Aqueous ammonium-ion supercapacitors have attracted much attention due to their high safety, economic, and environmental advantages, but the development of high-performance electrode material for NH4+ storage has lagged behind that of other carriers. Herein, we designed an organic-inorganic hybrid material (LDH-Vo@PANI) as the cathode for efficient NH4+ storage via interface engineering and defect engineering. The polyaniline coating enhanced the structural stability of NiCo-LDHs by constructing Ni/Co-N bonds, which inhibited their dissolution during charging and discharging. The oxygen vacancies effectively buffered the electrostatic interaction between NH4+ and NiCo-LDHs, thereby increasing the diffusion rate of NH4+. Furthermore, density functional theory (DFT) calculations strongly demonstrate the positive effects of PANI coating and oxygen vacancies on the NH4+ adsorption capacity and conductive properties of the electrode material. Therefore, the LDH-Vo@PANI exhibits an area capacitance of up to 2091 mF cm-2 at 1 mA cm-2 while maintaining a high rate performance of 55.8%. The assembled supercapacitor exhibits an ultra-high energy density of 75 Wh kg-1 and a power density of 788 W kg-1 and maintains 99.48% initial capacitance retention and 100% Coulomb efficiency after 10,000 cycles. This work provides a strategy with universal applicability for the development of high-performance ammonium storage electrode material.
{"title":"Polyaniline Interface Engineering Enabled Oxygen Vacancy-enriched NiCo-LDHs for Ammonium-ion Supercapacitors","authors":"Hucheng Fu, Yanchen Chen, Yizhang Yang, Juguo Dai, Ningjun Zhou, Dongxu Li, Qiuyan Luo, Xiaohong Wang, Rong Jia, Hanzhong Ren, Qiaoyun Qin, Yiting Xu, Lizong Dai","doi":"10.1039/d5qi00083a","DOIUrl":"https://doi.org/10.1039/d5qi00083a","url":null,"abstract":"Aqueous ammonium-ion supercapacitors have attracted much attention due to their high safety, economic, and environmental advantages, but the development of high-performance electrode material for NH4+ storage has lagged behind that of other carriers. Herein, we designed an organic-inorganic hybrid material (LDH-Vo@PANI) as the cathode for efficient NH4+ storage via interface engineering and defect engineering. The polyaniline coating enhanced the structural stability of NiCo-LDHs by constructing Ni/Co-N bonds, which inhibited their dissolution during charging and discharging. The oxygen vacancies effectively buffered the electrostatic interaction between NH4+ and NiCo-LDHs, thereby increasing the diffusion rate of NH4+. Furthermore, density functional theory (DFT) calculations strongly demonstrate the positive effects of PANI coating and oxygen vacancies on the NH4+ adsorption capacity and conductive properties of the electrode material. Therefore, the LDH-Vo@PANI exhibits an area capacitance of up to 2091 mF cm-2 at 1 mA cm-2 while maintaining a high rate performance of 55.8%. The assembled supercapacitor exhibits an ultra-high energy density of 75 Wh kg-1 and a power density of 788 W kg-1 and maintains 99.48% initial capacitance retention and 100% Coulomb efficiency after 10,000 cycles. This work provides a strategy with universal applicability for the development of high-performance ammonium storage electrode material.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"49 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744737","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}
Jingbin Huang, Bin Hu, Yunlin Li, Jie Zhu, Jing Jiang, Han Zhao, Jingxian Zhou, Lin Jin, Renbing Wu
Rationally design of highly efficient and stable electrocatalysts for alkaline hydrogen evolution reaction (HER) toward anion exchange membrane water electrolyzer (AEMWE) is urgently needed but remains quite challenging. Herein, we develop core-shell-structured MoS2/CoS heterostructure (MCS-1) with optimized shell thickness (60 nm) toward this challenge. The experimental and density functional theory (DFT) calculations disclose that the introduction of CoS into MoS2 not only can promote initial H2O adsorption/dissociation process and optimize Gibbs free energy of hydrogen adsorption (ΔGH*), but also induce the fast transfer of the adsorbed hydroxyl, thus avoiding the blocking and poisoning of the active sites. Accordingly, MCS-1 exhibits remarkably enhanced HER performances with lower overpotentials of 64 and 149 mV at 10 and 100 mA cm−2. More importantly, by using MCS-1 as both the cathode and anode to assemble AEMWE device, which can achieve a current density of 200 mA cm−2 at a low voltage of 1.63 V, and stable operation over 500 h in alkaline media. This work provides a new perspective on designing highly efficient and stable alkaline HER catalysts for AEMWE.
