Xiaopei Li, Xianxu Chu, Kefan Ying, Xi Chen, Peng Sun, Haiyun Xu, Lu Li, Jie Zhang, Wenjuan Li
The five novel nickel organic complexes featuring different electron-rich and electron-deficient groups were synthesized as electrocatalysts by using N-(aryl/alkyl)-2-isonicotinoylhydrazine-1-carbothioamide compounds in coordination with nickel acetate tetrahydrate and 1,10-phenanthroline. These Ni-complexes were characterized using infrared and Raman spectroscopy and were subsequently employed for the oxygen evolution reaction (OER) in water splitting under alkaline conditions. The overpotential and Tafel slope for Ni-based complex Ni-1 were as low as 454 mV and 111.90 mV dec-1, respectively, at a current density of 10 mA cm-2, indicating excellent electrochemical performance. Furthermore, Ni-1 demonstrated good electrochemical stability, with only minor voltage fluctuations observed during the continuous bubble generation over a 40 hours electrolysis period and nickel maintains a +2 oxidation state (Ni2+) in the complex both before and after the OER test via characterization of N2p spectra by X-ray photoelectron spectroscopy (XPS) measurements. This study confirms the electronic effect of substituent groups on the water-splitting ability of Ni-complexes bearing the two different organic ligands, showing that the overpotential and Tafel slope increase with a decrease in the electron-donating capacity of the substituent groups.
通过使用 N-（芳基/烷基）-2-异烟酰肼-1-硫代酰胺化合物与四水醋酸镍和 1,10-菲罗啉配位，合成了五种具有不同富电子和缺电子基团的新型镍有机络合物作为电催化剂。利用红外光谱和拉曼光谱对这些镍络合物进行了表征，随后将其用于碱性条件下水分离中的氧进化反应（OER）。在电流密度为 10 mA cm-2 时，镍基络合物 Ni-1 的过电位和 Tafel 斜率分别低至 454 mV 和 111.90 mV dec-1，表明其具有优异的电化学性能。此外，通过 X 射线光电子能谱（XPS）测量 N2p 光谱，Ni-1 还表现出良好的电化学稳定性，在 40 小时的连续电解产生气泡过程中仅观察到轻微的电压波动，并且在 OER 测试前后，复合物中的镍均保持 +2 氧化态（Ni2+）。这项研究证实了取代基团对含有两种不同有机配体的镍络合物分水能力的电子效应，表明过电位和塔菲尔斜率随着取代基团电子供能能力的降低而增加。
{"title":"Synthesis of Novel Organic Ni (II) N-isonicotinoylhydrazine-Carbothioamide Complexes and their Application in the Oxygen Evolution Reactions","authors":"Xiaopei Li, Xianxu Chu, Kefan Ying, Xi Chen, Peng Sun, Haiyun Xu, Lu Li, Jie Zhang, Wenjuan Li","doi":"10.1039/d5qi00033e","DOIUrl":"https://doi.org/10.1039/d5qi00033e","url":null,"abstract":"The five novel nickel organic complexes featuring different electron-rich and electron-deficient groups were synthesized as electrocatalysts by using N-(aryl/alkyl)-2-isonicotinoylhydrazine-1-carbothioamide compounds in coordination with nickel acetate tetrahydrate and 1,10-phenanthroline. These Ni-complexes were characterized using infrared and Raman spectroscopy and were subsequently employed for the oxygen evolution reaction (OER) in water splitting under alkaline conditions. The overpotential and Tafel slope for Ni-based complex Ni-1 were as low as 454 mV and 111.90 mV dec-1, respectively, at a current density of 10 mA cm-2, indicating excellent electrochemical performance. Furthermore, Ni-1 demonstrated good electrochemical stability, with only minor voltage fluctuations observed during the continuous bubble generation over a 40 hours electrolysis period and nickel maintains a +2 oxidation state (Ni2+) in the complex both before and after the OER test via characterization of N2p spectra by X-ray photoelectron spectroscopy (XPS) measurements. This study confirms the electronic effect of substituent groups on the water-splitting ability of Ni-complexes bearing the two different organic ligands, showing that the overpotential and Tafel slope increase with a decrease in the electron-donating capacity of the substituent groups.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"88 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847022","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 incorporation of difluoroboron into the side arms of polyhedral oligomeric silsesquioxanes (POSSs) opens up new possibilities for the construction of metal-free photocatalysts with tailored properties. Herein, we report the design and synthesis of novel difluoroboron complexes of POSSs (POSS-tert-BF2, POSS-sal-BF2 and POSS-npht-BF2) derived from imine-functionalized POSSs, which were utilized as efficient photocatalysts. The complexes demonstrated exceptional photocatalytic performance in the aerobic oxidation of sulfides to sulfoxides, significantly outperforming their silsesquioxane-free counterparts. POSS-tert-BF2 demonstrated a high singlet oxygen quantum yield of 48%. This study highlights the feasibility of intramolecular cooperative activity in catalytic reactions and identifies key factors influencing its effectiveness. Furthermore, it underscores the potential of POSS as a versatile building block for the development of advanced photocatalytic materials.
