Inorganic Chemistry Frontiers最新文献

Ionic Radius-Dependent Self-Assembly of Lanthanide Organic Polyhedra: Structural Diversities and Luminescent Properties

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2025-02-20 DOI: 10.1039/d5qi00265f

Jing Su, Yin Fan, Xiao-Fang Duan, Jing-Yao Zhou, Lipeng Zhou, Chong-Bin Tian, Qing-Fu Sun

{"title":"Ionic Radius-Dependent Self-Assembly of Lanthanide Organic Polyhedra: Structural Diversities and Luminescent Properties","authors":"Jing Su, Yin Fan, Xiao-Fang Duan, Jing-Yao Zhou, Lipeng Zhou, Chong-Bin Tian, Qing-Fu Sun","doi":"10.1039/d5qi00265f","DOIUrl":"https://doi.org/10.1039/d5qi00265f","url":null,"abstract":"The synthesis of nonclassical polyhedra is at the forefront of supramolecular research for their unique anisotropic interior cavities. However, due to the difficulty in controlling the topology of Ln supramolecular systems, the preparation of nonclassical lanthanide organic polyhedral (LOPs) remains a challenge. Herein, we explore the ionic radius dependent self-assembly of LOPs using rectangular tetra-tropic ligand L. Due to the rectangular, other than square, geometry of the ligand panels, the assembly of it with lanthanide ions located in the middle of Ln series affords the irregular tetragonal antiprismatic Ln8L4 (Ln = Sm3+, Eu3+, Tb3+, Dy3+ and Ho3+) with two faces are unoccupied by ligands L. Interestingly, such tetragonal antiprism possesses an oblate internal cavity, which binds four THF molecules in the solid-state structure. With an increase in radius, the larger La3+ and Nd3+ ions, produces a distinct architecture, the sandwich square, Ln4L2. In contrast, the smaller Er3+ and Lu3+ ions give rise to a mixture of both Ln8L4 and Ln6L3. Once adding excess Ln3+ ions, the structure transformation from Ln8L4 to Ln6L3 occur. Structural comparisons of La4L2 and Sm8L4 reveal that the differences in architecture within these systems are governed by both the ionic radii of the lanthanides and the conformational flexibility of the ligands. Photophysical investigations disclose that the ligand L exhibits a sensitizing ability toward Sm3+, Tb3+ and Dy3+ ions, displaying their characteristic luminescence emission, with a new record-setting luminescent quantum yield of 92.74% being observed for Tb8L4. This work provides new insights to understand the effect of lanthanide size on the resulting assemblies and opens new avenues to develop nonclassical LOPs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"208 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462511","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}

引用次数: 0

Electrostatic Regulation of Zn2+ Ion Concentration on Electrodes and Its Impact on Electrochemical Performance

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2025-02-20 DOI: 10.1039/d5qi00097a

Yijun Yu, Lei Liu, Puning Liu, Wannian Jiang, Zhonghua Zhang, Xiaosong Guo, Lin Zhang, Jun Zheng, Guicun Li

{"title":"Electrostatic Regulation of Zn2+ Ion Concentration on Electrodes and Its Impact on Electrochemical Performance","authors":"Yijun Yu, Lei Liu, Puning Liu, Wannian Jiang, Zhonghua Zhang, Xiaosong Guo, Lin Zhang, Jun Zheng, Guicun Li","doi":"10.1039/d5qi00097a","DOIUrl":"https://doi.org/10.1039/d5qi00097a","url":null,"abstract":"The solvation structure of electrolytes, particularly the distribution and composition of contact ion pairs (CIP) and solvent-separated ion pairs (SSIP), is a prominent focus in battery research, serving as a critical determinant for understanding and interpreting battery electrochemical behavior. In this work, a phosphate-enriched protective layer (ZAP) was fabricated on the Zn electrode via a simply displacement reaction to modify the adsorption properties of the Zn electrode, thereby influencing the composition of CIP and SSIP at the electrode-electrolyte interface. Experimental results revealed that the ZAP layer significantly reduced the overpotential for Zn deposition, particularly in low-concentration electrolytes and under high deposition currents. Through a series of characterizations and theoretical calculations, it was found that the ion concentrations at the electrode-electrolyte interface played a pivotal role in governing interfacial electrochemistry, surpassing the influence of the CIP-to-SSIP ratio in the bulk electrolyte. Moreover, the ZAP layer could effectively suppress side reactions and enhance cycling stability of batteries. This study introduces a simple and cost-effective approach for protecting Zn anodes and emphasizes the critical importance of interfacial ion concentrations in electrochemical analysis.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"15 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451953","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}

