Inorganic Chemistry Frontiers最新文献

{"title":"High entropy sulfide nanoparticles as redox catalysts for lithium-sulfur batteries","authors":"Yiqian Li, Yuehan Hao, USMAN ALI, Mingxin Sui, Qi Zhang, Lingyu Zhang, Lu Li, Bingqiu Liu, Chungang Wang","doi":"10.1039/d4qi03229b","DOIUrl":"https://doi.org/10.1039/d4qi03229b","url":null,"abstract":"High entropy sulfide (HES) exhibits high catalytic activity and structural stability due to the synergistic effect and high entropy effect of various metals. However, the conventional approach for synthesizing HES typically necessitates elevated temperatures to ensure homogeneous blending of multiple elements, which directly results in nanoparticle agglomeration and unsatisfactory electrochemical performance. Herein, we propose the HES as a novel separator modifier for lithium-sulfur batteries, which overcomes the limited adsorption-catalytic synergy of conventional single metal sulfides. Ultrafine FeCoNiCrMnS₂ nanospheres (HES NSs) are synthesized via a facile template method, where the multi-metal synergy enables simultaneous suppression of polysulfide shuttling and acceleration of redox kinetics. The ultrafine HES nanocrystals can expose a sufficient number of active sites, which serve as an efficient LiPSs barrier to inhibit side reactions and as an additional collector to enhance the polysulfide redox reaction. As a result, the battery employing HES//PP separators exhibits outstanding cycle stability (906.8 mAh g-1 at 1.0 C after 1000 cycles). This study not only showcases the potential application of HES as a separator modifier for Li-S batteries but also provides novel insights into exploring other high-entropy materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"45 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143889713","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":"Linker-Cluster Cooperativity in Confinement of Proline-Functionalized Zr-Based Metal-Organic Frameworks and its Effect on the Organocatalytic Aldol Reaction","authors":"Zarfishan Dilruba, Ardeshir Dadgar Yeganeh, Sofia Kolin, Sadia Noor, Hassan Shatla, Carl Wieland, Bo-Hung Yu, Katrin Gugeler, Anna Zens, Johannes Kästner, Deven Estes, Kristyna Pluhackova, Simon Krause, Sabine Laschat","doi":"10.1039/d4qi02724h","DOIUrl":"https://doi.org/10.1039/d4qi02724h","url":null,"abstract":"Metal organic frameworks (MOFs) provide unique opportunities for molecular heterogeneous catalysis by mimicking the active sites of enzymes. However, understanding and controlling the interaction between the metal node and the organic linker carrying the catalytic unit and the resulting confinement effects remain challenging. Here, in a combined theoretical and experimental approach Zr-UiO-67-MOFs with ortho-N-acylproline-functionalized biphenyl-dicarboxylate linkers were prepared and compared with the corresponding MOFs with regioisomeric meta-linkers. As benchmark catalysis the organocatalytic aldol reaction of p-nitrobenzaldehyde and cyclohexanone was studied. Experimental results revealed that the ortho-linker accelerated the aldol reactions, whereas the regioisomeric meta-linker decreased the reaction rate, which was rationalized by pore blocking of the meta-linker via molecular dynamics simulations. Moreover, the acid modulator used in the MOF preparation also played a critical role in the formation of acetal byproducts through competing acid catalysis. Our study provides novel insights into the cooperative catalysis between the linker-attached organocatalyst and the MOF metal center.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143889714","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":"Mutual Restriction-Driven Anomalous Multistage Piezochromic Behavior in Copper(I) Thiocyanate/Isoquinoline Coordination Polymers","authors":"Zhenxing Yang, Chunguang Zhai, Jianqi Shang, Lingyan Dang, Yuchen Shang, Jiangya Xu, Yupu Zheng, Xiaolu Qi, Rui Shi, Mingguang Yao","doi":"10.1039/d5qi00685f","DOIUrl":"https://doi.org/10.1039/d5qi00685f","url":null,"abstract":"Piezochromic materials exhibiting pressure-responsive photoluminescence have emerged as promising candidates for advanced optoelectronic applications. Coordination polymers incorporating copper(I) thiocyanate and π-conjugated ligands present particular interest due to their structural adaptability and tunable emission properties. We herein report the first comprehensive investigation of the anomalous piezochromic behavior in the coordination polymer [Cu(SCN)(iqi)]n (iqi=isoquinoline), employing in situ high-pressure spectroscopy measurements. The emission intensity of [Cu(SCN)(iqi)]n initially increases, then slightly decreases, followed by a stable plateau, and eventually decreases under compression, accompanied by a red-shift in the emission spectra. Through combined spectral analysis