Inorganic Chemistry最新文献_第9页

Enhanced Formic Acid Dehydrogenation over Basic Site-Rich Pd/Al2O3 Hollow Sphere Catalyst 富碱性Pd/Al2O3空心球催化剂强化甲酸脱氢

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-06-16 DOI: 10.1021/acs.inorgchem.5c01771

Shuai Wei, Hui Liang, Xuan Xu, Jun-Hao Hu, Yu Li, An-Qi Xu, Ye-Qiang Tang, Wen-Zhu Yu, Ling-Ling Guo, Peng Wang

{"title":"Enhanced Formic Acid Dehydrogenation over Basic Site-Rich Pd/Al2O3 Hollow Sphere Catalyst","authors":"Shuai Wei, Hui Liang, Xuan Xu, Jun-Hao Hu, Yu Li, An-Qi Xu, Ye-Qiang Tang, Wen-Zhu Yu, Ling-Ling Guo, Peng Wang","doi":"10.1021/acs.inorgchem.5c01771","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01771","url":null,"abstract":"Formic acid (FA) is regarded as a safe and practical hydrogen carrier owing to its favorable storage and handling characteristics. However, achieving efficient and selective FA dehydrogenation under mild conditions remains a significant challenge. In this study, the decomposition pathway of FA was found to be highly dependent on the acid–base characteristics of the catalyst support, with basic surfaces preferentially favoring the dehydrogenation route. Therefore, a morphology-regulated strategy was developed to modulate the distribution of basic sites on alumina, revealing a direct structure–function relationship that governs the catalytic behavior. Al2O3 hollow spheres (HS), featuring abundant surface basicity, were synthesized via a hydrothermal method and used as supports for Pd catalysts alongside Al2O3 nanobelts (NB) and nanoparticles (NP). Mechanistic studies integrating catalytic evaluation, in situ DRIFTS, and CO2-TPD analyses demonstrated that the Pd/Al2O3–HS catalyst, owing to its support enriched in basic sites, simultaneously facilitates formate formation and promotes the generation of the Pd–HCOO* intermediate, thereby enhancing H2 production. This synergy results in superior catalytic performance (TOF = 4606 h–1) with no detectable CO formation. The increased basicity of the support markedly improved the hydrogen evolution during formic acid decomposition, highlighting a strong correlation between support basicity and catalytic efficiency.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305432","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Coupling Transition Metal Chalcogenides with Metal Nanoclusters for Steering Photoredox Catalysis. 过渡金属硫族化合物与金属纳米簇的耦合控制光氧化还原催化。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-06-16 DOI: 10.1021/acs.inorgchem.5c01919

Lifeng Cai,Yu-Shan Cai,Wei Zhao,Jie Liang,Qing Chen,Fang-Xing Xiao

{"title":"Coupling Transition Metal Chalcogenides with Metal Nanoclusters for Steering Photoredox Catalysis.","authors":"Lifeng Cai,Yu-Shan Cai,Wei Zhao,Jie Liang,Qing Chen,Fang-Xing Xiao","doi":"10.1021/acs.inorgchem.5c01919","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01919","url":null,"abstract":"Metal nanocluster (NC)-mediated photocatalytic CO2 conversion is an emerging avenue for achieving carbon neutrality, yet it remains underexplored due to the ultrashort charge lifespan of metal NCs. To surmount this obstacle, metal NC/transition metal chalcogenide (TMC) heterostructures are constructed via a ligand-initiated electrostatic self-assembly buildup. In this meticulously designed nanoarchitecture, glutathione (GSH)-protected metal NCs [Aux@GSH, Au22(GSH)18, Ag9(GSH)6, Ag16(GSH)9, Ag31(GSH)19] are uniformly anchored on the two-dimensional (2D) TMC (CdS, ZnIn2S4, CdIn2S4, In2S3) framework, leading to well-defined metal NC/TMC composite photosystems. The favorable energy level alignment between these metal NCs and TMCs synergistically endows metal NC/TMC heterostructures with markedly increased photoredox activities, encompassing photocatalytic CO2 reduction, H2 production, and aromatic alcohol oxidation under visible light, far surpassing the corresponding pristine TMC counterparts. Alloy NCs (AuxAg1-x, AuxCu1-x)/TMCs are also constructed to demonstrate the universality of the heterostructures. The generation of a type II charge transport pathway between metal NCs and TMCs is unveiled to account for the photoredox mechanisms. Our work will provide an interesting idea for tuning charge transfer over metal NCs for photocatalysis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144295881","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Nickel-Induced Activation of Iron Foam for the Oxygen-Evolution Reaction: A Multimodal Study of Structure and Dynamics. 镍诱导泡沫铁的析氧反应：结构和动力学的多模态研究。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-06-16 DOI: 10.1021/acs.inorgchem.5c01959

