Yuanhui Zheng, Haijiang Qiu, Song Yang, Min Li, Haixin Chen, Yongqi Zhang, Xin Chen
Recent progress in the field of carbon dots (CDs) has highlighted their significant potential, attributed to their exceptional optical properties and diverse applications, most notably in the realm of white light-emitting diodes (WLEDs). CDs are recognized for their broad spectrum of emission, adjustable fluorescence, and excellent thermal stability, making them ideal candidates for use in WLEDs. However, the challenge lies in synthesizing CDs that can emit long-wavelength, multicolor light from a single host material. This research presents a highly efficient dual-core-shell structured white-emitting phosphor, denoted as ZnS:Mn-CDs@SiO2, which has achieved an impressive photoluminescence quantum yield (PLQY) of 25.8% and an expansive full width at half maximum (FWHM) of 131 nm. The successful implementation of this novel material has led to the creation of WLEDs with Commission Internationale de l'Eclairage (CIE) coordinates at (0.32, 0.38) and a correlated color temperature (CCT) of 5856 K, marking a significant stride in the development of high-performance WLEDs.
{"title":"Enhancing White Light-Emitting Diode Performance with Ultra-Wide Spectrum ZnS:Mn-CDs@SiO2 Dual Core@Shell Composite","authors":"Yuanhui Zheng, Haijiang Qiu, Song Yang, Min Li, Haixin Chen, Yongqi Zhang, Xin Chen","doi":"10.1039/d4qi01099j","DOIUrl":"https://doi.org/10.1039/d4qi01099j","url":null,"abstract":"Recent progress in the field of carbon dots (CDs) has highlighted their significant potential, attributed to their exceptional optical properties and diverse applications, most notably in the realm of white light-emitting diodes (WLEDs). CDs are recognized for their broad spectrum of emission, adjustable fluorescence, and excellent thermal stability, making them ideal candidates for use in WLEDs. However, the challenge lies in synthesizing CDs that can emit long-wavelength, multicolor light from a single host material. This research presents a highly efficient dual-core-shell structured white-emitting phosphor, denoted as ZnS:Mn-CDs@SiO2, which has achieved an impressive photoluminescence quantum yield (PLQY) of 25.8% and an expansive full width at half maximum (FWHM) of 131 nm. The successful implementation of this novel material has led to the creation of WLEDs with Commission Internationale de l'Eclairage (CIE) coordinates at (0.32, 0.38) and a correlated color temperature (CCT) of 5856 K, marking a significant stride in the development of high-performance WLEDs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"7 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142713124","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}
Zero-dimensional (0-D) heterometallic halides containing multiple metal-halogen units are emerging optoelectronic materials with diverse photophysical properties. In this work, eight 0-D ionic compounds, including heterometallic halides [(Tp)3CuX]MX6 (Tp = protonated thiomorpholine; X = Cl, Br; M = Sb, Bi), monometallic halides (Tp)3MX6 (M = Bi when X = Cl; M = Bi, Sb when X = Br), and (Tp)Br have been synthesized. Their structures and photoluminescence have been comparatively studied. Inserting a CuX unit into the three (Tp)+ cation moieties of (Tp)3MX6 results in the formation of [(Tp)3CuX]MX6 with a complex cation of [(Tp)3CuX]3+. The assembly of two distinct metal-halogen units in the heterometallic halide enables charge transfer between the complex cation and anion unit, as verified by DFT calculations, and meanwhile achieves the wide modulation of the luminescent color (green to red region) resulting from the integration of both complex cationic and anionic emission centers in one single lattice of [(Tp)3CuBr]MBr6. The luminescence mechanisms of monometallic and heterometallic halides are elucidated by detailed structural and spectral comparisons. Moreover, the compound [(Tp)3CuBr]SbBr6 shows significant potential for low-temperature optical temperature sensing applications based on the fluorescence intensity ratio of its dual emissions, with absolute sensitivity (Sa) and relative sensitivity (Sr) values of 0.078 K-1 and 5.38% K-1, respectively. This study not only provides a new strategy for developing heterometallic halide photoluminescence materials, but also offers new ideas for a better understanding of the photophysical mechanism of 0-D heterometallic halides.
