Weiping Huang, Jin chang Liu, Feng Wang, Wei Xu, Zi-Meng Tao, David Middleton, Cheng-Dong Liu, Shu-Qin Qin, Wen-Cai Ye, Ren-Wang Jiang
Liquid water is essential for life, but many other substances that exist in the liquid state under standard conditions can have severe detrimental effects on living organisms and the environment. Isolation of these substances and determination of their three-dimensional structures are important to understand and, ultimately, to eliminate their harmful effects. Unfortunately, the mobility and disorder inherent in liquid molecules presents major challenges for their structure elucidation. Consequently, very few structures of liquid molecules have been determined with certainty. Here, a hexazirconium-based MOF [ZrFMOF, Zr6(μ3-O)8(COO)8(H2O)8(DEF)7] was synthesized and shown to act as a host framework to capture and facilitate the crystal structure determination of a series of liquid molecules. In this respect, ZrFMOF serves as robust pre-organized single crystalline coating (PSCC) on the target guest. ZrFMOF successfully encapsulated 12 toxic liquid molecules through weak interactions within two binding cavities (A and B), enabling accurate structural determination of individual guest molecules, two mixtures and an unknown liquid, all without the need of activation. Three distinct binding modes were identified, involving cavities A, B and A and B together. Furthermore, ZrFMOF showed excellent adsorption capacities on iodine, various dyes and polyfluoroalkyl substances (PFAS), which was confirmed by solid state NMR. Especially, ZrFMOF was so far the strongest absorbent on PFAS (absorption capacity 1.23 mg/mg). In summary, it is demonstrated for the first time that ZrFMOF is a versatile PSCC material that can be used to sequester and identify a range of toxic liquid molecules, and remove three kinds of pollutants (iodine, dyes and PFAS) in water.
{"title":"Encapsulation of toxic liquid molecules and adsorption of water pollutants by a versatile pre-organized single crystalline coating material","authors":"Weiping Huang, Jin chang Liu, Feng Wang, Wei Xu, Zi-Meng Tao, David Middleton, Cheng-Dong Liu, Shu-Qin Qin, Wen-Cai Ye, Ren-Wang Jiang","doi":"10.1039/d4qi02919d","DOIUrl":"https://doi.org/10.1039/d4qi02919d","url":null,"abstract":"Liquid water is essential for life, but many other substances that exist in the liquid state under standard conditions can have severe detrimental effects on living organisms and the environment. Isolation of these substances and determination of their three-dimensional structures are important to understand and, ultimately, to eliminate their harmful effects. Unfortunately, the mobility and disorder inherent in liquid molecules presents major challenges for their structure elucidation. Consequently, very few structures of liquid molecules have been determined with certainty. Here, a hexazirconium-based MOF [ZrFMOF, Zr6(μ3-O)8(COO)8(H2O)8(DEF)7] was synthesized and shown to act as a host framework to capture and facilitate the crystal structure determination of a series of liquid molecules. In this respect, ZrFMOF serves as robust pre-organized single crystalline coating (PSCC) on the target guest. ZrFMOF successfully encapsulated 12 toxic liquid molecules through weak interactions within two binding cavities (A and B), enabling accurate structural determination of individual guest molecules, two mixtures and an unknown liquid, all without the need of activation. Three distinct binding modes were identified, involving cavities A, B and A and B together. Furthermore, ZrFMOF showed excellent adsorption capacities on iodine, various dyes and polyfluoroalkyl substances (PFAS), which was confirmed by solid state NMR. Especially, ZrFMOF was so far the strongest absorbent on PFAS (absorption capacity 1.23 mg/mg). In summary, it is demonstrated for the first time that ZrFMOF is a versatile PSCC material that can be used to sequester and identify a range of toxic liquid molecules, and remove three kinds of pollutants (iodine, dyes and PFAS) in water.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"32 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539072","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}
Chang Liu, Wenjing Tian, Mao-Yin Ran, Pan Gao, Panpan Jing, Yi Liu, Hua Lin
Multi-component chalcogenidometalates have garnered significant attention due to their promising applications in solar energy conversion devices, including photodetectors, solar cells, and photocatalysts. Photocurrent response is not only a fundamental property of photodetectors but also serves as a key indicator of the solar energy conversion efficiency in potential semiconductor devices. Despite the growing interest, a clear and universal guideline for designing chalcogenide materials with excellent photocurrent response remains elusive, primarily due to the substantial variations in their chemical compositions and crystal structures. In this review, we present a comprehensive compilation of reported multi-component chalcogenidometalates, including main group chalcogenides with binary and ternary anionic frameworks, and discuss their photocurrent response performance. Additionally, we also highlight other special chalcogenide systems, focusing on their photocurrent response characteristics. For the first time, we systematically summarize the intricate relationships between chemical composition, crystal structure, electronic band structure, and photocurrent response in these materials. Finally, we believe that this review provides a valuable structural perspective on the photocurrent response of multi-component chalcogenidometalates, offering useful insights for the design and application of advanced solar energy conversion materials.
