Inorganic Chemistry Frontiers最新文献

{"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":"Enhanced photoelectrochemical water splitting performance of hematite photoanodes via uniform Ti and gradient Ge co-doping","authors":"Chunlian Hu, Junhao Wu, Congzhao Dong, Xiao Fang, Pengfei Feng, Bonan Li, Baochun Ma, Yong Ding","doi":"10.1039/d5qi00700c","DOIUrl":"https://doi.org/10.1039/d5qi00700c","url":null,"abstract":"The photoelectrochemical (PEC) water oxidation reaction on hematite (α-Fe2O3) photoanodes has certain limitations, especially poor conductivity and rapid carrier recombination. To address the above issues, uniform Ti doping and gradient Ge doping were used to construct Ti-Ge co-doping hematite (Ti-Ge:Fe2O3). A series of characterization tests showed that uniform Ti doping increased the carrier concentration and conductivity, while gradient Ge doping improved the charge separation efficiency. Meanwhile, Ti-Ge co-doping hematite constructed a gradient energy band structure, which played a contributing role in improving the charge separation efficiency. The co-doping of other metal elements with Ti was carried out, all of which showed significant effects in improving the PEC performance. This suggested that the Ti:M (M=metal elements) co-doping hematite in improving PEC performance was universal. In addition, when the NiFeOOH co-catalyst was loaded on Ti-Ge:Fe2O3, the onset potential shifted negatively 150 mV and photocurrent density significantly improved, which was about 9.7 times higher than that of bare Fe2O3. This work provides a novel strategy of improvement of PEC performance on hematite by co-doping engineering.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872417","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}

{"title":"Strong NIR Electrochemiluminescence from Lanthanide Ions Sensitized with a Carbon-Rich Ruthenium Chelate","authors":"Jing Yu, Miaoxia Liu, Tuan-Anh Phan, Laurent Bouffier, Lucie Norel, Stéphane Rigaut, Neso Sojic","doi":"10.1039/d5qi00450k","DOIUrl":"https://doi.org/10.1039/d5qi00450k","url":null,"abstract":"We report on intense electrochemiluminescence (ECL) emission from the redox switching of a series of heterobimetallic systems consisting of lanthanide complexes emitting in the near-infrared (NIR) range (Yb3+, Nd3+) associated with a redox-active carbon-rich ruthenium bipyridyl antenna chelate. The NIR ECL emission was achieved successfully using the same molecular scaffold. The electrochemical reactions between the antenna and the sacrificial ECL coreactant allows for this low-potential redox modulation of NIR luminescence of Yb3+ and Nd3+. This strategy offers interesting new insights into NIR ECL systems based on inorganic complexes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"48 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866472","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":"Harnessing the Dual Role of DMSO in the Synthesis of SbOCl·DMSO: An Excellent UV Nonlinear Optical Crystal with Unique 1D Spiral Chain","authors":"Xiande Peng, Xiangyuan Li, Yingzi Zhang, Xuehua Dong, Ling Huang, Liling Cao, Daojiang Gao, Guohong Zou","doi":"10.1039/d5qi00758e","DOIUrl":"https://doi.org/10.1039/d5qi00758e","url":null,"abstract":"Ultraviolet (UV) nonlinear optical (NLO) materials are essential for applications such as laser micromachining and optical parametric oscillations. An ideal UV NLO material should exhibit a large second-harmonic generation (SHG) coefficient, moderate birefringence and a short UV cut-off edge. However, achieving these properties simultaneously in a single material remains a significant challenge due to their distinct structural requirements. In this study, we report the synthesis of a novel UV NLO material, SbOCl·DMSO, which features an optimized 1D helical chain structure. For the first time, the polar organic molecule dimethyl sulfoxide (DMSO) is introduced into the SbCl<small>₃</small> system, where it coordinates with Sb atom via Sb-O bonds, modifying the chain structure. This unique 1D [SbOCl]<small>_∞</small> helical chain enhances the compound’s polarizability and optical anisotropy, leading to excellent optical properties. SbOCl·DMSO exhibits a large SHG coefficient of 4.4 × KDP, moderate birefringence of 0.084@546 nm and a short UV cut-off edge of 331 nm, making it a highly promising candidate for UV NLO applications. This work highlights the importance of synergistic molecular design and provides a new strategy for the development of high-performance frequency-doubling crystals.