{"title":"Unveiling enhanced mechanism of alkaline hydrogen evolution kinetics on molybdenum-cobalt sulfides for efficient anion exchange membrane water electrolyzer","authors":"Jingbin Huang, Bin Hu, Yunlin Li, Jie Zhu, Jing Jiang, Han Zhao, Jingxian Zhou, Lin Jin, Renbing Wu","doi":"10.1039/d4qi03314k","DOIUrl":"https://doi.org/10.1039/d4qi03314k","url":null,"abstract":"Rationally design of highly efficient and stable electrocatalysts for alkaline hydrogen evolution reaction (HER) toward anion exchange membrane water electrolyzer (AEMWE) is urgently needed but remains quite challenging. Herein, we develop core-shell-structured MoS2/CoS heterostructure (MCS-1) with optimized shell thickness (60 nm) toward this challenge. The experimental and density functional theory (DFT) calculations disclose that the introduction of CoS into MoS2 not only can promote initial H2O adsorption/dissociation process and optimize Gibbs free energy of hydrogen adsorption (ΔGH*), but also induce the fast transfer of the adsorbed hydroxyl, thus avoiding the blocking and poisoning of the active sites. Accordingly, MCS-1 exhibits remarkably enhanced HER performances with lower overpotentials of 64 and 149 mV at 10 and 100 mA cm−2. More importantly, by using MCS-1 as both the cathode and anode to assemble AEMWE device, which can achieve a current density of 200 mA cm−2 at a low voltage of 1.63 V, and stable operation over 500 h in alkaline media. This work provides a new perspective on designing highly efficient and stable alkaline HER catalysts for AEMWE.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"88 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744736","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}
Vinícius Acir Glitz, Daniele Cocco Durigon, Andre Luiz Amorim, Yara S. Ricken, Adailton J Bortoluzzi, Antonio Luiz Braga, Ebbe Nordlander, Giovanni Finoto Caramori, Rosely Peralta
Manganese carbonyl compounds can release CO when exposed to light, potentially becoming photochemically activated CO-releasing molecules (photoCORMs). Several studies have demonstrated the behavior in the ground state when irradiated with light. However, much remains to be discovered about the chemistry of photoCORMs with uncoordinated ligand moieties and the excited states of these compounds. This research fills that gap via the synthesis, characterization, and study of the excited states of five manganese(I) complexes containing a potentially bi- or tridentate ligand framework (κn- Se,N,Se; n=2,3). The obtained compounds, [Mn(κ2-L)(CO)3Br], retain a uncoordinated selenium-donor moiety. CO-release assays using violet light revealed the formation of a biscarbonyl intermediate. TD-DFT calculations showed that in [Mn(κ2-L)(CO)3Br], the first two excited states are involved. Generalized Kohn-Sham energy decomposition analysis indicated that the strongest metal-carbonyl interaction in the ground state (carbonyl trans to bromide) became the weakest in the excited state. DFT calculations confirmed the coordination of free selenium upon CO loss, forming [Mn(κ3-L)(CO)2Br], for which two configurational isomers (meridional and facial) may occur, with the first being more favored. The total interaction energies of the two carbonyls are similar, indicating the release of both. The Potential Energy curves indicate that the excited states involved are dissociative in nature.