{"title":"Integrating Multiple Emission Centers for Photoluminescence Regulation in Copper-Antimony/Bismuth Halides","authors":"Abdusalam Ablez, HaoWei Lin, Sheng-Mao Zhang, Guo-Yang Chen, Jia-Hua Luo, Kezhao Du, Zeping Wang, Xiao-Ying Huang","doi":"10.1039/d4qi02614d","DOIUrl":"https://doi.org/10.1039/d4qi02614d","url":null,"abstract":"Zero-dimensional (0-D) heterometallic halides containing multiple metal-halogen units are emerging optoelectronic materials with diverse photophysical properties. In this work, eight 0-D ionic compounds, including heterometallic halides [(Tp)3CuX]MX6 (Tp = protonated thiomorpholine; X = Cl, Br; M = Sb, Bi), monometallic halides (Tp)3MX6 (M = Bi when X = Cl; M = Bi, Sb when X = Br), and (Tp)Br have been synthesized. Their structures and photoluminescence have been comparatively studied. Inserting a CuX unit into the three (Tp)+ cation moieties of (Tp)3MX6 results in the formation of [(Tp)3CuX]MX6 with a complex cation of [(Tp)3CuX]3+. The assembly of two distinct metal-halogen units in the heterometallic halide enables charge transfer between the complex cation and anion unit, as verified by DFT calculations, and meanwhile achieves the wide modulation of the luminescent color (green to red region) resulting from the integration of both complex cationic and anionic emission centers in one single lattice of [(Tp)3CuBr]MBr6. The luminescence mechanisms of monometallic and heterometallic halides are elucidated by detailed structural and spectral comparisons. Moreover, the compound [(Tp)3CuBr]SbBr6 shows significant potential for low-temperature optical temperature sensing applications based on the fluorescence intensity ratio of its dual emissions, with absolute sensitivity (Sa) and relative sensitivity (Sr) values of 0.078 K-1 and 5.38% K-1, respectively. This study not only provides a new strategy for developing heterometallic halide photoluminescence materials, but also offers new ideas for a better understanding of the photophysical mechanism of 0-D heterometallic halides.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"17 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142713123","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}
Hongbo Zhou, Xuan Hao, Jiexin Guan, Yilin Deng, Zi Wei, Yashu Liu, Guoxing Zhu
Correction for ‘Coordination tuning of Ni/Fe complex-based electrocatalysts for enhanced oxygen evolution’ by Hongbo Zhou et al., Inorg. Chem. Front., 2024, 11, 8110–8122, https://doi.org/10.1039/D4QI01934B.
对 Hongbo Zhou 等人的 "Coordination tuning of Ni/Fe complex-based electrocatalysts for enhanced oxygen evolution "的更正，Inorg.Chem.Front., 2024, 11, 8110-8122, https://doi.org/10.1039/D4QI01934B。
{"title":"Correction: Coordination tuning of Ni/Fe complex-based electrocatalysts for enhanced oxygen evolution","authors":"Hongbo Zhou, Xuan Hao, Jiexin Guan, Yilin Deng, Zi Wei, Yashu Liu, Guoxing Zhu","doi":"10.1039/d4qi90086c","DOIUrl":"https://doi.org/10.1039/d4qi90086c","url":null,"abstract":"Correction for ‘Coordination tuning of Ni/Fe complex-based electrocatalysts for enhanced oxygen evolution’ by Hongbo Zhou <em>et al.</em>, <em>Inorg. Chem. Front.</em>, 2024, <strong>11</strong>, 8110–8122, https://doi.org/10.1039/D4QI01934B.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142696656","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}
Transition metal dichalcogenides (TMDCs)/metal oxide are increasing recognized as competitive sensing materials to detect at room temperature (RT). However, the unsatisfactory properties causing by low sensitivity, slow response, and weak discriminating ability towards interfering gases preclude their further applications in advanced sensing platforms. Herein, a Bi2S3/CuO heterostructure was demonstrated for H2S detection with highly sensitive and rapidly responding at RT. The Bi2S3/CuO sensor exhibited a greatly improved response (31.2 to 1 ppm H2S) with impressive response kinetics (7.5 s), surpassing that of pure Bi2S3 by a factor of 5 and 17, respectively. Besides, the sensor exhibits outstanding selectivity, repeatability, low detection limit (25 ppb), humidity tolerance and long-term stability. The distinctive enhancement of sensing capabilities primarily results from the synergistic influence of the heterostructure configuration and increased surface-adsorbed oxygen. The strategy of constructing heterostructures between a metal oxide and TMDC offers fundamental insights to develop room-temperature sensors.