{"title":"Structural diversity and photocurrent responses of multi-component chalcogenidometalates","authors":"Chang Liu, Wenjing Tian, Mao-Yin Ran, Pan Gao, Panpan Jing, Yi Liu, Hua Lin","doi":"10.1039/d5qi00110b","DOIUrl":"https://doi.org/10.1039/d5qi00110b","url":null,"abstract":"Multi-component chalcogenidometalates have garnered significant attention due to their promising applications in solar energy conversion devices, including photodetectors, solar cells, and photocatalysts. Photocurrent response is not only a fundamental property of photodetectors but also serves as a key indicator of the solar energy conversion efficiency in potential semiconductor devices. Despite the growing interest, a clear and universal guideline for designing chalcogenide materials with excellent photocurrent response remains elusive, primarily due to the substantial variations in their chemical compositions and crystal structures. In this review, we present a comprehensive compilation of reported multi-component chalcogenidometalates, including main group chalcogenides with binary and ternary anionic frameworks, and discuss their photocurrent response performance. Additionally, we also highlight other special chalcogenide systems, focusing on their photocurrent response characteristics. For the first time, we systematically summarize the intricate relationships between chemical composition, crystal structure, electronic band structure, and photocurrent response in these materials. Finally, we believe that this review provides a valuable structural perspective on the photocurrent response of multi-component chalcogenidometalates, offering useful insights for the design and application of advanced solar energy conversion materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"32 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546084","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}
Dan Wu, Cong-Min Fan, Wusi Luo, Yingzhi Jin, Qinchuan He, Yiqun Wang
Metal organic frameworks (MOFs) have been widely studied in the field of microwave absorption due to high porosity and large specific surface area. The weak dielectric loss limits enhancement of their absorption performance. In this study, hollow alloyed CoFe-ZIF/CNFs composite fibers were successfully synthesized by electrospinning and high-temperature carbonization. The carbon fiber with dielectric loss wraps hollow alloyed CoFe-ZIF nanocage with magnetic loss to form a bamboo-shaped composite fiber to achieve magnetoelectric synergy. The construction of the hollow structure of hollow alloyed CoFe-ZIF nanocage and the combination of carbon fiber not only enriches a large number of heterogeneous interfaces, but also optimizes the impedance matching, which is beneficial to the attenuation dissipation of EMW. The results show that hollow alloyed CoFe-ZIF/CNFs composite fibers exhibit excellent electromagnetic wave absorption performance. When the filling is only 10wt%, the minimum reflection loss is -59.61 dB, and the effective absorption bandwidth reaches 6.64 GHz. This study used the combination of MOFs alloy cages and carbon fibers to regulate the absorbing properties, providing new insights into the preparation and application of 1D structural composite absorber.