{"title":"Polyhedral oligomeric silsesquioxane difluoroboron complexes as cooperative octo-site catalysts for the photooxidation of sulfides to sulfoxides","authors":"Mateusz Janeta, Sławomir Szafert","doi":"10.1039/d5qi00323g","DOIUrl":"https://doi.org/10.1039/d5qi00323g","url":null,"abstract":"The incorporation of difluoroboron into the side arms of polyhedral oligomeric silsesquioxanes (POSSs) opens up new possibilities for the construction of metal-free photocatalysts with tailored properties. Herein, we report the design and synthesis of novel difluoroboron complexes of POSSs (<strong>POSS-tert-BF<small><sub>2</sub></small></strong>, <strong>POSS-sal-BF<small><sub>2</sub></small></strong> and <strong>POSS-npht-BF<small><sub>2</sub></small></strong>) derived from imine-functionalized POSSs, which were utilized as efficient photocatalysts. The complexes demonstrated exceptional photocatalytic performance in the aerobic oxidation of sulfides to sulfoxides, significantly outperforming their silsesquioxane-free counterparts. <strong>POSS-tert-BF<small><sub>2</sub></small></strong> demonstrated a high singlet oxygen quantum yield of 48%. This study highlights the feasibility of intramolecular cooperative activity in catalytic reactions and identifies key factors influencing its effectiveness. Furthermore, it underscores the potential of POSS as a versatile building block for the development of advanced photocatalytic materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841523","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}
Jose Cammarata, Maximilian Schimpf, Daniel Scott, Robert Wolf
The development of efficient, direct strategies for the transformation of white phosphorus (P4) into useful monophosphorus compounds, as alternatives to the current wasteful and hazardous indirect processes, remains a significant challenge. Encouragingly, recent reports have shown that the reduction of P4 with organotin hydrides and subsequent functionalisation with electrophiles allows for the efficient synthesis of an array of industrially relevant monophosphines in a ‘one-pot’ manner. However, despite the practical and conceptual simplicity, the appeal of this method is limited by the inherent toxicity of most organotin derivatives. Here, we address this problem through experimental and computational studies of the reactivity of lighter and less toxic hydrogermane and hydrosilane homologues of organotin hydrides (R3EH, E = Ge or Si) towards P4. These hydroelementation reactions can be employed to directly transform P4 into useful monophosphorus compounds, in a simple ‘one-pot’ fashion similar to the original organotin-based systems.