and structural considerations, we attribute this unique behavior to the pressure-induced interplay between enhanced charge transfer efficiency and structural deformation. Our findings highlight the potential of copper(I)-based coordination polymers as versatile platforms for developing pressure-sensitive optical devices and smart sensory materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"36 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143885161","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":"Microwave quasi-solid-state-constructed low-content Pt on CeO2 with strong electronic interactions for efficient electrocatalytic acidic overall water splitting","authors":"Jing Li, Qihao Wang, Ruotong Guo, Yingxia Zong, Jun Xing, Weiping Xiao, Guangrui Xu, Dehong Chen, Lei Wang, Zexing Wu","doi":"10.1039/d5qi00536a","DOIUrl":"https://doi.org/10.1039/d5qi00536a","url":null,"abstract":"Defective engineering is crucial for developing extremely effective electrocatalysts for the hydrogen evolution reaction (HER). Herein, low-content platinum (Pt) loaded onto cerium dioxide (CeO<small>₂</small>) cubes with oxygen vacancies (O<small>_V</small>) was developed <em>via</em> an ultrafast microwave quasi-solid-state approach (Pt/CeO<small>₂</small>-O<small>_V</small>) within 60 s. The turnover frequency (TOF) and mass activity verify that the Pt/CeO<small>₂</small>-O<small>_V</small> sample demonstrates favorable HER activity owing to the generated O<small>_V</small> and the introduction of Pt, which reduce electrical resistance and enhance metal–support electronic interactions. The as-synthesized Pt/CeO<small>₂</small>-O<small>_V</small> sample demonstrates a low overpotential of 10 mV to reach 10 mA cm<small>⁻²</small> coupled with a small Tafel slope of 25.6 mV dec<small>⁻¹</small> in 0.5 M H<small>₂</small>SO<small>₄</small>, while also exhibiting remarkable long-term stability. This research paves the way for developing catalysts with exceptional catalytic activity and stability, holding promise in advanced green energy conversion through defect engineering and strong electronic interaction.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"73 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143885162","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":"Reverse Quantum Wells in Gradient-Doped CdS for Photocatalytic H2O2 Production","authors":"Xiaoying Bo, Caijie Yang, Bolun Li, Yikang Fan, Jiaoyan Li, Hengming Huang, Jiahui Kou, Chunhua Lu","doi":"10.1039/d5qi00742a","DOIUrl":"https://doi.org/10.1039/d5qi00742a","url":null,"abstract":"The photocatalytic O2 reduction to produce H2O2 offers significant environmental benefits. However, its efficiency is hindered by rapid charge recombination and sluggish catalytic kinetics in the catalyst. Traditional elemental doping has been employed to mitigate these issues, but its efficacy is limited as heteroatoms within the bulk often trap charge carriers. To address these challenges, we propose a gradient doping strategy. Unlike uniform doping, gradient doping introduces additional active sites on the catalyst surface. Our engineered gradient Mn-doped CdS photocatalyst demonstrated a remarkable H2O2 generation rate of 1874 μmol g−1 h−1, with an apparent quantum efficiency of 65.2% at 475 nm. The gradient distribution of Mn creates reverse quantum wells within the CdS matrix, which significantly enhances charge extraction from the bulk to the surface. The surface enrichment of Mn not only facilitates the adsorption and activation of O2 but also promotes the formation of the crucial *OOH intermediate, thereby accelerating H2O2 production.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"65 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143885163","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":"Enhancing electrocatalytic hydrogen evolution efficiency: tuning catalyst support pore size to optimize hydrogen adsorption–desorption kinetics","authors":"Yong Zhou, Bin Yang, Bing Li, Xiaoyang Liu","doi":"10.1039/d5qi00769k","DOIUrl":"https://doi.org/10.1039/d5qi00769k","url":null,"abstract":"Developing an electrocatalyst for the hydrogen evolution reaction (HER) with a facile synthesis method and superior catalytic performance is crucial for achieving cost-effective, environmentally sustainable, and efficient hydrogen energy production. Noble metal nanoparticles have been extensively utilized as HER electrocatalysts due to their high catalytic activity, tunable composition, and electronic structure. However, their widespread application is limited by high costs. A promising strategy to enhance the utilization efficiency of noble metals involves the fabrication of noble metal–carbon composites with optimized hydrogen evolution kinetics. In this study, a SiO<small>₂</small>-template method