Inorganic Chemistry Frontiers最新文献

{"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}

{"title":"Cycloaddition Reactivity of Yb@D3h-C74: the Carbon Cage Size Matters","authors":"Muqing Chen, wh xiang, Xinde Li, Jinpeng Xin, Peng Jin, Yongfu Qiu, Zhiyu Cheng, Shangfeng Yang","doi":"10.1039/d5qi00649j","DOIUrl":"https://doi.org/10.1039/d5qi00649j","url":null,"abstract":"Divalent endohedral metallofullerenes (Di-EMFs) featuring a closed-shell electronic configuration and two-electron transfer from the inner cluster to outer cage exhibit a more evenly distributed charge over the whole cage, resulting in a low chemical reactivity and thus limited chemical modification approaches. Up to date, the reported chemical modifications of Di-EMFs are limited to those with large carbon cages based on C<small>₈₀</small>, C<small>₈₂</small>, and C<small>₈₄</small>, whereas the chemical reactivity of Di-EMFs bearing cage smaller than C<small>₈₀</small> remains unknown. Herein, on the basis of synthesis of a medium-sized Di-EMF Yb@<em>D</em><small>_3h</small>-C<small>₇₄</small>, we investigated its 1,3-dipolar cycloaddition reaction, and found its unusually high chemical reactivity at room temperature, significantly different from the reported Di-EMFs with larger carbon cages for which cycloaddition reactions generally require light irradiation or heating conditions. As a result, four monoadducts of Yb@D<small>_3h</small>-C<small>₇₄</small>, labelled as<strong> 2a</strong>-<strong>2d</strong>, were obtained, among which the molecular structure of <strong>2a</strong> was unambiguously determined by single-crystal X-ray crystallography. The addition sites were far from the carbon cage region adjacent to the inner Yb cation, and this addition pattern is different to those of the reported Di-EMFs with larger carbon cage size. Theoretical calculations rationally explained the high reactivity of Yb@D<small>_3h</small>C<small>₇₄</small> as well as its addition pattern.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"73 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841526","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":"Pressure Induced Blue Shift Emission and Its Influence on the Band Gap in an Emerging 3D Semiconductor †","authors":"Xia-Ying Zhao, Lei Yue, Meng-Yu Xu, Gui-Fang Zhang, Xi-Yan Dong, Yong-Li Wei, Quanjun Li","doi":"10.1039/d5qi00550g","DOIUrl":"https://doi.org/10.1039/d5qi00550g","url":null,"abstract":"Metal-organic chalcogenolate is one of excellent hybrid semiconductors, yet reports on their precise structures remain limited due to their large structural periodicity. Understanding the relationship between their structure and optical properties remained a significant challenge. External pressure is recognized as a clean and effective method for tuning the structure and properties of optical materials. In this study, we obtained a three-dimensional silver chalcogenolate {Ag10[(CH3)2CHS]8(CN)2}n, which exhibited bright orange-red emission upon ultra-violet excitation at atmospheric pressure. Notably this compound showed unique piezoresponse to varying pressures. During compression, the emission centers experienced a blue shift of nearly 130 nm, followed by a red shift. Both mechanical stress and phase conversion contribute to this complex piezochromic behavior. In situ high-pressure X-ray diffraction measurements and Raman spectroscopy confirmed phase transitions during the color change. Density functional theory simulations further verified the direct band gap semiconductor characteristics of this compound and suggested how the atomic contributions to the band structure. This work not only sheds light on the structural and optical responses to hydrostatic pressure but also explores their relationship in this 3D silver chalcogenolate, offering a new perspective on studying the nature of metal-organic frameworks semiconductors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841524","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":"Nitrogen-Activation and Charge-Transfer Lanthanide Oxide Promoters for Enhanced Photocatalytic Ammonia Synthesis","authors":"Hongda Li, Bijun Zhou, Xiao Miao, Xu Zhu, Shiyu Chen, Xiaoyu Jiang, Pengyan Li","doi":"10.1039/d5qi00655d","DOIUrl":"https://doi.org/10.1039/d5qi00655d","url":null,"abstract":"Lanthanide metals possess multiple oxidation states, being emerging as a frontier toward the nitrogen fixation, yet the knowledge regarding their photocatalytic mechanism and active sites is very limited. Herein, a series of LnOy/MoS2 (Ln = La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu) photocatalysts for nitrogen fixation are successfully designed and synthesized. The experimental results demonstrate that the load of LnOy redox promoters (Ln = Ce, Eu or Tb, the following is also) significantly increases the effective reaction-active sites and promotes the separation and transfer of carriers, thereby improving photocatalytic performance. The visible-light-driven nitrogen fixation activities of LnOy/MoS2 composites are significantly enhanced, achieving remarkable rates of 342.8 μmol g⁻¹ h⁻¹ for CeOy/MoS2, 369.1 μmol g⁻¹ h⁻¹ for EuOy/MoS2, and 457.3 μmol g⁻¹ h⁻¹ for TbOy/MoS2, which are substantially higher than that of pristine MoS2 (46.1 μmol g⁻¹ h⁻¹). Theoretical calculations reveal that LnOy loading promote the adsorption and activation of N₂ molecules, with the Tb site exhibiting the strongest adsorption capacity (ΔG=1.46 eV) and superior electron transfer efficiency, as confirmed by PL spectroscopy and photocurrent response analysis. This work provides fundamental insights into the role of lanthanide oxides in regulating photocatalytic nitrogen activation and offers a strategic framework for designing high-performance lanthanide-based catalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841775","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}