{"title":"Hydrosilylation and hydrogermylation of white phosphorus","authors":"Jose Cammarata, Maximilian Schimpf, Daniel Scott, Robert Wolf","doi":"10.1039/d5qi00869g","DOIUrl":"https://doi.org/10.1039/d5qi00869g","url":null,"abstract":"The development of efficient, direct strategies for the transformation of white phosphorus (P<small><sub>4</sub></small>) into useful monophosphorus compounds, as alternatives to the current wasteful and hazardous indirect processes, remains a significant challenge. Encouragingly, recent reports have shown that the reduction of P<small><sub>4</sub></small> with organotin hydrides and subsequent functionalisation with electrophiles allows for the efficient synthesis of an array of industrially relevant monophosphines in a ‘one-pot’ manner. However, despite the practical and conceptual simplicity, the appeal of this method is limited by the inherent toxicity of most organotin derivatives. Here, we address this problem through experimental and computational studies of the reactivity of lighter and less toxic hydrogermane and hydrosilane homologues of organotin hydrides (R<small><sub>3</sub></small>EH, E = Ge or Si) towards P<small><sub>4</sub></small>. These hydroelementation reactions can be employed to directly transform P<small><sub>4</sub></small> into useful monophosphorus compounds, in a simple ‘one-pot’ fashion similar to the original organotin-based systems.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"31 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847023","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}
Divalent endohedral metallofullerenes (Di-EMFs) featuring a closed-shell electronic configuration and two-electron transfer from the inner cluster to outer cage exhibit a more evenly distributed charge over the whole cage, resulting in a low chemical reactivity and thus limited chemical modification approaches. Up to date, the reported chemical modifications of Di-EMFs are limited to those with large carbon cages based on C80, C82, and C84, whereas the chemical reactivity of Di-EMFs bearing cage smaller than C80 remains unknown. Herein, on the basis of synthesis of a medium-sized Di-EMF Yb@D3h-C74, we investigated its 1,3-dipolar cycloaddition reaction, and found its unusually high chemical reactivity at room temperature, significantly different from the reported Di-EMFs with larger carbon cages for which cycloaddition reactions generally require light irradiation or heating conditions. As a result, four monoadducts of Yb@D3h-C74, labelled as 2a-2d, were obtained, among which the molecular structure of 2a was unambiguously determined by single-crystal X-ray crystallography. The addition sites were far from the carbon cage region adjacent to the inner Yb cation, and this addition pattern is different to those of the reported Di-EMFs with larger carbon cage size. Theoretical calculations rationally explained the high reactivity of Yb@D3hC74 as well as its addition pattern.
{"title":"Cycloaddition Reactivity of Yb@D3h-C74: the Carbon Cage Size Matters","authors":"Muqing Chen, wh xiang, Xinde Li, Jinpeng Xin, Peng Jin, Yongfu Qiu, Zhiyu Cheng, Shangfeng Yang","doi":"10.1039/d5qi00649j","DOIUrl":"https://doi.org/10.1039/d5qi00649j","url":null,"abstract":"Divalent endohedral metallofullerenes (Di-EMFs) featuring a closed-shell electronic configuration and two-electron transfer from the inner cluster to outer cage exhibit a more evenly distributed charge over the whole cage, resulting in a low chemical reactivity and thus limited chemical modification approaches. Up to date, the reported chemical modifications of Di-EMFs are limited to those with large carbon cages based on C<small><sub>80</sub></small>, C<small><sub>82</sub></small>, and C<small><sub>84</sub></small>, whereas the chemical reactivity of Di-EMFs bearing cage smaller than C<small><sub>80</sub></small> remains unknown. Herein, on the basis of synthesis of a medium-sized Di-EMF Yb@<em>D</em><small><sub>3h</sub></small>-C<small><sub>74</sub></small>, we investigated its 1,3-dipolar cycloaddition reaction, and found its unusually high chemical reactivity at room temperature, significantly different from the reported Di-EMFs with larger carbon cages for which cycloaddition reactions generally require light irradiation or heating conditions. As a result, four monoadducts of Yb@D<small><sub>3h</sub></small>-C<small><sub>74</sub></small>, labelled as<strong> 2a</strong>-<strong>2d</strong>, were obtained, among which the molecular structure of <strong>2a</strong> was unambiguously determined by single-crystal X-ray crystallography. The addition sites were far from the carbon cage region adjacent to the inner Yb cation, and this addition pattern is different to those of the reported Di-EMFs with larger carbon cage size. Theoretical calculations rationally explained the high reactivity of Yb@D<small><sub>3h</sub></small>C<small><sub>74</sub></small> as well as its addition pattern.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"73 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841526","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}