{"title":"Taming a Silent Killer: Uncovering the Role of Excited States and Uncoordinated Selenium Moieties in the CO Photorelease Mechanism of Manganese(I) Carbonyl Compounds","authors":"Vinícius Acir Glitz, Daniele Cocco Durigon, Andre Luiz Amorim, Yara S. Ricken, Adailton J Bortoluzzi, Antonio Luiz Braga, Ebbe Nordlander, Giovanni Finoto Caramori, Rosely Peralta","doi":"10.1039/d5qi00162e","DOIUrl":"https://doi.org/10.1039/d5qi00162e","url":null,"abstract":"Manganese carbonyl compounds can release CO when exposed to light, potentially becoming photochemically activated CO-releasing molecules (photoCORMs). Several studies have demonstrated the behavior in the ground state when irradiated with light. However, much remains to be discovered about the chemistry of photoCORMs with uncoordinated ligand moieties and the excited states of these compounds. This research fills that gap via the synthesis, characterization, and study of the excited states of five manganese(I) complexes containing a potentially bi- or tridentate ligand framework (κ<small><sup>n</sup></small>- Se,N,Se; n=2,3). The obtained compounds, [Mn(κ<small><sup>2</sup></small>-L)(CO)<small><sub>3</sub></small>Br], retain a uncoordinated selenium-donor moiety. CO-release assays using violet light revealed the formation of a biscarbonyl intermediate. TD-DFT calculations showed that in [Mn(κ<small><sup>2</sup></small>-L)(CO)<small><sub>3</sub></small>Br], the first two excited states are involved. Generalized Kohn-Sham energy decomposition analysis indicated that the strongest metal-carbonyl interaction in the ground state (carbonyl trans to bromide) became the weakest in the excited state. DFT calculations confirmed the coordination of free selenium upon CO loss, forming [Mn(κ<small><sup>3</sup></small>-L)(CO)<small><sub>2</sub></small>Br], for which two configurational isomers (meridional and facial) may occur, with the first being more favored. The total interaction energies of the two carbonyls are similar, indicating the release of both. The Potential Energy curves indicate that the excited states involved are dissociative in nature.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"73 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758347","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}
Jianzhuang Jiang, Xu Ding, Xin Zhou, Xiao Wang, Hailong Wang
Interfacial charge transfer and active sites play the important role in the performance of heterogeneous photocatalysts. Reticular chemistry in covalent organic frameworks (COFs) ensures the construction of isomeric architectures made up of different donor and acceptor monomers for tuning the charge transfer dynamics and active sites. Herein, five D-A dual-pore COFs have been prepared from the reaction of naphthalene-2,6-diamine donor with different tetraaldehyde acceptor. The experimental results disclose that the linker engineering, by changing the heteroatoms and conjugation systems from benzooxadiazole, benzothiadiazole, benzoselenadiazole, naphthothiadiazole, to naphthoselenadiazole, tunes the electron-accepting capacity of corresponding D-A COFs. Among five samples, the naphthothiadiazole-derived COF has the optimal charge transfer and active sites, exhibiting the highest hydrogen evolution rate of ca. 35 mmol g−1 h−1 with the help of 3 wt % Pt under visible-light irradiation (˃ 420 nm). This work illustrates the linker engineering strategy with the simultaneous adjustment of interfacial charge transfer and active sites enables the enhancement of hydrogen generation effciency, inputting new vigor to develop the COF photocatalysts one the basis of the reticular synthesis toolkit.
