Inorganic Chemistry Frontiers最新文献

{"title":"Modulating Optical Properties through Cation Substitution: Composition-Property Relationships in MI3MIIIP3O9N:Eu2+ (MI=Na, K; MIII=Al, Ga, In)","authors":"Nakyung Lee, Justyna Zeler, Gosia Sojka, Eugeniusz Zych, Jakoah Brgoch","doi":"10.1039/d5qi00410a","DOIUrl":"https://doi.org/10.1039/d5qi00410a","url":null,"abstract":"Developing phosphors with narrow photoluminescence emission peaks and high chromatic stability holds significant importance in light-emitting diode (LED) display technologies, where a wide color gamut is essential to achieve the Rec. 2020 specifications. This research focuses on the optical properties of a solid solution: <em>M</em><small>^I</small><small>_2.97</small>Eu<small>_0.015</small><em>M</em><small>^III</small>P<small>₃</small>O<small>₉</small>N [<em>M</em><small>^I</small>=Na, K; <em>M</em><small>^III</small>=Al, (Al<small>_0.75</small>Ga<small>_0.25</small>), (Al<small>_0.5</small>Ga<small>_0.5</small>), (Al<small>_0.25</small>Ga<small>_0.75</small>), Ga, (Ga<small>_0.75</small>In<small>_0.25</small>), (Ga<small>_0.5</small>In<small>_0.5</small>)] to understand how the narrow-emitting photoluminescence in K<small>₃</small>AlP<small>₃</small>O<small>₉</small>N:Eu<small>²⁺</small> can evolve during host structure cation substitution. Photoluminescence measurements at low temperature (15 K) support that Eu<small>²⁺</small> replaces three crystallographically independent Na<small>⁺</small> sites in Na<small>_2.97</small>Eu<small>_0.015</small>AlP<small>₃</small>O<small>₉</small>N, similar to the parent K<small>⁺</small> phosphor, but substituting Ga<small>³⁺</small> and In<small>³⁺</small> for Al<small>³⁺</small> leads to a change in Eu<small>²⁺</small> site preference, narrowing the full-width-at-half-maximum (<em>fwhm</em>) of the emission peak. The chromatic stability and photoluminescence quantum yield are also enhanced with higher Ga<small>³⁺</small> content in the host but not with In<small>³⁺</small>. Thermoluminescence analysis indicates the relationship between trap states and the enhanced quantum yield with Ga<small>³⁺</small> leads to the series’ best performance. The analysis of the <em>M</em><small>^I</small><small>_2.97</small>Eu<small>_0.015</small><em>M</em><small>^III</small>P<small>₃</small>O<small>₉</small>N series offers insight into the potential method for modulating optical properties with cation substitution in the host structure.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862251","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":"High-efficiency metal selenide as electrocatalyst in separator for lithium-sulfur batteries","authors":"Yujuan Hu, Bo Jin, Hui Liu","doi":"10.1039/d5qi00452g","DOIUrl":"https://doi.org/10.1039/d5qi00452g","url":null,"abstract":"The well-framed construction of separator modifier with exquisite catalytic ability and adsorption effect for lithium polysulfides (LiPSs) is crucial for solving properly the challenges encountered by lithium-sulfur batteries (LSBs). Herein, a metal-organic framework (MOF) substrate with porous polyhedron is firstly designed, then the mixture of ZIF-67 and melamine is carbonized into N-doped carbon (NC) covered with cobalt nanoparticles that are surrounded by carbon nanotubes to obtain Co/NCC, which is finally selenized in situ to form CoSe/NCC with high adsorption effect and accelerated polysulfide conversion ability. The CoSe/NCC is coated onto the polypropylene (PP) separator (CoSe/NCC/PP) to inhibit the LiPSs shuttle passing through the separator. Multi-walled carbon nanotubes (MWCNTs) are accustomed to fusing sulfur as a positive electrode (MWCNTs/S). The CoSe/NCC with high conductivity and sulfiphilic property possesses many active sites and anchors LiPSs, thus promoting multistage redox reaction kinetics. The electrochemical tests show that the initial discharge capacity of a lithium-sulfur battery with a CoSe/NCC/PP separator and a MWCNTs/S cathode is 1270 mAh g−1 at 0.5 C, and the discharge capacity is kept at 932 mAh g−1 after 100 cycles, with a capacity retention rate of 73%. In addition, it has also good cyclic performance under high current densities of 1 and 5 C. This work provides ideas and methods for the application of metal selenides as separator modification materials in LSBs, which would be expected to be applied to other rechargeable batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866464","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":"Atomically precise metal nanocluster sandwich heterojunction for robust and efficient photocatalytic CO2 reduction to methanol","authors":"Rui Lu, Aimin Yao, Yali Dai, Haijiao Yin, Chengqi Li, Yuanxin Du, Manzhou Zhu","doi":"10.1039/d5qi00424a","DOIUrl":"https://doi.org/10.1039/d5qi00424a","url":null,"abstract":"Developing heterogeneous nanocatalyst with well-defined structure and excellent reactivity and stability is vital for understanding catalytic mechanism and practical industrial application. Herein, we report the construction of atomically precise metal nanocluster sandwich heterojunction (MIL-125-NH2-Au25(L-Cys)18/g-C3N4, M-A/C for short). Compared with the binary counterparts, the M-A/C efficiently and selectively photocatalyzes CO2 reduction to methanol under visible light irradiation with remarkably enhanced activity and stability, due to the protective shell. Moreover, the ternary M-A/C heterojunction not only broadens light absorption region, strengthens CO2 adsorption, but also expands interface charge transfer channel, benefiting for photocatalytic performance. Additionally, the integrating of precise structure and in situ spectrometry unveils the evolution from CO2 to CH3OH. This work opens a promising avenue to design highly-efficient and robust atomically precise metal cluster-based heterojunction catalyst.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"17 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862253","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":"Selective Electrocatalytic Reduction of Carbon Dioxide to Methane by Guanidine-based Metal-Organic Cage","authors":"Ziang Zhang, Yang Yang, Jinfeng Wang, Xu Jing, Chunying Duan","doi":"10.1039/d5qi00756a","DOIUrl":"https://doi.org/10.1039/d5qi00756a","url":null,"abstract":"In the context of energy shortages and environmental disasters, converting the greenhouse gas carbon dioxide into high-value carbon-based energy provides a practical pathway for achieving a sustainable artificial carbon cycle. However, integrating CO₂ capture with electrocatalysis remains challenging. Herein, we constructed a guanidine-based metal-organic cage as a homogeneous electrocatalyst to encapsulate and activate the adduct in-situ formed by CO₂ and ethanolamine, significantly lowering the reduction potential of CO₂ and achieving a record-low potential for CO₂ reduction to methane (0.16 V vs. reversible hydrogen electrode, RHE). Our research demonstrates that under the condition of -0.04 V vs. RHE, the Faradaic efficiency (FE) for methane reaches 69.8%, with a selectivity exceeding 99% for continuous operation over 18 hours.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"3 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862252","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":"High capacitive performances obtained in sandwich structured Bi0.5Na0.5TiO3-based dielectric ceramics","authors":"Tengyue Liu, Ben Jia, Jiaqi Wang, Yuliang Zhou, Peng Zheng, Wangfeng Bai, Qiaolan Fan, Liang Zheng, Yang Zhang","doi":"10.1039/d5qi00499c","DOIUrl":"https://doi.org/10.1039/d5qi00499c","url":null,"abstract":"As power electronics continue to advance and environmental concerns grow, high energy storage lead-free ceramic capacitors have become pivotal in dielectric materials research. However, the inherent compromise between improved dielectric polarization properties and increased breakdown strength persists as a primary constraint in advancing energy storage capabilities. To break through this shackle, sandwich structured Bi<small>_0.5</small>Na<small>_0.5</small>TiO<small>₃</small>-based lead-free ceramics are designed by alternatively arranging the relaxor ferroelectric layer with high polarization and the linear-like dielectric layer with high electric field breakdown and fabricated through tape casting and solid state sintering in this work. The material demonstrates exceptional energy storage capability featuring a record recoverable density of 11.02 J cm<small>⁻³</small> and superior efficiency (79.1%) at 800 kV cm<small>⁻¹</small>. Remarkably, it maintains stable capacitive behavior across wide frequency (1–100 Hz) and temperature (30–160 °C) ranges, and fatigue cycles (1–10<small>⁵</small>). This breakthrough demonstrates that sandwich architecture synergistically resolves the polarization–breakdown strength paradox in lead-free ceramics, achieving simultaneous dielectric reinforcement and energy storage enhancement through interfacial engineering optimization.