Xia-Ying Zhao, Lei Yue, Meng-Yu Xu, Gui-Fang Zhang, Xi-Yan Dong, Yong-Li Wei, Quanjun Li
Metal-organic chalcogenolate is one of excellent hybrid semiconductors, yet reports on their precise structures remain limited due to their large structural periodicity. Understanding the relationship between their structure and optical properties remained a significant challenge. External pressure is recognized as a clean and effective method for tuning the structure and properties of optical materials. In this study, we obtained a three-dimensional silver chalcogenolate {Ag10[(CH3)2CHS]8(CN)2}n, which exhibited bright orange-red emission upon ultra-violet excitation at atmospheric pressure. Notably this compound showed unique piezoresponse to varying pressures. During compression, the emission centers experienced a blue shift of nearly 130 nm, followed by a red shift. Both mechanical stress and phase conversion contribute to this complex piezochromic behavior. In situ high-pressure X-ray diffraction measurements and Raman spectroscopy confirmed phase transitions during the color change. Density functional theory simulations further verified the direct band gap semiconductor characteristics of this compound and suggested how the atomic contributions to the band structure. This work not only sheds light on the structural and optical responses to hydrostatic pressure but also explores their relationship in this 3D silver chalcogenolate, offering a new perspective on studying the nature of metal-organic frameworks semiconductors.
{"title":"Pressure Induced Blue Shift Emission and Its Influence on the Band Gap in an Emerging 3D Semiconductor †","authors":"Xia-Ying Zhao, Lei Yue, Meng-Yu Xu, Gui-Fang Zhang, Xi-Yan Dong, Yong-Li Wei, Quanjun Li","doi":"10.1039/d5qi00550g","DOIUrl":"https://doi.org/10.1039/d5qi00550g","url":null,"abstract":"Metal-organic chalcogenolate is one of excellent hybrid semiconductors, yet reports on their precise structures remain limited due to their large structural periodicity. Understanding the relationship between their structure and optical properties remained a significant challenge. External pressure is recognized as a clean and effective method for tuning the structure and properties of optical materials. In this study, we obtained a three-dimensional silver chalcogenolate {Ag10[(CH3)2CHS]8(CN)2}n, which exhibited bright orange-red emission upon ultra-violet excitation at atmospheric pressure. Notably this compound showed unique piezoresponse to varying pressures. During compression, the emission centers experienced a blue shift of nearly 130 nm, followed by a red shift. Both mechanical stress and phase conversion contribute to this complex piezochromic behavior. In situ high-pressure X-ray diffraction measurements and Raman spectroscopy confirmed phase transitions during the color change. Density functional theory simulations further verified the direct band gap semiconductor characteristics of this compound and suggested how the atomic contributions to the band structure. This work not only sheds light on the structural and optical responses to hydrostatic pressure but also explores their relationship in this 3D silver chalcogenolate, offering a new perspective on studying the nature of metal-organic frameworks semiconductors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841524","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}
Lanthanide metals possess multiple oxidation states, being emerging as a frontier toward the nitrogen fixation, yet the knowledge regarding their photocatalytic mechanism and active sites is very limited. Herein, a series of LnOy/MoS2 (Ln = La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu) photocatalysts for nitrogen fixation are successfully designed and synthesized. The experimental results demonstrate that the load of LnOy redox promoters (Ln = Ce, Eu or Tb, the following is also) significantly increases the effective reaction-active sites and promotes the separation and transfer of carriers, thereby improving photocatalytic performance. The visible-light-driven nitrogen fixation activities of LnOy/MoS2 composites are significantly enhanced, achieving remarkable rates of 342.8 μmol g⁻¹ h⁻¹ for CeOy/MoS2, 369.1 μmol g⁻¹ h⁻¹ for EuOy/MoS2, and 457.3 μmol g⁻¹ h⁻¹ for TbOy/MoS2, which are substantially higher than that of pristine MoS2 (46.1 μmol g⁻¹ h⁻¹). Theoretical calculations reveal that LnOy loading promote the adsorption and activation of N₂ molecules, with the Tb site exhibiting the strongest adsorption capacity (ΔG=1.46 eV) and superior electron transfer efficiency, as confirmed by PL spectroscopy and photocurrent response analysis. This work provides fundamental insights into the role of lanthanide oxides in regulating photocatalytic nitrogen activation and offers a strategic framework for designing high-performance lanthanide-based catalysts.