{"title":"Rapid room-temperature H2S detection based on Bi2S3/CuO heterostructures: the synergy of increased surface-adsorbed oxygen and heterojunction effect","authors":"Chengcheng Hu, Meiling Yu, Zhenze Zhou, Chenda Wei, You Wang, Juanyuan Hao","doi":"10.1039/d4qi01542h","DOIUrl":"https://doi.org/10.1039/d4qi01542h","url":null,"abstract":"Transition metal dichalcogenides (TMDCs)/metal oxide are increasing recognized as competitive sensing materials to detect at room temperature (RT). However, the unsatisfactory properties causing by low sensitivity, slow response, and weak discriminating ability towards interfering gases preclude their further applications in advanced sensing platforms. Herein, a Bi2S3/CuO heterostructure was demonstrated for H2S detection with highly sensitive and rapidly responding at RT. The Bi2S3/CuO sensor exhibited a greatly improved response (31.2 to 1 ppm H2S) with impressive response kinetics (7.5 s), surpassing that of pure Bi2S3 by a factor of 5 and 17, respectively. Besides, the sensor exhibits outstanding selectivity, repeatability, low detection limit (25 ppb), humidity tolerance and long-term stability. The distinctive enhancement of sensing capabilities primarily results from the synergistic influence of the heterostructure configuration and increased surface-adsorbed oxygen. The strategy of constructing heterostructures between a metal oxide and TMDC offers fundamental insights to develop room-temperature sensors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"64 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142696658","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}
Pietro Mariani, xiao sun, Simone Mascotto, Luisa Raimondo, Adele Sassella, Damiano Monticelli, Enrico Berretti, Alessandro Lavacchi, Matus Stredansky, Cinzia Cepek, Silvia Mostoni, Carlo Santoro, Barbara Di Credico, Roberto Scotti, Massimiliano D'Arienzo
The surface transformation and defects evolution of Cu-doped SrTiO3 upon copper exsolution by exploiting a multi-technique approach which integrates, for the first time, common methods describing exsolution like XAS, XPS and STEM with unconventional strategies, namely electron paramagnetic resonance (EPR) and UV-Vis diffuse reflectance (UV-DRS). XAS and EPR indicated that copper occurs in the matrix in a disordered coordination environment as amorphous Cu2O and CuO located at the surface and as substitutional Cu2+ lattice species with distorted octahedral structure. Interestingly, EPR unveiled that, during exsolution, Cu2+ surface sites with disordered coordination primarily migrate undergoing selective reduction, while a delay is observed for the lattice defects. UV-DRS resulted a valid alternative to HRTEM to determine the size of exsolved nanoparticles by tracking the plasmon resonance effect. Moreover, when XANES showed the complete regain of the pristine state of Cu after reoxidation, both UV-DRS and EPR highlighted that the original features are not entirely restored. These outcomes suggest that the chemical environment of exsolvable species is much more heterogeneous and the exsolution process much less straightforward than expected. Thus, alternative and original characterization techniques should be exploited to provide a solid methodological benchmark for an effective evaluation of this phenomenon.
{"title":"Critical assessment of exsolution process in Cu-doped SrTiO3 by a combined spectroscopic approach.","authors":"Pietro Mariani, xiao sun, Simone Mascotto, Luisa Raimondo, Adele Sassella, Damiano Monticelli, Enrico Berretti, Alessandro Lavacchi, Matus Stredansky, Cinzia Cepek, Silvia Mostoni, Carlo Santoro, Barbara Di Credico, Roberto Scotti, Massimiliano D'Arienzo","doi":"10.1039/d4qi02391a","DOIUrl":"https://doi.org/10.1039/d4qi02391a","url":null,"abstract":"The surface transformation and defects evolution of Cu-doped SrTiO3 upon copper exsolution by exploiting a multi-technique approach which integrates, for the first time, common methods describing exsolution like XAS, XPS and STEM with unconventional strategies, namely electron paramagnetic resonance (EPR) and UV-Vis diffuse reflectance (UV-DRS). XAS and EPR indicated that copper occurs in the matrix in a disordered coordination environment as amorphous Cu2O and CuO located at the surface and as substitutional Cu2+ lattice species with distorted octahedral structure. Interestingly, EPR unveiled that, during exsolution, Cu2+ surface sites with disordered coordination primarily migrate undergoing selective reduction, while a delay is observed for the lattice defects. UV-DRS resulted a valid alternative to HRTEM to determine the size of exsolved nanoparticles by tracking the plasmon resonance effect. Moreover, when XANES showed the complete regain of the pristine state of Cu after reoxidation, both UV-DRS and EPR highlighted that the original features are not entirely restored. These outcomes suggest that the chemical environment of exsolvable species is much more heterogeneous and the exsolution process much less straightforward than expected. Thus, alternative and original characterization techniques should be exploited to provide a solid methodological benchmark for an effective evaluation of this phenomenon.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142684775","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}