引用次数: 0

Inch-sized single crystal of radiation-sensitive copper-based hybrid perovskite for direct X-ray detection

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2025-02-20 DOI: 10.1039/d5qi00263j

Yicong Lv, Xiantan Lin, Fafa Wu, Zengshan Yue, Fen Zhang, Xiaoqi Li, Qingyin Wei, Kai Li, Qianxi Wang, Junhua Luo, Xitao Liu

{"title":"Inch-sized single crystal of radiation-sensitive copper-based hybrid perovskite for direct X-ray detection","authors":"Yicong Lv, Xiantan Lin, Fafa Wu, Zengshan Yue, Fen Zhang, Xiaoqi Li, Qingyin Wei, Kai Li, Qianxi Wang, Junhua Luo, Xitao Liu","doi":"10.1039/d5qi00263j","DOIUrl":"https://doi.org/10.1039/d5qi00263j","url":null,"abstract":"Metal halide perovskites, particularly lead-based compounds, manifest great potential in X-ray detection due to their exceptional light absorption coefficients, superior carrier mobility and cost-effective preparation methods. Despite recent significant advancements, the limitations of lead toxicity hinder their further application and encourage the exploration of environmentally friendly alternatives. Herein, a novel lead-free two-dimensional (2D) copper-based halide perovskite (2FEA)2CuCl4 (2FEA = 2,2-difluoroethylamine) single crystal is developed, which exhibits a highly sensitive response to X-ray illumination. Especially, an inch-sized single crystal of (2FEA)2CuCl4 with dimensions up to 30 × 28 × 0.5 mm3 is grown using a low-cost cooling crystallization method. Direct X-ray detectors fabricated from these single crystals demonstrated an exceptionally high sensitivity of 1106.44 μC Gyair-1 cm-2 at a 10 V bias, approximately 43 times higher than that of the conventional radiation-sensitive semiconductor α-Se (~25 μC Gyair-1 cm-2). Furthermore, (2FEA)2CuCl4 exhibits a stable baseline with the low dark current drift of 5.056 × 10-7 nA cm-1 s-1 V-1 and the low limit of detection of 130.1 nGyair s-1 at 10 V bias. These findings manifest the great potential of 2D copper-based hybrid perovskites for the next generation of highly sensitive X-ray detection, which sheds light on the rational crystal design of “green” radiation-sensitive hybrid perovskites.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451954","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}

引用次数: 0

Regulating the coordination environment of single-atom catalysts anchored on nitrogen-doped graphene for efficient nitrogen reduction

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2025-02-20 DOI: 10.1039/d4qi03239j