{"title":"Nitrogen-Activation and Charge-Transfer Lanthanide Oxide Promoters for Enhanced Photocatalytic Ammonia Synthesis","authors":"Hongda Li, Bijun Zhou, Xiao Miao, Xu Zhu, Shiyu Chen, Xiaoyu Jiang, Pengyan Li","doi":"10.1039/d5qi00655d","DOIUrl":"https://doi.org/10.1039/d5qi00655d","url":null,"abstract":"Lanthanide metals possess multiple oxidation states, being emerging as a frontier toward the nitrogen fixation, yet the knowledge regarding their photocatalytic mechanism and active sites is very limited. Herein, a series of LnOy/MoS2 (Ln = La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu) photocatalysts for nitrogen fixation are successfully designed and synthesized. The experimental results demonstrate that the load of LnOy redox promoters (Ln = Ce, Eu or Tb, the following is also) significantly increases the effective reaction-active sites and promotes the separation and transfer of carriers, thereby improving photocatalytic performance. The visible-light-driven nitrogen fixation activities of LnOy/MoS2 composites are significantly enhanced, achieving remarkable rates of 342.8 μmol g⁻¹ h⁻¹ for CeOy/MoS2, 369.1 μmol g⁻¹ h⁻¹ for EuOy/MoS2, and 457.3 μmol g⁻¹ h⁻¹ for TbOy/MoS2, which are substantially higher than that of pristine MoS2 (46.1 μmol g⁻¹ h⁻¹). Theoretical calculations reveal that LnOy loading promote the adsorption and activation of N₂ molecules, with the Tb site exhibiting the strongest adsorption capacity (ΔG=1.46 eV) and superior electron transfer efficiency, as confirmed by PL spectroscopy and photocurrent response analysis. This work provides fundamental insights into the role of lanthanide oxides in regulating photocatalytic nitrogen activation and offers a strategic framework for designing high-performance lanthanide-based catalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841775","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 development of efficient nonprecious-metal catalysts for urea oxidation reaction (UOR) to improve the efficiency of electrocatalytic water splitting for hydrogen production remains a challenge. Herein, we synthesized an ultra-small β-Ni(OH)2 quantum dots catalyst with abundant edges (US-β-Ni(OH)2 QDs) by a coupling approach of co-precipitation and anionic exchange. The obtained US-β-Ni(OH)2 QDs catalyst exhibits high activity toward UOR, and the required potential is only 1.48 V (vs. RHE) to arrive at 151 mA·cm-2. Notably, the US-β-Ni(OH)2 QDs catalyst reflects 4.1 and 96 times higher current density than the β-Ni(OH)2 nanosheets (38.34 mA cm–2) and Pt mesh electrode (1.57 mA cm–2) at the potential of 1.48 V (vs. RHE). The catalytic reaction mechanism indicates that the US-β-Ni(OH)2 QDs catalyst with the ultra-small size (~3 nm) has more abundant edges compared to the β-Ni(OH)2 nanosheets, which provides abundant active sites for catalytic reactions. Moreover, it was found that the Ni-OH bonding of the edge in US-β-Ni(OH)2 QDs is more active than the edge and basic plane of β-Ni(OH)2 nanosheets, which promotes the conversion from Ni2+ to Ni3+ and the adsorption of urea molecules, reducing the energy barrier of UOR reaction and thus improving the UOR performance. This work provides a new approach for synthesizing ultra-small hydroxide quantum dots catalysts with efficient UOR activity but low cost.