{"title":"Enhanced Interfacial Polarization Loss Induced by Hollow Engineering of Hollow Alloyed CoFe-ZIF Nanocage/Carbon Nanofibers for Efficient Microwave Absorption","authors":"Dan Wu, Cong-Min Fan, Wusi Luo, Yingzhi Jin, Qinchuan He, Yiqun Wang","doi":"10.1039/d5qi00118h","DOIUrl":"https://doi.org/10.1039/d5qi00118h","url":null,"abstract":"Metal organic frameworks (MOFs) have been widely studied in the field of microwave absorption due to high porosity and large specific surface area. The weak dielectric loss limits enhancement of their absorption performance. In this study, hollow alloyed CoFe-ZIF/CNFs composite fibers were successfully synthesized by electrospinning and high-temperature carbonization. The carbon fiber with dielectric loss wraps hollow alloyed CoFe-ZIF nanocage with magnetic loss to form a bamboo-shaped composite fiber to achieve magnetoelectric synergy. The construction of the hollow structure of hollow alloyed CoFe-ZIF nanocage and the combination of carbon fiber not only enriches a large number of heterogeneous interfaces, but also optimizes the impedance matching, which is beneficial to the attenuation dissipation of EMW. The results show that hollow alloyed CoFe-ZIF/CNFs composite fibers exhibit excellent electromagnetic wave absorption performance. When the filling is only 10wt%, the minimum reflection loss is -59.61 dB, and the effective absorption bandwidth reaches 6.64 GHz. This study used the combination of MOFs alloy cages and carbon fibers to regulate the absorbing properties, providing new insights into the preparation and application of 1D structural composite absorber.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539140","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}
Yingying Wang, Tao Pan, Sicong Zhang, Qing Li, Huan Pang
Rechargeable aqueous zinc-ion batteries (AZIBs) are considered the most promising energy storage devices due to their high theoretical specific capacity, safety, and low cost. Metal–organic frameworks are emerging porous materials characterized by adjustable structures and active metal centers. This review summarizes the application of MOFs in the preparation of electrodes for AZIBs, particularly focusing on various design strategies. Moreover, we provide electrochemical performance comparisons under different strategies and propose future development challenges.
{"title":"MOF-based electrode materials for aqueous zinc-ion batteries: design strategy and future challenges","authors":"Yingying Wang, Tao Pan, Sicong Zhang, Qing Li, Huan Pang","doi":"10.1039/d5qi00159e","DOIUrl":"https://doi.org/10.1039/d5qi00159e","url":null,"abstract":"Rechargeable aqueous zinc-ion batteries (AZIBs) are considered the most promising energy storage devices due to their high theoretical specific capacity, safety, and low cost. Metal–organic frameworks are emerging porous materials characterized by adjustable structures and active metal centers. This review summarizes the application of MOFs in the preparation of electrodes for AZIBs, particularly focusing on various design strategies. Moreover, we provide electrochemical performance comparisons under different strategies and propose future development challenges.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"67 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532746","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}
QiYing Yang, Changhui Sun, Lanju Sun, Hangning Liu, Linghao Su, Chuanli Ma, Jie Wang, Liangyu Gong, Zhenhua Yan
The electrochemical synthesis of hydrogen peroxide (H₂O₂) through the two-electron oxygen reduction reaction (2e-ORR) offers a promising alternative to the traditional anthraquinone process. However, this method often suffers from sluggish kinetics. In this study, we introduce a novel bismuth-doped cerium oxide (Bi-CeO₂) composite, featuring hollow nanospheres and triangular nanoplate structures with highly dispersed Bi dopants on the CeO₂ matrix. Notably, the morphology of the Bi-CeO₂ can be dynamically tuned between spheres and plates by adjusting the amounts of Bi dopants. This innovative 1%-Bi-CeO₂ catalyst exhibits exceptional H₂O₂ selectivity at 62.3% and significantly enhanced H₂O₂ yield, reaching 1.16 mol gcat -1 h -1 at 0.1 V with a high Faraday efficiency of 56.0%. Density functional theory (DFT) calculations reveal that Bi dopants effectively lower the free energy barrier for *OOH intermediate formation, thereby accelerating H₂O₂ production. Additionally, when integrated into a dual-cathode system, the 1%-Bi-CeO₂ demonstrates superior performance in removing organic dyes such as rhodamine B (RhB). This work offers a groundbreaking approach to designing high-efficiency heteroatom-doped catalysts for 2e-ORR, paving the way for more effective electrochemical systems..