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"46 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862254","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":"Designing biomimetic catalytic systems for CO2 reduction to formate using NAD(P)H","authors":"Chanwoo Park, Chaeyeon Kwon, Young Hyun Hong","doi":"10.1039/d5qi00608b","DOIUrl":"https://doi.org/10.1039/d5qi00608b","url":null,"abstract":"Artificial photosynthesis refers to a synthetic method of transforming solar radiation into storable fuels that are suitable for transport and practical applications, mimicking the natural photosynthesis found in plants and algae. Successfully replicating this natural energy conversion system could represent a major breakthrough in renewable energy technology, simultaneously providing clean fuel and reducing atmospheric carbon dioxide levels. Growing concerns over excessive CO<small>₂</small> emissions have led to considerable interest in developing technologies that convert CO<small>₂</small> into value-added fuels and raw materials by artificial photosynthesis. Essential processes such as photon absorption, charge transfer, water splitting, NAD(P)<small>⁺</small> reduction, and carbon dioxide fixation have attracted significant research interest. Nevertheless, these individual processes have predominantly been studied independently. For the combination of NAD(P)H oxidation and CO<small>₂</small> reduction reactions, formate dehydrogenase (FDH) is a key enzyme in natural CO<small>₂</small> recycling systems, catalysing both the oxidation of formate to CO<small>₂</small> and the reduction of CO<small>₂</small> to formate <em>via</em> electron transfer involving NAD(P)H/NAD(P)<small>⁺</small>. Mimicking the metal active sites of such enzymes is crucial for designing efficient catalysts for CO<small>₂</small> conversion. However, no biomimetic <em>in vivo</em> catalysts have been reported for formate production from CO<small>₂</small> using NAD(P)H. This review focuses on catalytic studies involving the conversion of CO<small>₂</small> into formic acid using NAD(P)H with FDH as well as FDH-mimetic metal complexes. It covers enzymatic, photochemical, and electrochemical methods for CO<small>₂</small> reduction, highlighting the structure and mechanism of FDH and recent advances in the design of FDH mimetics. Additionally, this review explores strategies for enhancing the stability of the catalyst and catalytic performance through molecular tuning, offering insights into future research directions for developing efficient and sustainable CO<small>₂</small> reduction systems.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"46 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858168","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":"Modulation of Se Vacancy on NiSe2@CoSe2 Heterostructures to Optimize Ethanol Electrooxidation Activity for Efficient Hybrid Water Splitting and Zinc-Ethanol-Air Batteries","authors":"Jiahui Li, Feilong Fang, Zilong Li, Yongqi Jian, Junmin Zhu, Fangyan Xie, Jian Chen, Yanshuo Jin, Nan Wang, Xiyun Zhang, Hui Meng","doi":"10.1039/d5qi00621j","DOIUrl":"https://doi.org/10.1039/d5qi00621j","url":null,"abstract":"This work constructs a NiSe2@CoSe2 heterostructure with Se vacancies via electrochemical activation, increased the density of active sites, fine-tuned the electronic structure of the material and optimized Co 3d orbital spin states, and enabled superior ethanol oxidation (1.33 V @ j10), reducing energy consumption by 60% in water splitting and 20% in Zn-ethanol-air batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"31 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853755","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":"Synthesis of Novel Organic Ni (II) N-isonicotinoylhydrazine-Carbothioamide Complexes and their Application in the Oxygen Evolution Reactions","authors":"Xiaopei Li, Xianxu Chu, Kefan Ying, Xi Chen, Peng Sun, Haiyun Xu, Lu Li, Jie Zhang, Wenjuan Li","doi":"10.1039/d5qi00033e","DOIUrl":"https://doi.org/10.1039/d5qi00033e","url":null,"abstract":"The five novel nickel organic complexes featuring different electron-rich and electron-deficient groups were synthesized as electrocatalysts