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"21 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866462","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":"Cumulative 2c-2e vs 3c-2e π-Back Donations: Conformation Preferences in Germylene Gold(I) Complexes","authors":"Lifang Wu, Zhang Rong, Xinran Wang, Wenyao Zeng, Lanhui Zhang, Yining Gao, Jiyong Liu, Lingbing Kong, Jiaxin Chen, Liliang Wang","doi":"10.1039/d5qi00539f","DOIUrl":"https://doi.org/10.1039/d5qi00539f","url":null,"abstract":"The first homoleptic and heteroleptic cationic germylene-gold(I) complexes <strong>3</strong>, <strong>4</strong>, and <strong>7</strong> have been synthesized and structurally characterized, accompanied by the discovery of novel types of π-back donations. These complexes exhibit distinct conformation preferences (vertical vs quasi-planar) modulated by the π-acidity of germylene and NHC ligands. Our bonding analyses further indicated that the homoleptic complex <strong>3</strong> exhibits marvelous cumulative two-center-two-electron (2c-2e) π-back donations, whereas the heteroleptic complexes <strong>4</strong> and <strong>7</strong> demonstrate extraordinary three-center-two-electron (3c-2e) π-back donations. These findings offer a comprehensive explanation for the atypical disruption of extensive π-systems, along with the transition from quasi-planar to vertical conformations.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"9 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866465","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":"Pushing Boundaries in Single Molecule Magnets: An Ab Initio Perspective on Harnessing Higher Oxidation States for Unprecedented Lanthanide SMM Performance","authors":"Tanu Sharma, Rajanikanta Rana, Abinash Swain, Gopalan Rajaraman","doi":"10.1039/d5qi00907c","DOIUrl":"https://doi.org/10.1039/d5qi00907c","url":null,"abstract":"The recent breakthrough of attaining blocking temperature near liquid N2 temperature rekindled the interest in lanthanide-based Single Molecule Magnets (SMMs) towards end-user applications. Within this realm, several challenges are present, with a key objective being the further enhancement of the blocking temperature. As the current set of molecules based on DyIII has already reached their maximum potential barrier height for magnetization reversal (Ueff), chemical insights-based developments are hampered. In this connection, using Density Functional Theory (DFT) and ab initio Complete Active Space Self-Consistent Field (CASSCF) methods, we have explored the possibility of obtaining lanthanide SMMs in high-valent oxidation states such as +4 and +5. We begin with various small models of [LnO2]+, [LnO2], and [LnO2]− (Ln varying from Ce to Lu) systems to correlate the nature of the lanthanides to the SMM characteristics. We have also extended our study to include five complexes reported earlier possessing +4 and +5 oxidation states to offer clues to improve the SMM characteristics. Our calculations reveal several advantages in fine-tuning the oxidation states in lanthanide SMMs, and this includes (i) the lanthanide-ligand covalency found to increase as compared to the LnIII counterpart (ii) yield barrier height for magnetization reversal as high as 8424 cm−1, an unprecedented value among any models reported (iii) among various ways to stabilize such high-oxidation states, encapsulation yields several targets, with HoO2@SWCNT(4,4) predicted to yield an impressive energy barrier of ~5400 cm⁻¹ (iv) stronger lanthanide-ligand bonds were also found to quench spin-phonon relaxation, as they offset the vibrations that cause this relaxation. This potentially yields larger blocking temperatures, offering a novel strategy for a new class of lanthanide SMMs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"25 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872381","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":"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":"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}