{"title":"Linker Engineering of Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Evolution","authors":"Jianzhuang Jiang, Xu Ding, Xin Zhou, Xiao Wang, Hailong Wang","doi":"10.1039/d5qi00417a","DOIUrl":"https://doi.org/10.1039/d5qi00417a","url":null,"abstract":"Interfacial charge transfer and active sites play the important role in the performance of heterogeneous photocatalysts. Reticular chemistry in covalent organic frameworks (COFs) ensures the construction of isomeric architectures made up of different donor and acceptor monomers for tuning the charge transfer dynamics and active sites. Herein, five D-A dual-pore COFs have been prepared from the reaction of naphthalene-2,6-diamine donor with different tetraaldehyde acceptor. The experimental results disclose that the linker engineering, by changing the heteroatoms and conjugation systems from benzooxadiazole, benzothiadiazole, benzoselenadiazole, naphthothiadiazole, to naphthoselenadiazole, tunes the electron-accepting capacity of corresponding D-A COFs. Among five samples, the naphthothiadiazole-derived COF has the optimal charge transfer and active sites, exhibiting the highest hydrogen evolution rate of ca. 35 mmol g−1 h−1 with the help of 3 wt % Pt under visible-light irradiation (˃ 420 nm). This work illustrates the linker engineering strategy with the simultaneous adjustment of interfacial charge transfer and active sites enables the enhancement of hydrogen generation effciency, inputting new vigor to develop the COF photocatalysts one the basis of the reticular synthesis toolkit.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744735","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}
Yi-Yin Yang, Lin He, Peng-Fei Xie, Peng Dong, Hao Quan, Tao Li, Lingzhe Fang, Dong Feng, Yubo Xing, Jin-Cheng Li
The great interest of rechargeable Zn-air batteries (ZABs) ignites extensive research on efficient and robust electrocatalysts for oxygen reduction/evolution reactions (ORR/OER). Herein, a novel ORR/OER bifunctional catalyst is developed using carbon-nanotube wall nanoengineering. Thereinto, FeNi nanoparticles insert the wall by carbothermic reaction for the sake of boosting the OER, while isolated Fe atoms in iron-phthalocyanine anchored on the wall by π-π coupling interaction are used to catalyze the ORR. Accordingly, the resulting electrocatalyst exhibits outstanding ORR and OER activities such as a small potential difference of 0.67 V. In situ Raman spectroscopy measurements verify the presence of reconstruction transformation from alloying phase to high-activity spinel counterpart during the OER process. When used in ZABs, large peak power densities of 208.5 mW cm–2 under liquid-state electrolyte and 150.1 mW cm–2 in solid-state electrolyte are demonstrated. Furthermore, outstanding battery durability is illustrated by the small and stable charge-discharge voltage gap of 0.78 V at 10 mA cm–2 after 1400 cycling. This study offers a novel method to fabricate bifunctional ORR/OER electrocatalysts and possibly extends to multi-site catalysts.
{"title":"A Carbon-Nanotube Wall Nanoengineering Strategy to Stabilize FeNi Nanoparticles and Fe Single Atoms for Rechargeable Zn-Air Batteries","authors":"Yi-Yin Yang, Lin He, Peng-Fei Xie, Peng Dong, Hao Quan, Tao Li, Lingzhe Fang, Dong Feng, Yubo Xing, Jin-Cheng Li","doi":"10.1039/d4qi03361b","DOIUrl":"https://doi.org/10.1039/d4qi03361b","url":null,"abstract":"The great interest of rechargeable Zn-air batteries (ZABs) ignites extensive research on efficient and robust electrocatalysts for oxygen reduction/evolution reactions (ORR/OER). Herein, a novel ORR/OER bifunctional catalyst is developed using carbon-nanotube wall nanoengineering. Thereinto, FeNi nanoparticles insert the wall by carbothermic reaction for the sake of boosting the OER, while isolated Fe atoms in iron-phthalocyanine anchored on the wall by π-π coupling interaction are used to catalyze the ORR. Accordingly, the resulting electrocatalyst exhibits outstanding ORR and OER activities such as a small potential difference of 0.67 V. In situ Raman spectroscopy measurements verify the presence of reconstruction transformation from alloying phase to high-activity spinel counterpart during the OER process. When used in ZABs, large peak power densities of 208.5 mW cm–2 under liquid-state electrolyte and 150.1 mW cm–2 in solid-state electrolyte are demonstrated. Furthermore, outstanding battery durability is illustrated by the small and stable charge-discharge voltage gap of 0.78 V at 10 mA cm–2 after 1400 cycling. This study offers a novel method to fabricate bifunctional ORR/OER electrocatalysts and possibly extends to multi-site catalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"183 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744733","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}