by using N-(aryl/alkyl)-2-isonicotinoylhydrazine-1-carbothioamide compounds in coordination with nickel acetate tetrahydrate and 1,10-phenanthroline. These Ni-complexes were characterized using infrared and Raman spectroscopy and were subsequently employed for the oxygen evolution reaction (OER) in water splitting under alkaline conditions. The overpotential and Tafel slope for Ni-based complex Ni-1 were as low as 454 mV and 111.90 mV dec-1, respectively, at a current density of 10 mA cm-2, indicating excellent electrochemical performance. Furthermore, Ni-1 demonstrated good electrochemical stability, with only minor voltage fluctuations observed during the continuous bubble generation over a 40 hours electrolysis period and nickel maintains a +2 oxidation state (Ni2+) in the complex both before and after the OER test via characterization of N2p spectra by X-ray photoelectron spectroscopy (XPS) measurements. This study confirms the electronic effect of substituent groups on the water-splitting ability of Ni-complexes bearing the two different organic ligands, showing that the overpotential and Tafel slope increase with a decrease in the electron-donating capacity of the substituent groups.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"88 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847022","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":"Polyhedral oligomeric silsesquioxane difluoroboron complexes as cooperative octo-site catalysts for the photooxidation of sulfides to sulfoxides","authors":"Mateusz Janeta, Sławomir Szafert","doi":"10.1039/d5qi00323g","DOIUrl":"https://doi.org/10.1039/d5qi00323g","url":null,"abstract":"The incorporation of difluoroboron into the side arms of polyhedral oligomeric silsesquioxanes (POSSs) opens up new possibilities for the construction of metal-free photocatalysts with tailored properties. Herein, we report the design and synthesis of novel difluoroboron complexes of POSSs (<strong>POSS-tert-BF<small>₂</small></strong>, <strong>POSS-sal-BF<small>₂</small></strong> and <strong>POSS-npht-BF<small>₂</small></strong>) derived from imine-functionalized POSSs, which were utilized as efficient photocatalysts. The complexes demonstrated exceptional photocatalytic performance in the aerobic oxidation of sulfides to sulfoxides, significantly outperforming their silsesquioxane-free counterparts. <strong>POSS-tert-BF<small>₂</small></strong> demonstrated a high singlet oxygen quantum yield of 48%. This study highlights the feasibility of intramolecular cooperative activity in catalytic reactions and identifies key factors influencing its effectiveness. Furthermore, it underscores the potential of POSS as a versatile building block for the development of advanced photocatalytic materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841523","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":"Hydrosilylation and hydrogermylation of white phosphorus","authors":"Jose Cammarata, Maximilian Schimpf, Daniel Scott, Robert Wolf","doi":"10.1039/d5qi00869g","DOIUrl":"https://doi.org/10.1039/d5qi00869g","url":null,"abstract":"The development of efficient, direct strategies for the transformation of white phosphorus (P<small>₄</small>) into useful monophosphorus compounds, as alternatives to the current wasteful and hazardous indirect processes, remains a significant challenge. Encouragingly, recent reports have shown that the reduction of P<small>₄</small> with organotin hydrides and subsequent functionalisation with electrophiles allows for the efficient synthesis of an array of industrially relevant monophosphines in a ‘one-pot’ manner. However, despite the practical and conceptual simplicity, the appeal of this method is limited by the inherent toxicity of most organotin derivatives. Here, we address this problem through experimental and computational studies of the reactivity of lighter and less toxic hydrogermane and hydrosilane homologues of organotin hydrides (R<small>₃</small>EH, E = Ge or Si) towards P<small>₄</small>. These hydroelementation reactions can be employed to directly transform P<small>₄</small> into useful monophosphorus compounds, in a simple ‘one-pot’ fashion similar to the original organotin-based systems.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"31 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847023","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}