Tian-Zhu Ma, Liu-Yi Liu, You-Liang Zeng, Ke Ding, Wenting Liu, Xushen Xiong, Zong-Wan Mao
G-quadruplexes (G4s), as a special nucleic acid secondary structure, is a promising therapeutic target for enhancing immune response. We designed a bifunctional (two Pt-Cl bond) PyPDSplatin complex (BiPP) by coupling PyPDS with cisplatin.Due to the retention of two chlorine atoms, BiPP can covalently bind to two sites on G4s, thereby enhancing binding stability. BiPP retains the classical cisplatin structure, which helps to maintain it in a neutral or weakly charged state, facilitating the passage of dichloroplatin complexes across the cell membrane. BiPP not only significantly bolstered the antitumor efficacy of chemotherapy but also induced the damage to G4s, facilitating their efflux from the nucleus and thereby activating the synergistic interplay between the absent in melanoma 2-apoptosis-associated speck-like protein containing a CARD (AIM2-ASC) and cyclic GMP-AMP synthase-stimulator of the interferon gene (cGAS-STING) pathways. Moreover, BiPP initiated a molecular cascade that triggers pyroptosis by down-regulating baculoviral IAP repeat containing 7 (BIRC7) gene expression. During this process, caspase-3 is activated to cleave gasdermin E (GSDME), releasing its N-terminal domain(GSDNE-N), which subsequently instigates pyroptosis. This interaction culminates in the formation of a highly integrated antitumor immune network in conjunction with the BIRC7-caspase-3-GSDME system. Our findings not only unveil the pivotal role played by the G4s in the context of antitumor immunity, but also open an avenue for the application of G4-guided chemotherapy agents in immunotherapy.
{"title":"G-quadruplex-guided bifunctional platinum complex induce multiple pyroptosis pathways for antitumor therapy","authors":"Tian-Zhu Ma, Liu-Yi Liu, You-Liang Zeng, Ke Ding, Wenting Liu, Xushen Xiong, Zong-Wan Mao","doi":"10.1039/d4qi02098g","DOIUrl":"https://doi.org/10.1039/d4qi02098g","url":null,"abstract":"G-quadruplexes (G4s), as a special nucleic acid secondary structure, is a promising therapeutic target for enhancing immune response. We designed a bifunctional (two Pt-Cl bond) PyPDSplatin complex (BiPP) by coupling PyPDS with cisplatin.Due to the retention of two chlorine atoms, BiPP can covalently bind to two sites on G4s, thereby enhancing binding stability. BiPP retains the classical cisplatin structure, which helps to maintain it in a neutral or weakly charged state, facilitating the passage of dichloroplatin complexes across the cell membrane. BiPP not only significantly bolstered the antitumor efficacy of chemotherapy but also induced the damage to G4s, facilitating their efflux from the nucleus and thereby activating the synergistic interplay between the absent in melanoma 2-apoptosis-associated speck-like protein containing a CARD (AIM2-ASC) and cyclic GMP-AMP synthase-stimulator of the interferon gene (cGAS-STING) pathways. Moreover, BiPP initiated a molecular cascade that triggers pyroptosis by down-regulating baculoviral IAP repeat containing 7 (BIRC7) gene expression. During this process, caspase-3 is activated to cleave gasdermin E (GSDME), releasing its N-terminal domain(GSDNE-N), which subsequently instigates pyroptosis. This interaction culminates in the formation of a highly integrated antitumor immune network in conjunction with the BIRC7-caspase-3-GSDME system. Our findings not only unveil the pivotal role played by the G4s in the context of antitumor immunity, but also open an avenue for the application of G4-guided chemotherapy agents in immunotherapy.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"34 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142684776","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 sluggish kinetics of oxygen reduction reaction (ORR) at the cathode in those proton exchange membrane fuel cells (PEMFCs) and metal-air batteries usually require high-performance catalysts to reduce the reaction overpotential for practical applications. Among various electrocatalysts, the most effective platinum group metal (PGM) catalysts suffer from the drawbacks of high cost, scarcity, and poor cycling stability. Platinum group metal-free (PGM-free) catalysts, especially transition metal and nitrogen co-doped carbon (TM-N-C) catalysts, including single atom catalysts, single atom and clusters/nanoparticles catalysts have received increasing attention due to their low-cost, high atom-utilization and remarkable ORR performance recently. However, the TM-N-C catalysts with different local coordination environments typically exhibit completely different ORR catalytic activity and selectivity in both alkaline and acidic media. Therefore, the research progresses of TM-N-C catalysts with regulated coordination environment for enhanced ORR performance are systematically summarized in this review. Specially, the strategies for regulating the coordination environment of TM-N-C catalysts are emphasized, including coordination number regulation, types of N regulation, heteroatom coordination or doping in M-Nx, and synergies of clusters or nanoparticles to M-Nx. Finally, key challenges and prospects regarding the future development of catalysts with regulated coordination environment for ORR in the emerging field are discussed.