Mei-Ling Ren, Ze-Jiang Xu, Hua-Kai Li, Zi-Ao Qiu, Liang-Han Shen, Xiang Zhang, Chao Shi, Na Wang, Heng-Yun Ye, Le-Ping Miao
Three-dimensional (3D) hybrid metal-halogen perovskite multiferroic materials have great advantages in the application of ferroic-photoelectric devices because of their excellent physical properties, including ferroelectricity, ferroelasticity, large piezoelectric response, and high carrier mobility. At present, relatively few types of 3D hybrid metal-halogen perovskite multiferroic materials are known. This is mainly because their organic structure must conform to the Goldschmidt tolerance factor when constructing such materials. Moreover, their performance potential is limited by their lower Curie temperature (Tc). Here, we have successfully designed a novel 3D hybrid double perovskite (R-3P)2KBiCl6 (R-3P = (R)-3-hydroxypyrrolidinium, R3PBKC) by the synthesis strategy of generating K–O coordination bonds by H/OH substitution and introducing homochirality. It is noteworthy that R3PBKC has an abnormal high Tc (376 K) structural phase transition of P1–P1–P21–P6322, and the ferroelectric-ferroelastic multiferroicity of R3PBKC is verified by typical polarization electric field (P–E) hysteresis loops and the temperature-dependent evolution of ferroelastic domains. This study presents a simple and efficient molecular strategy to realize the construction of 3D hybrid perovskite ferroelectrics, which opens up a new research path for the design and development of 3D multiferroic materials.
{"title":"H/OH substitution constructing K–O coordinated bond and introducing homochirality for the design of a 3D hybrid double perovskite multiferroic","authors":"Mei-Ling Ren, Ze-Jiang Xu, Hua-Kai Li, Zi-Ao Qiu, Liang-Han Shen, Xiang Zhang, Chao Shi, Na Wang, Heng-Yun Ye, Le-Ping Miao","doi":"10.1039/d5qi00399g","DOIUrl":"https://doi.org/10.1039/d5qi00399g","url":null,"abstract":"Three-dimensional (3D) hybrid metal-halogen perovskite multiferroic materials have great advantages in the application of ferroic-photoelectric devices because of their excellent physical properties, including ferroelectricity, ferroelasticity, large piezoelectric response, and high carrier mobility. At present, relatively few types of 3D hybrid metal-halogen perovskite multiferroic materials are known. This is mainly because their organic structure must conform to the Goldschmidt tolerance factor when constructing such materials. Moreover, their performance potential is limited by their lower Curie temperature (Tc). Here, we have successfully designed a novel 3D hybrid double perovskite (R-3P)2KBiCl6 (R-3P = (R)-3-hydroxypyrrolidinium, R3PBKC) by the synthesis strategy of generating K–O coordination bonds by H/OH substitution and introducing homochirality. It is noteworthy that R3PBKC has an abnormal high Tc (376 K) structural phase transition of P1–P1–P21–P6322, and the ferroelectric-ferroelastic multiferroicity of R3PBKC is verified by typical polarization electric field (P–E) hysteresis loops and the temperature-dependent evolution of ferroelastic domains. This study presents a simple and efficient molecular strategy to realize the construction of 3D hybrid perovskite ferroelectrics, which opens up a new research path for the design and development of 3D multiferroic materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"76 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744739","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}
Xin-Tong Lv, Xiao-Dong Liu, Zhiping Zhou, Deng-Ke Cao
Two iridium complexes, namely [Ir(ppy)2(mbpymbh)]PF6 (1) and [Ir(dfppy)2(mbpymbh)]PF6 (2), exhibit unexpected photoreactivity, although the incorporated ligands ppyH, dfppyH and mbpymbh have no inherent photochemical activity. The molecular aggregates of 1 and 2, formed in a CH3CN–H2O (v/v = 1/9) mixed solvent, show photo-induced luminescence switching, with the emission-color change from red to orange for 1, while a transition from the off state to on state with an emission band at 566 nm for 2. These changes in luminescence are assigned to photo-induced oxidative cyclization of the acylhydrazone units in 1 and 2, thus generating photoproducts 1-O and 2-O. Complexes 1-O and 2-O were isolated and identified from their crystal structures. We discussed both the effect factors and the reaction mechanism of the photo-oxidation reactions for complexes 1 and 2, as well as the luminescence properties of complexes 1, 2, 1-O and 2-O. The discovery of photo-induced oxidative cyclization in this work not only provides a new class of photo-responsive luminescent materials, but also offers a novel synthesis method for 1,3,4-oxadiazole-based Ir(III) complexes.