{"title":"Homogeneous Bismuth Dopants Regulate Cerium Oxide Structure to Boost Hydrogen Peroxide Electrosynthesis via Two-Electron Oxygen Reduction","authors":"QiYing Yang, Changhui Sun, Lanju Sun, Hangning Liu, Linghao Su, Chuanli Ma, Jie Wang, Liangyu Gong, Zhenhua Yan","doi":"10.1039/d5qi00075k","DOIUrl":"https://doi.org/10.1039/d5qi00075k","url":null,"abstract":"The electrochemical synthesis of hydrogen peroxide (H₂O₂) through the two-electron oxygen reduction reaction (2e-ORR) offers a promising alternative to the traditional anthraquinone process. However, this method often suffers from sluggish kinetics. In this study, we introduce a novel bismuth-doped cerium oxide (Bi-CeO₂) composite, featuring hollow nanospheres and triangular nanoplate structures with highly dispersed Bi dopants on the CeO₂ matrix. Notably, the morphology of the Bi-CeO₂ can be dynamically tuned between spheres and plates by adjusting the amounts of Bi dopants. This innovative 1%-Bi-CeO₂ catalyst exhibits exceptional H₂O₂ selectivity at 62.3% and significantly enhanced H₂O₂ yield, reaching 1.16 mol gcat -1 h -1 at 0.1 V with a high Faraday efficiency of 56.0%. Density functional theory (DFT) calculations reveal that Bi dopants effectively lower the free energy barrier for *OOH intermediate formation, thereby accelerating H₂O₂ production. Additionally, when integrated into a dual-cathode system, the 1%-Bi-CeO₂ demonstrates superior performance in removing organic dyes such as rhodamine B (RhB). This work offers a groundbreaking approach to designing high-efficiency heteroatom-doped catalysts for 2e-ORR, paving the way for more effective electrochemical systems..","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"39 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532664","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}
The design of new radical bridging ligands that can effectively promote strong magnetic coupling with Ln(III) ions needs to focus on radicals that are susceptible to synthetic modifications and bear diffuse spin density on their donor atoms. To probe this, we introduced various substituents possessing different electron-withdrawing/donating capabilities into the redox active s-tetrazinyl centre. This allowed for the systematic tuning of the redox and optoelectronic properties of the tetrazinyl ring. The effect of the substitution on the strength of the Ln-rad magnetic coupling was investigated on a series of radical-bridged Ln metallocene complexes featuring the 3,6-dimethyl-1,2,4,5-tetrazine (dmtz) and the 3,6-dimethoxy-1,2,4,5-tetrazine (dmeotz); [(Cp*2Ln)2(dmtz•-)(THF)2][BPh4]·THF (Ln = Gd (1-Gd) or Dy (1-Dy); Cp* = pentamethylcyclopentadienyl; THF = tetrahydrofuran) and [(Cp*2Ln)2(dmeotz•-)(THF)][BPh4] (Ln = Gd (2-Gd) or Dy (2-Dy)). Cyclic voltammetry, UV-Vis absorption spectroscopy, SQUID magnetometry, as well as ab initio and density functional theory (DFT) calculations are combined to underline the trends observed in this study, while comparisons to the unsubstituted 1,2,4,5-tetrazine (tz) and the 3,6-dichloro-1,2,4,5-tetrazine (dctz) are made. Notably, an intricate interplay between orbital overlap, ligand substituent effects, and changes in the coordination environment is found to collectively dictate the magnitude of JGd-rad in the investigated systems. The strong magnetic coupling combined with the highly anisotropic DyIII ions, grant 1-Dy and 2-Dy with slow magnetic relaxation in the absence of an external applied field. For 1-Dy an opening of the hysteresis loop is observed with Hc = ~5000 Oe, one of the highest coercivities for a dinuclear organic radical-bridged single-molecule magnet.