{"title":"Developments and Perspectives of Transition Metal-Nitrogen-Carbon Catalysts with Regulated Coordination Environment for Enhanced Oxygen Reduction Reaction Performance","authors":"Wei-Wei Zhao, Wen-Jun Niu, Ru-Ji Li, Bing-Xin Yu, Chen-Yu Cai, Fu-Ming Wang, Li-Yang Xu","doi":"10.1039/d4qi02430c","DOIUrl":"https://doi.org/10.1039/d4qi02430c","url":null,"abstract":"The sluggish kinetics of oxygen reduction reaction (ORR) at the cathode in those proton exchange membrane fuel cells (PEMFCs) and metal-air batteries usually require high-performance catalysts to reduce the reaction overpotential for practical applications. Among various electrocatalysts, the most effective platinum group metal (PGM) catalysts suffer from the drawbacks of high cost, scarcity, and poor cycling stability. Platinum group metal-free (PGM-free) catalysts, especially transition metal and nitrogen co-doped carbon (TM-N-C) catalysts, including single atom catalysts, single atom and clusters/nanoparticles catalysts have received increasing attention due to their low-cost, high atom-utilization and remarkable ORR performance recently. However, the TM-N-C catalysts with different local coordination environments typically exhibit completely different ORR catalytic activity and selectivity in both alkaline and acidic media. Therefore, the research progresses of TM-N-C catalysts with regulated coordination environment for enhanced ORR performance are systematically summarized in this review. Specially, the strategies for regulating the coordination environment of TM-N-C catalysts are emphasized, including coordination number regulation, types of N regulation, heteroatom coordination or doping in M-Nx, and synergies of clusters or nanoparticles to M-Nx. Finally, key challenges and prospects regarding the future development of catalysts with regulated coordination environment for ORR in the emerging field are discussed.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"20 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142684854","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}
xianghao Kong, Jing Chai, Huijian Zhao, Ning Ye, Zhanggui Hu, Yicheng Wu, Conggang Li
The fabrication of nonlinear optical (NLO) materials that exhibits both pronounced second harmonic generation (SHG) response and broad ultraviolet (UV) transmission range remains a big challenge. In this study, we employed a flux method to extract a potential rare-earth borate UV NLO crystal, K7.5Lu2.5B15O30, by chemical cosubstitution strategy. The title compound crystallizes into a trigonal space group R32 with a three-dimensional structural framework consisting of [B5O10] and [LuO6] groups. Remarkably, K7.5Lu2.5B15O30 possesses a notably short cutoff edge of 198 nm and a wide band gap of 6.3 eV. Moreover, it demonstrates a strong phase-matched SHG efficiency of 1.2×KDP, which represents an optimal balance between a strong NLO effect and a wide UV transmission range. Besides, theoretical calculations and structural analyses unveil that the NLO properties observed in K7.5Lu2.5B15O30 are primarily attributable to the synergistic effect of the [B5O10] groups and [LuO6] octahedra. These findings indicate that K7.5Lu2.5B15O30 has potential applications as beryllium-free UV NLO materials
{"title":"Chemical substitution towards a rare-earth borate deep ultraviolet NLO crystal exhibiting a strong SHG response","authors":"xianghao Kong, Jing Chai, Huijian Zhao, Ning Ye, Zhanggui Hu, Yicheng Wu, Conggang Li","doi":"10.1039/d4qi02469a","DOIUrl":"https://doi.org/10.1039/d4qi02469a","url":null,"abstract":"The fabrication of nonlinear optical (NLO) materials that exhibits both pronounced second harmonic generation (SHG) response and broad ultraviolet (UV) transmission range remains a big challenge. In this study, we employed a flux method to extract a potential rare-earth borate UV NLO crystal, K7.5Lu2.5B15O30, by chemical cosubstitution strategy. The