{"title":"Ultra-small β-Ni(OH)2 Quantum Dots Catalyst with Abundant Edges for Efficient Urea Oxidation Reaction","authors":"Qishuang Zhu, Xianshu Qiao, Chuanjin Tian, Pengzhang Li, Yumin Liu, Wenyan Zhao, Liang Ma, Chang-An Wang","doi":"10.1039/d5qi00372e","DOIUrl":"https://doi.org/10.1039/d5qi00372e","url":null,"abstract":"The development of efficient nonprecious-metal catalysts for urea oxidation reaction (UOR) to improve the efficiency of electrocatalytic water splitting for hydrogen production remains a challenge. Herein, we synthesized an ultra-small β-Ni(OH)2 quantum dots catalyst with abundant edges (US-β-Ni(OH)2 QDs) by a coupling approach of co-precipitation and anionic exchange. The obtained US-β-Ni(OH)2 QDs catalyst exhibits high activity toward UOR, and the required potential is only 1.48 V (vs. RHE) to arrive at 151 mA·cm-2. Notably, the US-β-Ni(OH)2 QDs catalyst reflects 4.1 and 96 times higher current density than the β-Ni(OH)2 nanosheets (38.34 mA cm–2) and Pt mesh electrode (1.57 mA cm–2) at the potential of 1.48 V (vs. RHE). The catalytic reaction mechanism indicates that the US-β-Ni(OH)2 QDs catalyst with the ultra-small size (~3 nm) has more abundant edges compared to the β-Ni(OH)2 nanosheets, which provides abundant active sites for catalytic reactions. Moreover, it was found that the Ni-OH bonding of the edge in US-β-Ni(OH)2 QDs is more active than the edge and basic plane of β-Ni(OH)2 nanosheets, which promotes the conversion from Ni2+ to Ni3+ and the adsorption of urea molecules, reducing the energy barrier of UOR reaction and thus improving the UOR performance. This work provides a new approach for synthesizing ultra-small hydroxide quantum dots catalysts with efficient UOR activity but low cost.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"36 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841777","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}
We systematically investigated the superconducting properties of 2H-PtxTaS2 (0 ≤ x ≤ 0.08). As the platinum (Pt) content increases, the charge density wave (CDW) in 2H-TaS2, which appears at approximately 75 K, is progressively suppressed and completely disappears in Pt0.06TaS2. Meanwhile, the superconducting transition temperature (Tc) first increases and then decreases, reaching its maximum value of approximately 4.85 K at x = 0.06. This phenomenon suggests a competitive interplay between CDW and superconductivity (SC) in this system. Further measurements of the superconducting parameters of Pt0.06TaS2 indicate that the enhancement of Tc is primarily attributed to an increase in the density of states at the Fermi level.
{"title":"Superconductivity in Platinum-Intercalated 2H-TaS₂","authors":"Lijia Zhou, Xiangjiang Dong, Qiang Li, Xianran Xing","doi":"10.1039/d5qi00683j","DOIUrl":"https://doi.org/10.1039/d5qi00683j","url":null,"abstract":"We systematically investigated the superconducting properties of 2H-PtxTaS2 (0 ≤ x ≤ 0.08). As the platinum (Pt) content increases, the charge density wave (CDW) in 2H-TaS2, which appears at approximately 75 K, is progressively suppressed and completely disappears in Pt0.06TaS2. Meanwhile, the superconducting transition temperature (Tc) first increases and then decreases, reaching its maximum value of approximately 4.85 K at x = 0.06. This phenomenon suggests a competitive interplay between CDW and superconductivity (SC) in this system. Further measurements of the superconducting parameters of Pt0.06TaS2 indicate that the enhancement of Tc is primarily attributed to an increase in the density of states at the Fermi level.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"42 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841527","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}