{"title":"Unexpected photo-induced oxidative cyclization and luminescence switching in molecular aggregates of two acylhydrazone-based Ir(III) complexes","authors":"Xin-Tong Lv, Xiao-Dong Liu, Zhiping Zhou, Deng-Ke Cao","doi":"10.1039/d5qi00527b","DOIUrl":"https://doi.org/10.1039/d5qi00527b","url":null,"abstract":"Two iridium complexes, namely [Ir(ppy)<small><sub>2</sub></small>(mbpymbh)]PF<small><sub>6</sub></small> (<strong>1</strong>) and [Ir(dfppy)<small><sub>2</sub></small>(mbpymbh)]PF<small><sub>6</sub></small> (<strong>2</strong>), exhibit unexpected photoreactivity, although the incorporated ligands ppyH, dfppyH and mbpymbh have no inherent photochemical activity. The molecular aggregates of <strong>1</strong> and <strong>2</strong>, formed in a CH<small><sub>3</sub></small>CN–H<small><sub>2</sub></small>O (v/v = 1/9) mixed solvent, show photo-induced luminescence switching, with the emission-color change from red to orange for <strong>1</strong>, while a transition from the off state to on state with an emission band at 566 nm for <strong>2</strong>. These changes in luminescence are assigned to photo-induced oxidative cyclization of the acylhydrazone units in <strong>1</strong> and <strong>2</strong>, thus generating photoproducts <strong>1-O</strong> and <strong>2-O</strong>. Complexes <strong>1-O</strong> and <strong>2-O</strong> were isolated and identified from their crystal structures. We discussed both the effect factors and the reaction mechanism of the photo-oxidation reactions for complexes <strong>1</strong> and <strong>2</strong>, as well as the luminescence properties of complexes <strong>1</strong>, <strong>2</strong>, <strong>1-O</strong> and <strong>2-O</strong>. The discovery of photo-induced oxidative cyclization in this work not only provides a new class of photo-responsive luminescent materials, but also offers a novel synthesis method for 1,3,4-oxadiazole-based Ir(<small>III</small>) complexes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736779","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 key to developing aqueous zinc ion batteries (AZIBs) is to design advanced cathodes that match well with zinc anode. Metal-organic framework (MOF)-based materials have emerged as a research focus due to their unique benefits in energy storage. However, researchers lack clear guidance on MOFs and their derived materials as AZIBs electrode materials, as well as a systematic exploration of their Zn2+ storage mechanisms. Herein, we summarize recent research progress in pristine MOFs and derivatives for high-performance AZIBs. Moreover, we provide a detailed understanding of the energy storage mechanisms. Finally, we propose the challenges and perspectives about MOFs and derivatives for next-generation aqueous energy devices. This review promotes insights into innovations in MOF-based cathode materials and provides inspiration for future efficient energy storage and conversion technologies.