title compound crystallizes into a trigonal space group R32 with a three-dimensional structural framework consisting of [B5O10] and [LuO6] groups. Remarkably, K7.5Lu2.5B15O30 possesses a notably short cutoff edge of 198 nm and a wide band gap of 6.3 eV. Moreover, it demonstrates a strong phase-matched SHG efficiency of 1.2×KDP, which represents an optimal balance between a strong NLO effect and a wide UV transmission range. Besides, theoretical calculations and structural analyses unveil that the NLO properties observed in K7.5Lu2.5B15O30 are primarily attributable to the synergistic effect of the [B5O10] groups and [LuO6] octahedra. These findings indicate that K7.5Lu2.5B15O30 has potential applications as beryllium-free UV NLO materials","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"2 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678681","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}
Wei-Dong Liu, Han Xu, Chong-Yang Li, La-Sheng Long, Lansun Zheng, Xiang-Jian Kong
The study of magneto-optical effects based on the f-f emission and absorption of lanthanide ions has attracted considerable interest. In this work, we present a series of isostructural lanthanide-titanium-oxo clusters (LTOCs) Ln2Ti7 (Ln = La, Sm, Eu) using 3,5-di-tert-butylbenzoic acid as the ligand. A detailed comparison of the luminescence properties of Sm₂Ti₇ and Eu₂Ti₇ shows that Eu₂Ti₇ displays superior luminescence intensity, higher color purity red light, longer lifetime, and significantly higher quantum yield. These properties, along with its high stability in solution, make Eu₂Ti₇ an excellent candidate for magnetic circularly polarized luminescence (MCPL) studies. Under an external magnetic field, Eu₂Ti₇ exhibited strong MCPL signals, with the maximum |gMCPL| value being 0.04 T-1 from the 5D0→7F4 transition. In contrast, the weaker luminescence of Sm₂Ti₇ rendered MCPL analysis ineffective; however, its strong near-infrared absorption allowed for magnetic circular dichroism (MCD) studies. The MCD spectra of Sm₂Ti₇ revealed significant signals corresponding to f-f transitions in the 900-1600 nm range, with the maximum |gMCD| value observed at 1102 nm. This work provides valuable insights into the magneto-optical properties of Ln-based clusters, emphasizing the role of energy-level analysis for further research into their potential applications in magneto-optical devices.
{"title":"Magneto-Optical Response and Luminescence Properties of Lanthanide-Titanium-Oxo Clusters Eu₂Ti₇ and Sm₂Ti₇","authors":"Wei-Dong Liu, Han Xu, Chong-Yang Li, La-Sheng Long, Lansun Zheng, Xiang-Jian Kong","doi":"10.1039/d4qi02645d","DOIUrl":"https://doi.org/10.1039/d4qi02645d","url":null,"abstract":"The study of magneto-optical effects based on the f-f emission and absorption of lanthanide ions has attracted considerable interest. In this work, we present a series of isostructural lanthanide-titanium-oxo clusters (LTOCs) Ln2Ti7 (Ln = La, Sm, Eu) using 3,5-di-tert-butylbenzoic acid as the ligand. A detailed comparison of the luminescence properties of Sm₂Ti₇ and Eu₂Ti₇ shows that Eu₂Ti₇ displays superior luminescence intensity, higher color purity red light, longer lifetime, and significantly higher quantum yield. These properties, along with its high stability in solution, make Eu₂Ti₇ an excellent candidate for magnetic circularly polarized luminescence (MCPL) studies. Under an external magnetic field, Eu₂Ti₇ exhibited strong MCPL signals, with the maximum |gMCPL| value being 0.04 T-1 from the 5D0→7F4 transition. In contrast, the weaker luminescence of Sm₂Ti₇ rendered MCPL analysis ineffective; however, its strong near-infrared absorption allowed for magnetic circular dichroism (MCD) studies. The MCD spectra of Sm₂Ti₇ revealed significant signals corresponding to f-f transitions in the 900-1600 nm range, with the maximum |gMCD| value observed at 1102 nm. This work provides valuable insights into the magneto-optical properties of Ln-based clusters, emphasizing the role of energy-level analysis for further research into their potential applications in magneto-optical devices.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"253 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678744","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}