Lead-free (Na0.5Bi0.5)TiO3-based dielectric materials are promising for electrostatic energy storage due to their strong polarization response and environmental friendliness. However, challenges like high electric hysteresis loss (Wloss) and low electric breakdown strength (Eb) limit their recoverable energy density (Wrec) and energy conversion efficiency (η). A superparaelectric design with structure optimization has been proposed to overcome these restrictions. Based on this strategy, a series of (1 − x)(Na0.3Bi0.38Sr0.28)TiO3–xCa(Ta0.2Ti0.75)O3 (abbreviated as (1 − x)NBST–xCTT; x = 0.0, 0.1, 0.2, 0.3, and 0.4) ceramics were fabricated. Their phase structure gradually evolves from the rhombohedral and tetragonal coexistence (R&T) to the tetragonal and cubic coexistence (T&C), accompanied by the increasing proportion of weakly coupled and highly dynamic polar structures. This behavior enables the establishment of a superparaelectric relaxor ferroelectric (SPE-RFE) state, reducing Wloss, enhancing η, and improving dielectric stability. The improved microstructure with refined grains boosted Eb, further contributing to excellent performances. Notably, the optimized 0.6NBST-0.4CTT SPE-RFE ceramic, with high Eb, large polarization difference (ΔP), and slight Wloss, delivered a large Wrec of 6.90 J cm−3 with a high η of 92.55% at 600 kV cm−1, alongside excellent dielectric stability (−60 to 135 °C) following the EIA-X7R standard. Moreover, a high power density (∼125 MW cm−3) and an ultrafast charge–discharge rate (t0.9 ∼ 33 ns) were realized at 300 kV cm−1. Encouragingly, the 0.6NBST-0.4CTT SPE-RFE ceramic also exhibits excellent energy-storage/charge–discharge stabilities. These results highlight the promising potential of the 0.6NBST–0.4CTT SPE-RFE ceramic for electrostatic energy storage. They also confirm the effectiveness of this strategy and provide valuable guidance for advancing dielectric energy-storage materials/capacitors.
{"title":"A superparaelectric design with structure optimization enables superior energy-storage performances and stabilities in (Na0.5Bi0.5)TiO3-based ceramics","authors":"Xiangjun Meng, Ying Yuan, Bin Tang, Enzhu Li","doi":"10.1039/d5qi00216h","DOIUrl":"https://doi.org/10.1039/d5qi00216h","url":null,"abstract":"Lead-free (Na<small><sub>0.5</sub></small>Bi<small><sub>0.5</sub></small>)TiO<small><sub>3</sub></small>-based dielectric materials are promising for electrostatic energy storage due to their strong polarization response and environmental friendliness. However, challenges like high electric hysteresis loss (<em>W</em><small><sub>loss</sub></small>) and low electric breakdown strength (<em>E</em><small><sub>b</sub></small>) limit their recoverable energy density (<em>W</em><small><sub>rec</sub></small>) and energy conversion efficiency (<em>η</em>). A superparaelectric design with structure optimization has been proposed to overcome these restrictions. Based on this strategy, a series of (1 − <em>x</em>)(Na<small><sub>0.3</sub></small>Bi<small><sub>0.38</sub></small>Sr<small><sub>0.28</sub></small>)TiO<small><sub>3</sub></small>–<em>x</em>Ca(Ta<small><sub>0.2</sub></small>Ti<small><sub>0.75</sub></small>)O<small><sub>3</sub></small> (abbreviated as (1 − <em>x</em>)NBST–<em>x</em>CTT; <em>x</em> = 0.0, 0.1, 0.2, 0.3, and 0.4) ceramics were fabricated. Their phase structure gradually evolves from the rhombohedral and tetragonal coexistence (<em>R</em>&<em>T</em>) to the tetragonal and cubic coexistence (<em>T</em>&<em>C</em>), accompanied by the increasing proportion of weakly coupled and highly dynamic polar structures. This behavior enables the establishment of a superparaelectric relaxor ferroelectric (SPE-RFE) state, reducing <em>W</em><small><sub>loss</sub></small>, enhancing <em>η</em>, and improving dielectric stability. The improved microstructure with refined grains boosted <em>E</em><small><sub>b</sub></small>, further contributing to excellent performances. Notably, the optimized 0.6NBST-0.4CTT SPE-RFE ceramic, with high <em>E</em><small><sub>b</sub></small>, large polarization difference (Δ<em>P</em>), and