was employed to modulate the pore size of hollow mesoporous carbon spheres (HMCSs) by controlling the formation rate of SiO<small>₂</small>. Additionally, microwave-assisted pyrolysis of Ru carbonyl compounds enabled the rapid synthesis of ultrasmall Ru nanoclusters confined within HMCSs (Ru/HMCS-2-3) in only 15 minutes. The resulting Ru/HMCS-2-3 catalyst exhibited highly efficient Ru utilization and demonstrated HER activity superior to that of commercial Pt/C catalysts in alkaline solutions, achieving a current density of 10 mA cm<small>⁻²</small> at an overpotential of only 18.9 mV. Furthermore, Ru/HMCS-2-3 exhibited excellent cycling stability and durability, with no significant overpotential degradation observed after 1,000 cyclic voltammetry (CV) scans and negligible current density loss during a 48-hour chronoamperometry (<em>i</em>–<em>t</em>) test. <em>In situ</em> Raman spectroscopy, CV analysis in the hydrogen desorption region, and density functional theory (DFT) calculations revealed that the catalyst exhibits a strong H<small>₂</small>O adsorption, rapid H<small>₂</small>O dissociation at low overpotential, and excellent hydrogen adsorption–desorption kinetics. Additionally, the spatial confinement effect of HMCS-2 on Ru clusters contributed to its remarkable HER activity and stability. These findings highlight the potential of Ru/HMCS-2-3 as a highly efficient and durable HER electrocatalyst for sustainable hydrogen production.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"27 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143880268","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":"Deep-Ultraviolet Nonlinear-Optical Crystals LiBePO4 and BeP2O6 by Ionic Potential Modulation towards Uniform Arrangement of PO4 Groups","authors":"Xia Zhang, Jian-Qiang Shen, Hongxiao Lv, Penghui Guo, Yi-Gang Chen, Chun-Li Hu, Xian-Ming Zhang","doi":"10.1039/d5qi00779h","DOIUrl":"https://doi.org/10.1039/d5qi00779h","url":null,"abstract":"Uniform arrangement of functional groups is a key factor of improving nonlinear properties in nonlinear-optical (NLO) materials, but currently there is no feasible and guiding strategy to modulate the uniform arrangement. Herein, we first apply ionic potential concept to deep-ultraviolet (DUV, λ &lt; 200 nm) NLO phosphates for uniform arrangement of PO4 tetrahedral functional groups. Adopting Cs4LiBe4P7O24 with non-uniform arrangement of PO4 as structural model, by removing low ionic potential Cs+ and Li+ successively, two DUV NLO crystals LiBePO4 and BeP2O6 were synthesized. LiBePO4 features [Be3P3O18] six-membered ring constructed by alternate connection of BeO4 and PO4, when BeP2O6 exhibits two kinds of [PO3]∞ helical chains bridged by BeO4. Remarkably, arrangement of the PO4 in LiBePO4 and BeP2O6 successfully realizes uniform evolvement. As a result, LiBePO4 exhibits enhanced second-harmonic-generation (SHG) effect up to 4.3 × Cs4LiBe4P7O24, while BeP2O6 shows even more enhanced SHG effect, reaching 7.0 × Cs4LiBe4P7O24 (2.1 × KDP). Moreover, BeP2O6 exhibits short DUV absorption edge below 175 nm and the shortest SHG phase-matching output wavelength down to 211 nm. Also, the universality of the new ionic potential modulation strategy is supported through searching known NLO materials containing alkali/alkaline-earth metal cations.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"17 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143880239","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":"Rapid response and wide-band regulation of an electrochromic device achieved by ultra-small V2O5 nanodots and a Zn2+/Li+ electrolyte","authors":"Ling Wang, Bin Wang, Haizeng Li, Lixin Qiao","doi":"10.1039/d5qi00613a","DOIUrl":"https://doi.org/10.1039/d5qi00613a","url":null,"abstract":"The distinctive multicolor characteristics of vanadium oxide (V<small>₂</small>O<small>₅</small>) set it apart from other inorganic electrochromic materials. Nevertheless, its practical applications are considerably constrained by several factors, including solubility in aqueous electrolytes, inferior conductivity, and especially limited light modulation. In this study, we introduce an innovative approach for the preparation of ultra-small V<small>₂</small>O<small>₅</small> nanodots, which are expected to offer an increased number of active sites, thereby improving the efficiency of redox reactions. A comparative analysis of the performance of the V<small>₂</small>O<small>₅</small> electrode in different cation electrolytes shows that Li<small>⁺</small> serves as the most suitable match due to its small ionic radius and monovalent nature. As a result, the V<small>₂</small>O<small>₅</small> electrochromic electrode demonstrates exceptional electrochromic performance, characterized by its ability to undergo wide-band adjustments