Shuo Wang, Bo Zhu, Likai Yan

{"title":"Regulating the coordination environment of single-atom catalysts anchored on nitrogen-doped graphene for efficient nitrogen reduction","authors":"Shuo Wang, Bo Zhu, Likai Yan","doi":"10.1039/d4qi03239j","DOIUrl":"https://doi.org/10.1039/d4qi03239j","url":null,"abstract":"Electrocatalysts with excellent selectivity and activity towards the target product are pivotal for N2 conversion and utilization. In this study, we systematically explored the nitrogen reduction reaction (NRR) catalytic performance of Mo-based single-atom catalysts (Mo-N4-SACs) through density functional theory (DFT) calculations. We changed the coordination environment of the single atom by placing the active center of the SACs at the edge or basal plane of N-doped graphene or changing the coordination atom of the active center. Among the four Mo-N4-SACs studied, Mo-ZZG demonstrated remarkable catalytic activity and selectivity for N2 reduction to NH3 with a limiting potential (UL) of −0.26 V. After considering the solvation effect, the potential determination step was N2 → N2H, and only the UL was increased, specifically to −0.42 V. In order to reduce the UL of the Mo-ZZ-edge (−0.85 V) for the NRR by replacing the N atom with an S or O atom, the UL of the O1-ZZ-edge was reduced to −0.58 V. This well illustrated that the catalytic activity could be effectively improved by rationally adjusting the position and coordination atoms of a single atom. This work provides valuable insights into the rational design and screening of efficient catalysts for N2 reduction.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"11 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451955","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}

引用次数: 0

Coordination modulation of single-atom Zn sites to boost oxygen reduction performance

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2025-02-20 DOI: 10.1039/d4qi03126a

Siying Zhang, Xue Bai, Tianmi Tang, Weidong Ruan, Jingqi Guan

{"title":"Coordination modulation of single-atom Zn sites to boost oxygen reduction performance","authors":"Siying Zhang, Xue Bai, Tianmi Tang, Weidong Ruan, Jingqi Guan","doi":"10.1039/d4qi03126a","DOIUrl":"https://doi.org/10.1039/d4qi03126a","url":null,"abstract":"Rational design of highly active and durable oxygen reduction reaction (ORR) electrocatalysts to replace expensive platinum-based catalysts and significantly improve the electrocatalytic performance of rechargeable zinc-air batteries (ZABs) has become a key goal in the field of energy storage technology. Here, we modulate the coordination structure of single-atom Zn sites on N-doped graphene matrix by a rapid heating technology to enhance the ORR performance. In 0.1 M KOH solution, the half-wave potential (E1/2) of Zn-NG is 0.84 V, and it has good anti-Fenton reaction performance. The zinc-air battery assembled with Zn-NG as the cathode material has an open-circuit voltage (OCV) of up to 1.50 V, and exhibits a maximum power density of 158 mW cm-2 and excellent output stability for over 200 h. Theoretical calculations show that the Zn-N4G configuration exhibits lower ORR barrier than Zn-N2G and Zn-N3G structures. The rate-determining step on Zn-N2G and Zn-N3G is *O →* OH, and both show a reaction barrier significantly greater than 1.00 eV. In contrast, the rate-determining step on the Zn-N4G is *OH → * + H2O, and the energy barrier is only 0.68 eV, thus exhibiting better catalytic performance.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"82 10 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451952","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}

引用次数: 0

Correction: Monolithic green-sensitive photodetectors enabled by a ZnSnN2/GaN nanorods/silicon double heterojunction

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2025-02-19 DOI: 10.1039/d5qi90017d

Jeong Hyeon Kim, Juchan Hwang, Soon Joo Yoon, Jongmin Kim, Yoon Kyeung Lee, Kwangwook Park, Han Eol Lee

引用次数: 0

From Ca3Be(SeO3)4 to SrBe(SeO3)2: Two Unprecedented Alkaline Earth Metal Beryllium Selenites with Large Band Gaps and Enhanced Birefringence

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2025-02-19 DOI: 10.1039/d5qi00039d

Xinyi Wang, Xin Wen, Yuchen Yan, Jindong Chen, Guangsai Yang, Guang Peng, Ning Ye

引用次数: 0

P Vacancy-Induced Electron Redistribution and Phase Reconstruction of CoFeP for Overall Water Splitting at Industrial-Level Current Density

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2025-02-19 DOI: 10.1039/d4qi03351e