{"title":"Toward high durable aqueous zinc ion batteries: A review of MOFs/MOF derived cathode materials","authors":"Yi Liu, Xiang Wu, Yoshio Bando","doi":"10.1039/d5qi00555h","DOIUrl":"https://doi.org/10.1039/d5qi00555h","url":null,"abstract":"The key to developing aqueous zinc ion batteries (AZIBs) is to design advanced cathodes that match well with zinc anode. Metal-organic framework (MOF)-based materials have emerged as a research focus due to their unique benefits in energy storage. However, researchers lack clear guidance on MOFs and their derived materials as AZIBs electrode materials, as well as a systematic exploration of their Zn2+ storage mechanisms. Herein, we summarize recent research progress in pristine MOFs and derivatives for high-performance AZIBs. Moreover, we provide a detailed understanding of the energy storage mechanisms. Finally, we propose the challenges and perspectives about MOFs and derivatives for next-generation aqueous energy devices. This review promotes insights into innovations in MOF-based cathode materials and provides inspiration for future efficient energy storage and conversion technologies.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"103 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744738","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}
Muhammad Nafees, Fei He, Lili Feng, Muhammad Hanif, piaoping yang
Metal-based complexes continue to be an exciting avenue in the quest for novel therapeutic approaches to treat malignant tumours. This is due to their versatile coordination chemistry, tunable redox activity, and distinct mechanisms of action. Cancer cells proliferate by adopting various metabolic pathways to fulfil their bioenergetic and biosynthetic demands. These altered metabolic pathways also contribute to substantial resistance to clinically approved drugs such as cisplatin. Therefore, designing therapeutic agents targeting specific metabolic pathways in tumours is a promising approach and has been widely explored in recent years. In this perspective, we provide a detailed mechanistic overview of the state-of-the-art progress of metal-based compounds that target cancer bioenergetics and various metabolic pathways to inhibit cancer progression. We also provide a comprehensive analysis of the most relevant metal complexes that concurrently target metabolic pathways and stimulate immunological response, thereby eliciting a synergistic effect that enhances treatment efficacy and overcomes drug resistance issues. Gaining insights into the structural features of these metal-based compounds will open a new therapeutic window to treat nasty tumours.
{"title":"Harnessing Metal Complexes to Target Tumour Bioenergetics and Metabolic Vulnerabilities","authors":"Muhammad Nafees, Fei He, Lili Feng, Muhammad Hanif, piaoping yang","doi":"10.1039/d5qi00168d","DOIUrl":"https://doi.org/10.1039/d5qi00168d","url":null,"abstract":"Metal-based complexes continue to be an exciting avenue in the quest for novel therapeutic approaches to treat malignant tumours. This is due to their versatile coordination chemistry, tunable redox activity, and distinct mechanisms of action. Cancer cells proliferate by adopting various metabolic pathways to fulfil their bioenergetic and biosynthetic demands. These altered metabolic pathways also contribute to substantial resistance to clinically approved drugs such as cisplatin. Therefore, designing therapeutic agents targeting specific metabolic pathways in tumours is a promising approach and has been widely explored in recent years. In this perspective, we provide a detailed mechanistic overview of the state-of-the-art progress of metal-based compounds that target cancer bioenergetics and various metabolic pathways to inhibit cancer progression. We also provide a comprehensive analysis of the most relevant metal complexes that concurrently target metabolic pathways and stimulate immunological response, thereby eliciting a synergistic effect that enhances treatment efficacy and overcomes drug resistance issues. Gaining insights into the structural features of these metal-based compounds will open a new therapeutic window to treat nasty tumours.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"101 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734148","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}
Mishel Markovski, Abdallah Amedlous, Eddy Dib, Anna Kaleta, Francesco Dalena, Davide Salusso, Mathias Barreau, Diogenes Honorato Piva, Marco Giuseppe Geloso, Aymeric Magisson, Svetlana Mintova
This study investigates the impact of selenium in different oxidation states, specifically Se6+ and Se4+, on the structural features of MFI-type zeolites. Se4+ is characterized by trigonal pyramidal coordination, forming a [Se4+O3E]2− entity (E being an active lone pair of electrons). The three-coordinated [Se4+O3E]2− entity represents an “empty-corner tetrahedron”, analogous to four-coordinated [Se6+O4]2− and [SiO4]4− tetrahedra. Aiming to understand the impact of lone pair bearing complexes on MFI, Se4+ and Se6+ were introduced through a one-pot synthesis approach giving rise to Se(IV)-MFI and Se(VI)-MFI samples. Both the Se(IV)-MFI and Se(VI)-MFI samples exhibit monoclinic symmetry at room temperature, transitioning into orthorhombic symmetry at temperatures above 100 °C and reverting to monoclinic symmetry upon cooling. A significant difference was observed in terms of the silanol content, i.e. Se(IV)-MFI shows a lower concentration of SiOH compared to Se(VI)-MFI. These observations are coherently supported by 29Si and 77Se NMR, Se K-edge XAS, FT-IR, and Raman spectroscopy, suggesting that Se4+ oxycomplexes with a lone pair of electrons are more favorable for incorporation into the MFI framework compared to Se6+. 77Se NMR analyses revealed similar Se tetrahedral coordination in both Se(VI)-MFI and Se(IV)-MFI, indicating the stabilizing role i.e. oxidation of Se4+ to Se6+ directly during crystallization of MFI. Considering the differences in the silanol content and the similarities in Se coordination states in Se(IV)-MFI and Se(VI)-MFI, the transformation of “empty-corner tetrahedra” into regular tetrahedra i.e. selenite to selenate favors the introduction of Se in the MFI framework. These results provide valuable insights into the tunability of zeolite frameworks using selenium in different oxidation states.