Negah Hashemi,Mohammad Mahdi Najafpour

{"title":"Nickel-Induced Activation of Iron Foam for the Oxygen-Evolution Reaction: A Multimodal Study of Structure and Dynamics.","authors":"Negah Hashemi,Mohammad Mahdi Najafpour","doi":"10.1021/acs.inorgchem.5c01959","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01959","url":null,"abstract":"Iron/nickel (hydr)oxides are widely recognized as efficient catalysts for the oxygen-evolution reaction (OER) in alkaline media. In this study, the effect of Ni on Fe foam toward OER activity is investigated. Treatment with nickel(II) nitrate induces the emergence of oxidation and reduction peaks, whose intensity and position are modulated by the nickel concentration on the iron foam surface. Remarkably, the OER onset potential exhibits a 240 mV reduction in overpotential upon the incorporation of nickel ions. In-situ Raman spectroscopy reveals the formation of γ-NiO(OH) during OER. Although substantial Fe ions are incorporated into the nickel (hydr)oxide matrix, reduced OER activity and a negative potential shift in the Ni(II)/(III) peak suggest Fe leaching during OER. Based on our findings, we propose a structure featuring multiple active sites, including nickel-doped iron hydroxide, iron oxide, nickel hydroxide, and mixed nickel/iron hydroxides with varying stoichiometries. This work highlights nickel-induced activation of iron foam to enhance OER performance, offering valuable insights for designing advanced, cost-effective, and durable electrocatalysts for applications such as water splitting and renewable energy storage systems.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"43 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144295877","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-06-16

Hangyu Zhou, Xin Wang, Qingzhong Li* and Steve Scheiner*,

引用次数: 0

Mechanistic Investigation on the C-C Bond Cleavage of α-Hydroxy Ketone Catalyzed by Engineering P450 Monooxygenase Enzyme F182L-CYP199A4. 工程P450单加氧酶F182L-CYP199A4催化α-羟基酮C-C键断裂机理研究

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-06-16 Epub Date: 2025-06-05 DOI: 10.1021/acs.inorgchem.4c05390

Sujiao Zhao, Yongjun Liu

{"title":"Mechanistic Investigation on the C-C Bond Cleavage of α-Hydroxy Ketone Catalyzed by Engineering P450 Monooxygenase Enzyme F182L-CYP199A4.","authors":"Sujiao Zhao, Yongjun Liu","doi":"10.1021/acs.inorgchem.4c05390","DOIUrl":"10.1021/acs.inorgchem.4c05390","url":null,"abstract":"In addition to the typical oxygen insertion reaction, some cytochrome P450 also catalyze the C-C cleavage, and most P450 employs Cpd I to trigger lyase reactions. There is also evidence to support an alternative mechanism, in which a species earlier than the formation of Cpd I was suggested to perform the lyase reaction. To understand the detailed reaction mechanism, we performed quantum mechanics/molecular mechanics (QM/MM) calculations to explore the cleavage mechanism of mutated CYP199A4 (F182L-CYP199A4). Our calculation results reveal that the peroxoanion (Fe(III)-O-O2-) rather than oxo-ferrous (Fe(III)-O-O1-) and Cpd I is responsible for initiating the reaction. The Fe(III)-O-O2- nucleophilic directly attacks the carbonyl of the substrate, which first generates an unstable peroxo intermediate, followed by the Baeyer-Villiger-type oxidative cleavage of the C-C bond. During the reaction, complex electronic and structural rearrangements are involved. In the active site of F182L-CYP199A4, the formation of Cpd I is successfully slowed down owing to the absence of mediated water to promote two steps of protonation of Fe-coordinated dioxygen. In addition, Fe(III)-O-O2- shows higher reactivity than Fe(III)-O-O1- toward C-C cleavage. In general, the fact that CYP can also employ the peroxoanion to execute the C-C bond cleavage further enriches the catalytic chemistry of P450.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"11342-11356"},"PeriodicalIF":4.3,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232659","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