Xueling Wei, Yang Jiao, Xiangyu Zou, Yuchen GUO, Wenhu Li, Taotao Ai

{"title":"P Vacancy-Induced Electron Redistribution and Phase Reconstruction of CoFeP for Overall Water Splitting at Industrial-Level Current Density","authors":"Xueling Wei, Yang Jiao, Xiangyu Zou, Yuchen GUO, Wenhu Li, Taotao Ai","doi":"10.1039/d4qi03351e","DOIUrl":"https://doi.org/10.1039/d4qi03351e","url":null,"abstract":"Hydrogen production through water splitting using transition metal-based phosphide electrocatalysts represents a highly promising and sustainable energy conversion strategy. In this study, phosphating and vacancies engineering through Ar plasma-assisted is achieved via a single-step process. Taking CoFePv with phosphorus vacancies (Pv) as bifunctional electrocatalysts, it effectively promotes both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), thereby significantly facilitating overall water splitting (OWS) in alkaline media. In OER and HER processes, the driving potentials needed to attain current density of 1 A cm-2 are only 382 and 367 mV, respectively. Furthermore, the CoFePv (+, −) OWS electrolyzer is capable of maintaining a current density of 2 A cm⁻² at 1.98 V under simulated industrial settings (6 M KOH, 80°C). It also demonstrates stable performance at a current density of 0.5 A cm⁻² for a duration of 100 hours. In-situ Raman spectroscopy observations show that Pv induce rapid catalyst phase reconstruction, thereby significantly enhancing the OER performance of CoFePv. Density functional theory (DFT) calculations demonstrate that phosphorus vacancies can modulate the electronic properties of Co-Fe-P, facilitate electron transfer, as well as optimize the adsorption and desorption of reaction intermediates.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451956","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}

引用次数: 0

Organophosphonate- and dimethylarsinate-functionalized hexamolybdates(V) and their solution and gas phase properties

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2025-02-18 DOI: 10.1039/d4qi03215b

Vinaya Siby, Arun Pal, Bassem Bassil, Saurav Bhattacharya, Anusree Sundar, Juliane Oberstein, Damin Kim, Rizul Gupta, Alisher Kuanysh, Jana Hölscher, Dorothea Schmidt, Nikolai Kuhnert, Ulrich Kortz

引用次数: 0

A Potential UV Nonlinear-Optical Crystal with Strong Second-Harmonic Response: RbNa2Eu2(BO3)3

IF 7 1区化学

Inorganic Chemistry Frontiers Pub Date : 2025-02-18 DOI: 10.1039/d4qi03330b

Dan Li, Jingyu Shang, Ming Gao, Jiangtao fan, Zhangui Hu, Ping Peng, Yicheng Wu

{"title":"A Potential UV Nonlinear-Optical Crystal with Strong Second-Harmonic Response: RbNa2Eu2(BO3)3","authors":"Dan Li, Jingyu Shang, Ming Gao, Jiangtao fan, Zhangui Hu, Ping Peng, Yicheng Wu","doi":"10.1039/d4qi03330b","DOIUrl":"https://doi.org/10.1039/d4qi03330b","url":null,"abstract":"Ultraviolet (UV) nonlinear optical (NLO) crystals with second-harmonic generation (SHG) response can efficiently output UV coherent light, which has important applications in UV solid-state lasers. Herein, we designed and synthesized a novel Eu-based borate (NLO) crystal, RbNa2Eu2(BO3)3 (RNEBO), which introduces Eu to A3RE2(BO3)3 (A = alkali metal, RE = rare earth) system applied in the UV direction firstly and exhibits both strong SHG activity and widely optical transmission window. The RNEBO crystallizes into the non-centrosymmetric (NCS) space group Amm2, featuring a three-dimensional framework of [EuBO3]∞ layers with isolated [BO3]3- groups bridging in a coplanar arrangement. Meanwhile, the alkali metal cations Rb+ and Na+ were incorporated into the void of the anion framework to ensure coordination and charge balance. The distinctive internal structure endows RNEBO to possess large SHG response (~3.55 × KDP) and UV transmittance of 6.17% at 200nm. This finding confirms that RNEBO is a potentially UV NLO crystals and provides valuable insights for the exploration of Eu-based borate UV NLO crystals in the future.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435391","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}

引用次数: 0