attributable to the polarization reactions associated with cation insertion. As a proof of concept, we utilized V<small>₂</small>O<small>₅</small> nanodots and a Zn<small>²⁺</small>/Li<small>⁺</small> electrolyte to develop a multicolor transparent electrochromic display using zinc as the anode. Given the enhanced performance of the Zn<small>²⁺</small>/Li<small>⁺</small> electrolyte and the V<small>₂</small>O<small>₅</small> nanodot cathode, the prototype of the electrochromic display exhibits impressive performance, such as optical contrasts of 61.2% (728 nm) and 50.2% (1200 nm), a bleaching time of 8.5 s, a coloring time of 10.4 s, and an energy recovery efficiency of 31.65%. This work provides a significant material foundation for advancing vanadate-based electrochromic display technology and offers valuable insights into the selection of electrolytes for vanadate devices.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"6 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143880240","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":"Bifunctional Antioxidant for Concurrent Enhancement of Stability and Zinc-ion Storage Properties of Ti3C2Tx","authors":"Jie Wang, Guohao Li, Hailiang Hunan He, Xiaohui Li, Jiale Fan, Yingxinjie Wang, Xiuqiang Xie, Nan Zhang","doi":"10.1039/d5qi00001g","DOIUrl":"https://doi.org/10.1039/d5qi00001g","url":null,"abstract":"MXenes exhibit exceptional physicochemical properties, rendering them highly promising for applications in electrochemical energy storage devices. However, their easy oxidation and inherent tendency for self-stacking pose significant challenges, thereby limiting their utilization in practical application. In this study, sodium sulfide (Na2S) was used to enhance the stability of Ti3C2Tx under multiple environmental conditions. Additionally, compared to the reported antioxidation agents such as ascorbic acid (VC), sodium borohydride (NaBH4), sodium ascorbate (NaAc), and sodium bisulfite (NaHSO3), Na2S possesses an appropriate level of reducing strength, which was further used as the reducing agent to fabricate 3D macro-porous Ti3C2Tx/reduced graphene oxide (SMG) hydrogels at room temperature. This prevents the oxidation of Ti3C2Tx coming from the traditional heated gelation process and generates the porous structure conducive to the ion transport. As the free-standing cathode for zinc-ion storage, the SMG electrode possesses a high areal special capacity of 526.2 mF cm-2 at 2 mA cm-2, much higher than that of Ti3C2Tx/graphene oxide film (MG, 111.4 mF cm-2), together with outstanding cycle performance (83.2% capacity retention after 30000 cycles). This study presents Na2S as a bifunctional antioxidant for enhancing the stability of MXene and constructing 3D MXene-based aerogels at room temperature with exceptional zinc storage performance.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"76 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876266","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":"Temperature-dependent interfacial reactions between sulfide argyrodite solid electrolyte and lithium metal anode","authors":"Ye-Eun Park, SeoungJae Kang, Taehyun Kim, Huijeong Oh, KyungSu Kim, Woosuk Cho, Sangryun Kim","doi":"10.1039/d5qi00760g","DOIUrl":"https://doi.org/10.1039/d5qi00760g","url":null,"abstract":"Conventional lithium-ion batteries face increasing demand for higher energy density and improved safety. Lithium (Li) metal all-solid-state batteries are considered a promising solution to meet these challenges, owing to the high energy density of Li metal anode and the exceptional stability of solid electrolytes. However, challenges such as side reactions, dendrite formation, and interfacial instability of Li metal anodes with solid electrolytes remain unresolved. These issues are further exacerbated by the limited understanding of their temperature-dependent behavior, which is critical for elucidating the kinetics and thermodynamic stability of these systems. In this study, we elucidate how temperature-dependent interfacial interactions between the Li metal anode and a sulfide-based argyrodite solid electrolyte influence battery reactions. We find that elevated temperatures enhance ion migration kinetics and mitigate side reactions, but also induce concentration polarization of charge carriers. This trade-off relationship leads to stable interfacial Li cycling at intermediate temperature ranges (ca. 80 °C), but results in a significant resistance increase at the higher temperatures (ca. 120 °C) during cycling. These findings offer valuable insights for developing reliable Li metal electrode all-solid-state batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"73 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872378","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}