Transition metal oxides (TMOs) are considered a showing potential anode material for the lithium-ion batteries (LIBs) because of its high theoretical capacity. However, their use in LIBs is limited by factors such as low initial coulombic efficiency, substantial volume changes, and low electrical conductivity. Here, the amorphous MoO2 capped with different carbon is ingeniously designed by controlling the calcination temperature and different carbon sources. Electrochemical kinetic and material characterization show that the amorphous structure not only enhances its electronic conductivity, but also optimizes the lithium-ion (Li+) migration mode, thus improving its rate performance. Furthermore, the pore sizes produced by different carbon sources were found to have different effects on the performance of LIBs. Meanwhile, the Li+ storage mechanism of the amorphous MoO2-x@C was revealed by in-situ XRD analysis. As expected, the amorphous MoO2-x@C exhibits an excellent cycling stability, maintaining a discharge specific capacity of 601.4 mAh g−1 at 5.0 A g−1 for 800 cycles. Particularly, the MoO2-x@C||LiCoO2 full cell still possesses a capacity of 109.8 mAh g−1 at 0.2 C for 80 cycles. This endeavor will provide an experimental idea for the molybdenum-based oxide high-performance anode materials.
过渡金属氧化物（TMOs）因其理论容量高而被认为是锂离子电池（LIBs）的潜在负极材料。然而，由于初始库仑效率低、体积变化大和导电性低等因素，它们在锂离子电池中的应用受到了限制。在此，我们通过控制煅烧温度和不同的碳源，巧妙地设计了以不同碳为封端的无定形二氧化锰。电化学动力学和材料表征结果表明，非晶结构不仅增强了其电子导电性，还优化了锂离子（Li+）迁移模式，从而提高了其速率性能。此外，还发现不同碳源产生的孔隙大小对锂离子电池的性能有不同的影响。同时，原位 XRD 分析揭示了无定形 MoO2-x@C 的 Li+ 储存机制。正如预期的那样，非晶态 MoO2-x@C 表现出优异的循环稳定性，在 5.0 A g-1 的条件下，其放电比容量在 800 次循环后仍能保持在 601.4 mAh g-1 的水平。特别是，MoO2-x@C||钴酸锂全电池在 0.2 摄氏度条件下循环 80 次仍能保持 109.8 mAh g-1 的容量。这一尝试将为钼基氧化物高性能正极材料提供一种实验思路。
{"title":"Designing Different Carbon Capping Amorphous MoO2 to Enhance Electrochemical Performance in Lithium-Ion Batteries","authors":"Yali Cao, Gaoyuan Liu, Xinxin Yin, Jing Xie, Jindou Hu, Aize Hao, Zhenjiang Lu","doi":"10.1039/d4qi02198c","DOIUrl":"https://doi.org/10.1039/d4qi02198c","url":null,"abstract":"Transition metal oxides (TMOs) are considered a showing potential anode material for the lithium-ion batteries (LIBs) because of its high theoretical capacity. However, their use in LIBs is limited by factors such as low initial coulombic efficiency, substantial volume changes, and low electrical conductivity. Here, the amorphous MoO2 capped with different carbon is ingeniously designed by controlling the calcination temperature and different carbon sources. Electrochemical kinetic and material characterization show that the amorphous structure not only enhances its electronic conductivity, but also optimizes the lithium-ion (Li+) migration mode, thus improving its rate performance. Furthermore, the pore sizes produced by different carbon sources were found to have different effects on the performance of LIBs. Meanwhile, the Li+ storage mechanism of the amorphous MoO2-x@C was revealed by in-situ XRD analysis. As expected, the amorphous MoO2-x@C exhibits an excellent cycling stability, maintaining a discharge specific capacity of 601.4 mAh g−1 at 5.0 A g−1 for 800 cycles. Particularly, the MoO2-x@C||LiCoO2 full cell still possesses a capacity of 109.8 mAh g−1 at 0.2 C for 80 cycles. This endeavor will provide an experimental idea for the molybdenum-based oxide high-performance anode materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"63 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678683","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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