A Tetradentate Chelator for Reducing Damage Caused by Uranium. 一种减少铀危害的四齿螯合剂。

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-06-16 DOI: 10.1021/acs.inorgchem.5c00872

Yong Li,Bin Yang,Wangbo Qu,Jiao Lu,Zhou Wu,Jun Wang,Ruihong Yao,Yanli Li,Zhihao Lu,Shihai Yan,Zhirong Geng,Zhilin Wang

{"title":"A Tetradentate Chelator for Reducing Damage Caused by Uranium.","authors":"Yong Li,Bin Yang,Wangbo Qu,Jiao Lu,Zhou Wu,Jun Wang,Ruihong Yao,Yanli Li,Zhihao Lu,Shihai Yan,Zhirong Geng,Zhilin Wang","doi":"10.1021/acs.inorgchem.5c00872","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00872","url":null,"abstract":"The rapid advancement of the nuclear industry has precipitated significant challenges in nuclear pollution, with radionuclide uranium emerging as a formidable threat to human safety due to its potent chemical toxicity and radioactivity. The development of uranium chelators represents a pivotal strategy in mitigating the internal damage caused by nuclear exposure. While the US Food and Drug Administration has approved certain drugs for this purpose, issues such as low selectivity and high toxicity remain unresolved. In this study, a tetradentate chelating agent, MDDO was synthesized. Compared with the commercially available agent CaNa3-DTPA, MDDO exhibits markedly lower toxicity. In addition, the addition of MDDO markedly reduced the extent of cellular damage caused by uranium. In vivo studies have shown that immediate administration of MDDO achieves removal rates of uranyl ions at 49.6% in the kidneys and 52.0% in the femurs. These findings not only underscore the potential of MDDO as a uranium chelator but also pave the way for the development of radionuclide decorporation agents, offering fresh perspectives in the ongoing quest to enhance nuclear safety and public health.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"17 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144295880","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Biomimetic Peroxidase Model: Copper–Organic Framework Material Constructed with a Low-Symmetry Triazine Polycarboxylate Ligand for Visual Application as a Biosensing Platform 仿生过氧化物酶模型：低对称三嗪聚羧酸配体构建的铜-有机框架材料作为视觉应用的生物传感平台

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-06-16 DOI: 10.1021/acs.inorgchem.5c00386

Zi Yang Wang, Chen Wang, Jiaru Li, Yufei Wang, Yuxian Chi, Shan Jiang, Feng Ying Bai, Yong Heng Xing