{"title":"Exploring the substitution effect on the magnetic coupling of tetrazinyl-bridged Ln2 single-molecule magnets","authors":"Niki Mavragani, Alexandros Kitos, Gayfullina Rezeda, Akseli Mansikkamäki, Jani Moilanen, Muralee Murugesu","doi":"10.1039/d4qi02796e","DOIUrl":"https://doi.org/10.1039/d4qi02796e","url":null,"abstract":"The design of new radical bridging ligands that can effectively promote strong magnetic coupling with Ln(III) ions needs to focus on radicals that are susceptible to synthetic modifications and bear diffuse spin density on their donor atoms. To probe this, we introduced various substituents possessing different electron-withdrawing/donating capabilities into the redox active s-tetrazinyl centre. This allowed for the systematic tuning of the redox and optoelectronic properties of the tetrazinyl ring. The effect of the substitution on the strength of the Ln-rad magnetic coupling was investigated on a series of radical-bridged Ln metallocene complexes featuring the 3,6-dimethyl-1,2,4,5-tetrazine (dmtz) and the 3,6-dimethoxy-1,2,4,5-tetrazine (dmeotz); [(Cp*2Ln)2(dmtz•-)(THF)2][BPh4]·THF (Ln = Gd (1-Gd) or Dy (1-Dy); Cp* = pentamethylcyclopentadienyl; THF = tetrahydrofuran) and [(Cp*2Ln)2(dmeotz•-)(THF)][BPh4] (Ln = Gd (2-Gd) or Dy (2-Dy)). Cyclic voltammetry, UV-Vis absorption spectroscopy, SQUID magnetometry, as well as ab initio and density functional theory (DFT) calculations are combined to underline the trends observed in this study, while comparisons to the unsubstituted 1,2,4,5-tetrazine (tz) and the 3,6-dichloro-1,2,4,5-tetrazine (dctz) are made. Notably, an intricate interplay between orbital overlap, ligand substituent effects, and changes in the coordination environment is found to collectively dictate the magnitude of JGd-rad in the investigated systems. The strong magnetic coupling combined with the highly anisotropic DyIII ions, grant 1-Dy and 2-Dy with slow magnetic relaxation in the absence of an external applied field. For 1-Dy an opening of the hysteresis loop is observed with Hc = ~5000 Oe, one of the highest coercivities for a dinuclear organic radical-bridged single-molecule magnet.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"52 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532665","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}
CeO2 nanocrystals can be used as an excellent catalyst in ammonium perchlorate (AP) decomposition, and exploring their catalytic performance on specific crystal facets is crucial for a deeper understanding of the reaction mechanism. Herein, CeO2 nanorods (CeO2-R) with (110) facets, octahedra (CeO2-O) with (111) facets and cubes (CeO2-C) with (100) facets were successfully synthesized, and their activity in AP decomposition showed an order of CeO2-R>CeO2-C>CeO2-O. Specifically, the THTD decreased from 428.6 ℃ to 357.8 ℃, 385.4 ℃ and 410.6 ℃ for (110), (100) and (111) facet, respectively. The XPS and EPR results confirmed a direct positive correlation between the oxygen vacancies concentration on the facets and their catalytic performance, and through detailed tracking experiments with TG-MS, the following reasonable conclusion can be drawn: oxygen vacancies can not only facilitate the adsorption of NH3 which is the main decomposition product, but also reduce the band gap of CeO2, and then promotes the deep dissociation of NH3. This work presented a clear facet-dependent activity of CeO2 in the thermal decomposition of AP and comprehensively proved the supportive role of oxygen vacancies on different facets in the reaction.
{"title":"The facet-dependent catalytic performance of CeO2 nanocatalysts in the decomposition of ammonium perchlorate","authors":"Miao Zhang, Huixiang Wang, Shoufeng Xue, Wenting Lv, RuiSheng Qin, Weiwei Pan, Baoliang Lv","doi":"10.1039/d4qi03333g","DOIUrl":"https://doi.org/10.1039/d4qi03333g","url":null,"abstract":"CeO2 nanocrystals can be used as an excellent catalyst in ammonium perchlorate (AP) decomposition, and exploring their catalytic performance on specific crystal facets is crucial for a deeper understanding of the reaction mechanism. Herein, CeO2 nanorods (CeO2-R) with (110) facets, octahedra (CeO2-O) with (111) facets and cubes (CeO2-C) with (100) facets were successfully synthesized, and their activity in AP decomposition showed an order of CeO2-R>CeO2-C>CeO2-O. Specifically, the THTD decreased from 428.6 ℃ to 357.8 ℃, 385.4 ℃ and 410.6 ℃ for (110), (100) and (111) facet, respectively. The XPS and EPR results confirmed a direct positive correlation between the oxygen vacancies concentration on the facets and their catalytic performance, and through detailed tracking experiments with TG-MS, the following reasonable conclusion can be drawn: oxygen vacancies can not only facilitate the adsorption of NH3 which is the main decomposition product, but also reduce the band gap of CeO2, and then promotes the deep dissociation of NH3. This work presented a clear facet-dependent activity of CeO2 in the thermal decomposition of AP and comprehensively proved the supportive role of oxygen vacancies on different facets in the reaction.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"5 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532719","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}
In this work, morphological control on a series of sulfur–vacancy–rich CdS photocatalysts has been achieved toward the optimization of their performances in CO2 photoreduction. Results show that the sulfur–vacancy–rich CdS nano–platelets (p–CdS–Vs) exhibits the highest CO2 photoreduction activity with a CO yield of 4058.5 μmol h–1 g–1, which is 10 and 6 times those of the sulfur–vacancy–rich CdS nanowires (w–CdS–Vs, 372.8 μmol h–1 g–1) and nanorods (r–CdS–Vs, 638.7 μmol h–1 g–1), respectively, amongst the highest numbers for CdS–based photocatalysts reported hitherto. The superior CO2 photoreduction performance of p–CdS–Vs is attributable to its high efficiency of electron transport and suppressed recombination of photogenerated charge carriers. Mechanistic study indicates a critical role of surface sulfur vacancies that provide a microenvironment to trap unpaired electrons for the separation of photogenerated carriers so that photocatalytic efficiency of CO2–to–CO reduction is largely improved in this current system.