{"title":"The impact of “empty-corner” tetrahedra in the synthesis of MFI type zeolites: unveiling selenium stereoactivity","authors":"Mishel Markovski, Abdallah Amedlous, Eddy Dib, Anna Kaleta, Francesco Dalena, Davide Salusso, Mathias Barreau, Diogenes Honorato Piva, Marco Giuseppe Geloso, Aymeric Magisson, Svetlana Mintova","doi":"10.1039/d5qi00567a","DOIUrl":"https://doi.org/10.1039/d5qi00567a","url":null,"abstract":"This study investigates the impact of selenium in different oxidation states, specifically Se<small><sup>6+</sup></small> and Se<small><sup>4+</sup></small>, on the structural features of MFI-type zeolites. Se<small><sup>4+</sup></small> is characterized by trigonal pyramidal coordination, forming a [Se<small><sup>4+</sup></small>O<small><sub>3</sub></small>E]<small><sup>2−</sup></small> entity (E being an active lone pair of electrons). The three-coordinated [Se<small><sup>4+</sup></small>O<small><sub>3</sub></small>E]<small><sup>2−</sup></small> entity represents an “empty-corner tetrahedron”, analogous to four-coordinated [Se<small><sup>6+</sup></small>O<small><sub>4</sub></small>]<small><sup>2−</sup></small> and [SiO<small><sub>4</sub></small>]<small><sup>4−</sup></small> tetrahedra. Aiming to understand the impact of lone pair bearing complexes on MFI, Se<small><sup>4+</sup></small> and Se<small><sup>6+</sup></small> were introduced through a one-pot synthesis approach giving rise to Se(<small>IV</small>)-MFI and Se(<small>VI</small>)-MFI samples. Both the Se(<small>IV</small>)-MFI and Se(<small>VI</small>)-MFI samples exhibit monoclinic symmetry at room temperature, transitioning into orthorhombic symmetry at temperatures above 100 °C and reverting to monoclinic symmetry upon cooling. A significant difference was observed in terms of the silanol content, <em>i.e.</em> Se(<small>IV</small>)-MFI shows a lower concentration of SiOH compared to Se(<small>VI</small>)-MFI. These observations are coherently supported by <small><sup>29</sup></small>Si and <small><sup>77</sup></small>Se NMR, Se K-edge XAS, FT-IR, and Raman spectroscopy, suggesting that Se<small><sup>4+</sup></small> oxycomplexes with a lone pair of electrons are more favorable for incorporation into the MFI framework compared to Se<small><sup>6+</sup></small>. <small><sup>77</sup></small>Se NMR analyses revealed similar Se tetrahedral coordination in both Se(<small>VI</small>)-MFI and Se(<small>IV</small>)-MFI, indicating the stabilizing role <em>i.e.</em> oxidation of Se<small><sup>4+</sup></small> to Se<small><sup>6+</sup></small> directly during crystallization of MFI. Considering the differences in the silanol content and the similarities in Se coordination states in Se(<small>IV</small>)-MFI and Se(<small>VI</small>)-MFI, the transformation of “empty-corner tetrahedra” into regular tetrahedra <em>i.e.</em> selenite to selenate favors the introduction of Se in the MFI framework. These results provide valuable insights into the tunability of zeolite frameworks using selenium in different oxidation states.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"183 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723246","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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