{"title":"Biomimetic Peroxidase Model: Copper–Organic Framework Material Constructed with a Low-Symmetry Triazine Polycarboxylate Ligand for Visual Application as a Biosensing Platform","authors":"Zi Yang Wang, Chen Wang, Jiaru Li, Yufei Wang, Yuxian Chi, Shan Jiang, Feng Ying Bai, Yong Heng Xing","doi":"10.1021/acs.inorgchem.5c00386","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00386","url":null,"abstract":"Metal–organic frameworks (MOFs) have recently emerged as fascinating enzymatic mimics due to their active metal-redox centers and attractive structural adjustability. However, the design of MOFs based on low-symmetry triazine polycarboxylate ligands as peroxidase-like mimics remains largely unexplored. Herein, a novel Cu-MOF (complex 1) was prepared using [5,5′-((6-(bis(carboxymethyl)amino)-1,3,5-triazine-2,4-diyl)bis(azanediyl))diisophthalic acid, H6BATD] by a solvothermal method. Complex 1 presented a better affinity for the hydrogen peroxide substrate compared with the natural horseradish peroxidase (HRP) enzyme. Its peroxidase-like activity is related to the production of hydroxyl radicals (•OH) and superoxide radicals (•O2–), and the brief conversion mechanism is speculated based on XPS data. Based on this, the colorimetric method was utilized for the detection of H2O2 and partial biological molecules, especially ascorbic acid (AA) and glutathione (GSH), and the detection limits were as low as 0.38 μM for AA and 0.44 μM for GSH. In addition, smartphone-assisted recognition for AA sensing was realized, and complex 1 was employed as a peroxidase nanozyme for AA detection in fruits and pharmaceuticals. These findings not only throw light on the construction of MOFs with high enzyme-like activity but also on the structural expansion of novel MOFs based on a low-symmetry family of triazine derivative linkers.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"44 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305430","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

AIE-Active Zr-Organic Gels for Luminescent Solar Concentrators. 用于发光太阳能聚光器的活性zr -有机凝胶。

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-06-16 Epub Date: 2025-05-30 DOI: 10.1021/acs.inorgchem.5c01166

Haijiang Bian, Zipeng Wang, Qiang Jing, Haiguang Zhao, Zhe Zhang, Jianxin Song, Yuanqian Ai, Jing Ding, Xianjun Guo, Chao Wang, Wei Liu

{"title":"AIE-Active Zr-Organic Gels for Luminescent Solar Concentrators.","authors":"Haijiang Bian, Zipeng Wang, Qiang Jing, Haiguang Zhao, Zhe Zhang, Jianxin Song, Yuanqian Ai, Jing Ding, Xianjun Guo, Chao Wang, Wei Liu","doi":"10.1021/acs.inorgchem.5c01166","DOIUrl":"10.1021/acs.inorgchem.5c01166","url":null,"abstract":"Luminescent metal-organic gels (MOGs) have emerged as a novel class of soft materials characterized by their unique metal-ligand coordination frameworks, which endow them with high functionalization, plasticity, and chemical stability. This study introduces a zirconium-based organic gel (Zr-Gel) exhibiting aggregation-induced emission (AIE), readily synthesized on a large scale via a straightforward solvothermal route. The as-synthesized Zr-Gel exhibits a broader excitation range and higher excitation intensity than pure H4ETTC ligand, with a Stokes shift of approximately 0.50 eV and a high quantum yield of 84.24%. In contrast to metal-organic framework (MOF) materials composed of the same ligand and metal, the Zr-Gel retains a high fluorescence quantum yield even at excitation wavelengths down to 300 nm. Such exceptional properties make them highly promising as fluorescent materials for optoelectronic devices. As a proof of concept, we fabricated Zr-Gel-based filled luminescent solar concentrators (LSCs) that achieved an optical conversion efficiency (ηopt) of 1.70% under simulated sunlight illumination (100 mW cm-2). For comparison, coated LSCs based on PCN-94 and PCN-128 were also prepared, further validating the superior performance of Zr-Gel and highlighting the significant potential of MOGs for LSC applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"11705-11711"},"PeriodicalIF":4.3,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144186067","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-06-16

Sihong Li, Qijie Mo, Huan Lin, Chunying Chen* and Li Zhang*,

引用次数: 0

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-06-16

Mei-Qian Fu, Yu Xiong, Wei-Dong Yu*, Huiya Dai, Yujian Bian, Jiening Feng, Yin Zhang, Xiangnan Wang, Wei Li, Yi-Xin Li, Chao Liu and Jun Yan*,

引用次数: 0