{"title":"Morphological regulation of sulfur–vacancy–rich CdS for tunable CO2 photoreduction under visible irradiation","authors":"Lu-Wen Qiu, Wen-Ni Zhang, Lin-Ying Wang, Hao Li, Tian-Kuan Zhang, Mi-Xin Lin, Suqin Ci, Jian Lü","doi":"10.1039/d5qi00290g","DOIUrl":"https://doi.org/10.1039/d5qi00290g","url":null,"abstract":"In this work, morphological control on a series of sulfur–vacancy–rich CdS photocatalysts has been achieved toward the optimization of their performances in CO2 photoreduction. Results show that the sulfur–vacancy–rich CdS nano–platelets (p–CdS–Vs) exhibits the highest CO2 photoreduction activity with a CO yield of 4058.5 μmol h–1 g–1, which is 10 and 6 times those of the sulfur–vacancy–rich CdS nanowires (w–CdS–Vs, 372.8 μmol h–1 g–1) and nanorods (r–CdS–Vs, 638.7 μmol h–1 g–1), respectively, amongst the highest numbers for CdS–based photocatalysts reported hitherto. The superior CO2 photoreduction performance of p–CdS–Vs is attributable to its high efficiency of electron transport and suppressed recombination of photogenerated charge carriers. Mechanistic study indicates a critical role of surface sulfur vacancies that provide a microenvironment to trap unpaired electrons for the separation of photogenerated carriers so that photocatalytic efficiency of CO2–to–CO reduction is largely improved in this current system.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"84 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532666","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}
Runze Wang, Yanmei Ren, He Wen, Zhengjun Chen, Ping Wang
Tailored synthesis of earth-abundant alkaline hydrogen evolution electrocatalysts, featuring optimized metal/oxide heterointerfacial structures and rapid charge-/mass-transfer characteristics, remains a significant challenge in advancing water electrolysis as a viable technology for sustainable hydrogen production. Herein, we report the boride-mediated and carbon nanotubes (CNT)-scaffolded synthesis of a cobalt-based electrocatalyst that can effectively address the key factors influencing alkaline HER performance. Specifically, a cobalt foam (CF) supported composite catalyst (Co/CoO/CNT) was prepared via a three-step procedure: (1) combustion synthesis of CNT networks on a CF surface, (2) electroless plating of the boride precursor onto the surface of CNT-decorated CF, and (3) annealing treatment to induce solid-phase reaction between the boride and adjacent CoO. The boride-mediated synthesis allows for the formation of abundant Co/CoO heterointerfacial boundaries, which serve as active sites for alkaline HER. The pre-growth of CNT networks enables the construction of a hierarchical mesoporous–macroporous architecture, rendering improved active site accessibility and enhanced water transport and gas release in the catalyst layer. In addition, the incorporation of conductive CNTs helps improve charge-transfer kinetics. Benefiting from these favorable attributes, the Co/CoO/CNT/CF catalyst showed excellent alkaline HER performance, requiring only 17 and 185 mV overpotentials to afford current densities of 10 and 500 mA cm−2, respectively, and maintaining long-term stability at high current densities up to 1000 mA cm−2. Furthermore, the catalyst exhibited fairly good performance in alkaline natural seawater electrolysis, enabling stable hydrogen production at 500 mA cm−2 for over 100 hours.
