, with an overpotential of 500 mV at 1 mA cm⁻², compared to 570 mV in a pH 7.1 buffer. Additionally, this cooperative mixed-metal mixed-addenda strategy extends to the formation of 1-D polyoxometalate coordination frameworks (POMCFs), where oxidation state of precursor metals plays a vital role in determining the overall structural attributes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"19 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533814","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electroreduction of N2 and CO2 to urea via Pd-assisted hydrogenation on MOFs-derived CeO2 nanosheets","authors":"Xiaoyue Chen, Jia Liang, Guangmin Ren, Zhan Zhao, Xiangchao Meng","doi":"10.1039/d5qi01154j","DOIUrl":"https://doi.org/10.1039/d5qi01154j","url":null,"abstract":"Conversion of CO2 and N2 to urea by electrocatalytic methods under ambient conditions is a promising alternative to conventional urea synthesis method. However, the inherent adsorption and activation characteristics of inert reaction gas molecules and the kinetics of hydrogenation after C-N coupling result in the challenge of electrocatalytic synthesis of urea. In this work, the electrocatalytic conversion of CO2 and N2 to urea by Pd-assisted hydrogenation on CeO2 nanosheets derived from metal-organic framework materials (MOFs) under mild conditions was achieved urea yield rate with 83.89 µg h-1 mg-1cat. and Faradic efficiency (FE) of 11.92%. Combined experimental and theoretical computational analyses confirmed that the defective structures present in the prepared catalysts were conducive to the stabilization and activation of adsorbed CO2 and N2, and due to the effective promotion of hydrolysis dissociation by Pd, which provided abundant source of protons for further hydrogenation after C-N coupling. This work provides some insights into the promotion of hydrolysis dissociation to optimize the hydrogenation energy barriers after C-N coupling for electrocatalytic synthesis of urea.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"47 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533863","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Heterometallic Calcium–Alkali Metal Aryloxides as Catalysts for the Solvothermal Alcoholysis of Nylon-6 Waste","authors":"Rafał Petrus, Karolina Matuszak, Adrian Kowaliński, Tadeusz Lis","doi":"10.1039/d5qi00994d","DOIUrl":"https://doi.org/10.1039/d5qi00994d","url":null,"abstract":"In this study, we report the synthesis of homometallic and heterometallic calcium aryloxides: [Ca(sal-Me)2(MeOH)]n (1), [Ca3(sal-Me)6(MeOH)2] (2), [Ca2Li2(sal-Me)6(THF)2] (3), [Ca2Na2(sal-Me)6(MeOH)4] (4), and [Ca2K2(sal-Me)6(MeOH)4] (5). Compounds 1 and 2 were obtained via direct reaction of metallic calcium with methyl salicylate (Hsal-Me) in methanol (MeOH). A similar synthetic route, incorporating one equivalent of an alkali metal (M′ = Li, Na, K) and tetrahydrofuran (THF), was used to obtain the heterometallic derivatives 3-5. A central focus of this work is the synthesis of heterometallic Ca²⁺–M′⁺ complexes, of which only 13 examples have been previously documented. A detailed investigation of the reaction pathways led to the identification of intermediate compounds: [Ca3(sal-Me)6(THF)4] (2a), [CaLi6(sal-Me)8]‧(6), and [Ca3Na4(sal-Et)10(Hsal-Et)2] (7) (Hsal-Et = ethyl salicylate). Additionally, reactions conducted under atmospheric moisture conditions yielded the uncommon pentanuclear complexes [Ca4Na(μ5-OH)(sal-Et)8(MeOH)] (8) and [Ca4K(μ5-OH)(sal-Et)8(EtOH)] (9). Compounds 1-9, along with previously reported [M′₆(sal-Me)₆] (M′⁺ = Li⁺(10), Na⁺(11), K⁺(12)), [Mg₂(sal-Et)₄(EtOH)₂] (13), [Zn₄(sal-Me)₈] (14), [M₂M′₂(sal-Me)₆(THF)x] (M²⁺ = Mg²⁺; M′⁺ = Li⁺(15), Na⁺(16), K⁺(17); M²⁺ = Zn²⁺; M′⁺ = Li⁺(18), Na⁺(19), K⁺(20); x = 0, 2, 4), and [Mg₄Na₂(sal-Me)₆(sal)₂(THF)₄] (21) were evaluated as catalysts for the chemical recycling of polyamide waste. Among them, the heterometallic catalysts 2, 6, and 18–20 exhibited the highest catalytic activity in the methanolysis of nylon-6 at 220 °C. Particular emphasis is placed on the reaction conditions and the high efficiency of the catalysts. Key factors influencing catalytic activity and the reaction mechanism are also analyzed.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"27 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533748","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"NASICON-type Na1+xZr2SixP3-xO12 Electrolytes Progress and Perspectives for Solid-state Sodium Metal Batteries","authors":"Yuhuan Wang, Jilong Liu, Jianxiong Wang, Chunwen Sun","doi":"10.1039/d5qi01082a","DOIUrl":"https://doi.org/10.1039/d5qi01082a","url":null,"abstract":"All-solid-state sodium metal batteries (ASSMBs) are considered as the most attractive alternative to lithium-ion batteries on account of their remarkable safety and low cost. Solid-state electrolytes as a key component have great effects on the performance of ASSMBs. Sodium super ionic conductors (NASICON)-type Na1+xZr2SixP3-xO12 (NZSP) electrolytes with excellent mechanical stability, high thermal/chemical stability as well as high ionic conductivity have become one of the most promising electrolytes for ASSMBs. The good compatibility of NASICON-type electrolytes with Na metal anodes and high-voltage cathodes is of great significance for ASSMBs. This paper reviews the structural characteristics, ion transport mechanism, strategies for enhancing conductivity, and synthesis methods of Na1+xZr2SixP3-xO12 based ceramic