{"title":"Boride-mediated and carbon nanotube-scaffolded synthesis of cobalt-based electrocatalyst for efficient and stable alkaline hydrogen evolution at industrial-scale current density","authors":"Runze Wang, Yanmei Ren, He Wen, Zhengjun Chen, Ping Wang","doi":"10.1039/d4qi03298e","DOIUrl":"https://doi.org/10.1039/d4qi03298e","url":null,"abstract":"Tailored synthesis of earth-abundant alkaline hydrogen evolution electrocatalysts, featuring optimized metal/oxide heterointerfacial structures and rapid charge-/mass-transfer characteristics, remains a significant challenge in advancing water electrolysis as a viable technology for sustainable hydrogen production. Herein, we report the boride-mediated and carbon nanotubes (CNT)-scaffolded synthesis of a cobalt-based electrocatalyst that can effectively address the key factors influencing alkaline HER performance. Specifically, a cobalt foam (CF) supported composite catalyst (Co/CoO/CNT) was prepared <em>via</em> a three-step procedure: (1) combustion synthesis of CNT networks on a CF surface, (2) electroless plating of the boride precursor onto the surface of CNT-decorated CF, and (3) annealing treatment to induce solid-phase reaction between the boride and adjacent CoO. The boride-mediated synthesis allows for the formation of abundant Co/CoO heterointerfacial boundaries, which serve as active sites for alkaline HER. The pre-growth of CNT networks enables the construction of a hierarchical mesoporous–macroporous architecture, rendering improved active site accessibility and enhanced water transport and gas release in the catalyst layer. In addition, the incorporation of conductive CNTs helps improve charge-transfer kinetics. Benefiting from these favorable attributes, the Co/CoO/CNT/CF catalyst showed excellent alkaline HER performance, requiring only 17 and 185 mV overpotentials to afford current densities of 10 and 500 mA cm<small><sup>−2</sup></small>, respectively, and maintaining long-term stability at high current densities up to 1000 mA cm<small><sup>−2</sup></small>. Furthermore, the catalyst exhibited fairly good performance in alkaline natural seawater electrolysis, enabling stable hydrogen production at 500 mA cm<small><sup>−2</sup></small> for over 100 hours.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"31 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518272","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}
The emergence of antibiotic-resistant Staphylococcus aureus poses a huge threat to public health. Therefore, novel strategy to overcome antibiotic resistance are urgently needed. Auranofin, a marketed metallodrug for rheumatoid arthritis, has been recognized as a promising agent against multiple clinical isolates of S. aureus. However, until now, its antibacterial mechanism is not well understood. Herein, we verify that the catabolite control protein A (CcpA) from S. aureus is an important target for auranofin. Auranofin can directly bind to CcpA via two cysteine residues. Importantly, both in vitro and animal infection models assays demonstrated that auranofin can disrupt the biological activity of CcpA, which attenuates bacteria growth, inhibits the secretion of toxin and enhance efficacy of aminoglycoside antibiotic. Together, these findings further revealed the bactericidal mechanism of auranofin against S. aureus.
{"title":"Targeting catabolite control protein A from Staphylococcus aureus by auranofin","authors":"Wenjing Lin, Jingjing Chen, Ziying Huang, Haijun Li, Yushou Chen, Xuemin Duan, Yan-Shi Xiong, Bingjie Han, Guijuan Jiang, Jintao Wang, Xiangwen Liao","doi":"10.1039/d5qi00073d","DOIUrl":"https://doi.org/10.1039/d5qi00073d","url":null,"abstract":"The emergence of antibiotic-resistant Staphylococcus aureus poses a huge threat to public health. Therefore, novel strategy to overcome antibiotic resistance are urgently needed. Auranofin, a marketed metallodrug for rheumatoid arthritis, has been recognized as a promising agent against multiple clinical isolates of S. aureus. However, until now, its antibacterial mechanism is not well understood. Herein, we verify that the catabolite control protein A (CcpA) from S. aureus is an important target for auranofin. Auranofin can directly bind to CcpA via two cysteine residues. Importantly, both in vitro and animal infection models assays demonstrated that auranofin can disrupt the biological activity of CcpA, which attenuates bacteria growth, inhibits the secretion of toxin and enhance efficacy of aminoglycoside antibiotic. Together, these findings further revealed the bactericidal mechanism of auranofin against S. aureus.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"24 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518273","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}
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