electrolytes. Simultaneously, it also introduces the approaches to addressing the interfacial issues between Na1+xZr2SixP3-xO12 electrolytes and solid electrodes. Finally, the prospective research directions are also presented to tackle the challenges for the practical application of Na1+xZr2SixP3-xO12 electrolytes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"7 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144547009","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bioorthogonal activation and mitochondrial targeting of a near-infrared-emitting iridium(III) nitrone complex via cyclooctynylated phosphonium cations for enhanced cellular imaging and photodynamic therapy","authors":"Edward R. H. Walter, Lawrence Lee, Kam Keung Leung, Kenneth Kam-Wing Lo, Nicholas J Long","doi":"10.1039/d5qi01139f","DOIUrl":"https://doi.org/10.1039/d5qi01139f","url":null,"abstract":"In this work, we designed and synthesised a new cyclometallated iridium(III) nitrone complex [Ir(bpz)2(bpy-nitrone)](PF6) (1) (Hbpz = benzo[a]phenazine; bpy-nitrone = 4-((methyl(oxido)imino)methyl)-4’-methyl-2,2’-bipyridine) as a bioorthogonally activatable phototheranostic agent. Complex 1 displayed very weak emission and singlet oxygen (1O2) photosensitisation in solutions due to the quenching nitrone moiety. However, upon the strain-promoted alkyne–nitrone cycloaddition (SPANC) reaction with bicyclo[6.1.0]non-4-yne (BCN), which converted the nitrone unit to a non-quenching isoxazoline derivative, the complex exhibited a substantial increase in emission intensity in the near-infrared region and 1O2 generation efficiency. Given that mitochondria are a crucial target in cancer therapy, we prepared a series of BCN-functionalised phosphonium cations (BCN-Phos-n), each bearing different substituents, to serve as mitochondrial-targeting vectors for delivering complex 1 to the mitochondria via the bioorthogonal SPANC reaction. Notably, complex 1 exhibited more significant emission turn-on upon reaction with BCN-Phos-5 and BCN-Phos-6 (I/Io = 24.7 and 14.1, respectively), attributed to their increased hydrophobicity resulting from the methylation or methoxylation of the phenyl rings on the phosphonium cation. Live-cell confocal imaging and flow cytometric analyses revealed that complex 1 showed larger emission enhancement in HeLa cells pretreated with BCN-Phos-5 or BCN-Phos-6 compared to other BCN-Phos-n analogues. Co-staining experiments confirmed that the resultant luminescent isoxazoline cycloadducts predominantly accumulated in the mitochondria. Additionally, both dark and light-induced cytotoxicity of complex 1 increased upon pretreatment of the cells with BCN-Phos-5 or BCN-Phos-6. Our results demonstrate that the theranostic potential of transition metal nitrone complexes can be significantly enhanced via strategic structural manipulation of their bioorthogonal reaction partners.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"36 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144533751","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electron transport chain-inspired photodiode-like junction in metal-organic framework for directional multi-electron transfer in photocatalysis†","authors":"Yang An, Muhammad Saqaf Jagirani, Xu Zhang, Lanqiao Li, Yu Zou, Lei Qiao, Renhai Liu, Ibro Douka Abdoulkader, Rui Cai, Cheng He, Tiexin Zhang, Yusheng Shi, Chunying Duan","doi":"10.1039/d5qi00948k","DOIUrl":"https://doi.org/10.1039/d5qi00948k","url":null,"abstract":"It is highly desirable to mimic the ratchet-like multi-electron transfer of the electron transport chain (ETC) by artificial systems and impose dual-mode anaerobic denitrification and aerobic oxidation on organic compounds to produce value-added fine chemicals. But the extreme complexity of biological structures hampered their direct mimics. In this article, we report a new continuous and directional photoinduced-electron transfer (PET) method to mimic the ETC process of natural enzymes using metal-organic framework (MOF) as the platform, phenothiazine (<strong>PTH</strong>) ligand decorated with carboxylate coordination terminal was introduced into iron porphyrin PCN−222(Fe) by use of solvent-assisted ligand incorporation (SALI) process, electron-donating (<strong>D</strong>) <strong>PTH </strong>moiety and electron-accepting (<strong>A</strong>) iron porphyrin were spatially separated by the insulator-like high-polar Zr−carboxylate cluster. This <strong>D</strong>−<strong>A</strong> junction facilitated the photodiode-like directional electron transfer from <strong>PTH </strong>to the iron-porphyrin, thereby preventing back-electron transfer. The locally excessive distribution of <strong>PTH </strong>motifs, compared to neighboring iron-porphyrins, favored continuous electron injection. These advantages facilitated the more efficient photocatalytic performance of <strong>PTH</strong>@PCN−222(Fe) in the reduction of nitroarenes in N<small>₂</small> and the oxidation of benzylamines in O<small>₂</small> compared with the homogeneous mode. Femtosecond transient absorption (fs-TA) demonstrated more efficient intra-framework photoinduced electron transfer (PET) within <strong>PTH</strong>@PCN−222(Fe) compared to other counterparts, further indicating the superiority of this bioinspired supramolecular strategy.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"47 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144521238","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}