slight <em>W</em><small><sub>loss</sub></small>, delivered a large <em>W</em><small><sub>rec</sub></small> of 6.90 J cm<small><sup>−3</sup></small> with a high <em>η</em> of 92.55% at 600 kV cm<small><sup>−1</sup></small>, alongside excellent dielectric stability (−60 to 135 °C) following the EIA-X7R standard. Moreover, a high power density (∼125 MW cm<small><sup>−3</sup></small>) and an ultrafast charge–discharge rate (<em>t</em><small><sub>0.9</sub></small> ∼ 33 ns) were realized at 300 kV cm<small><sup>−1</sup></small>. Encouragingly, the 0.6NBST-0.4CTT SPE-RFE ceramic also exhibits excellent energy-storage/charge–discharge stabilities. These results highlight the promising potential of the 0.6NBST–0.4CTT SPE-RFE ceramic for electrostatic energy storage. They also confirm the effectiveness of this strategy and provide valuable guidance for advancing dielectric energy-storage materials/capacitors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"42 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837399","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}
Birefringent crystals that can modulate the polarization of light play an important role in modern scientific research. However, the birefringence of current commercial crystals is limited to inorganic compounds and the coefficients are generally lower than 0.3, rendering it challenging to fulfill stringent standard requirements. Therefore, developing the development of superior birefringent materials has emerged as a significant area of research. In this work, we synthesized a Hg-based nitrate Hg3O2(NO3)2·H2O, which is built by [(Hg3O2)2+]∞ layers and isolated NO3− anions. Hg3O2(NO3)2·H2O shows a large experimental birefringence (Δn = 0.25@546 nm). In order to improve birefringent property, we adopted π-conjugated organic molecule modified strategy to achieve high-performance metal nitrate birefringent crystals , and successfully synthesized a new Hg-based hybrid nitrate (CH5N3S)2Hg(NO3)2. The crystal structure of (CH5N3S)2Hg(NO3)2 is composed of [((CH5N3S)2Hg)2+]∞ units and isolated NO3− anions. Notably, it has an enhanced experimental birefringence (Δn = 0.32@546 nm), which is excellent among all metal nitrates. Structural analysis and theoretical calculations show that for Hg3O2(NO3)2·H2O, HgO2 and nitrate play a crucial role in optical anisotropy. For (CH5N3S)2Hg(NO3)2, the interaction between CH5N3S molecules and cations as well as nitrate play a crucial role in optical anisotropy. The research shows that the introduction of π-conjugated organic molecules is an effective strategy for developing high-performance birefringent materials.
{"title":"π-conjugated organic molecule modified strategy to achieve high-performance metal nitrate birefringent crystal","authors":"Yi-Lei Lv, Liang Ma, Guo-Ren Zhu, Bing-Wei Miao, Wen-Long Liu, Sheng-Ping Guo, Ru-Ling Tang","doi":"10.1039/d5qi00730e","DOIUrl":"https://doi.org/10.1039/d5qi00730e","url":null,"abstract":"Birefringent crystals that can modulate the polarization of light play an important role in modern scientific research. However, the birefringence of current commercial crystals is limited to inorganic compounds and the coefficients are generally lower than 0.3, rendering it challenging to fulfill stringent standard requirements. Therefore, developing the development of superior birefringent materials has emerged as a significant area of research. In this work, we synthesized a Hg-based nitrate Hg3O2(NO3)2·H2O, which is built by [(Hg3O2)2+]∞ layers and isolated NO3− anions. Hg3O2(NO3)2·H2O shows a large experimental birefringence (Δn = 0.25@546 nm). In order to improve birefringent property, we adopted π-conjugated organic molecule modified strategy to achieve high-performance metal nitrate birefringent crystals , and successfully synthesized a new Hg-based hybrid nitrate (CH5N3S)2Hg(NO3)2. The crystal structure of (CH5N3S)2Hg(NO3)2 is composed of [((CH5N3S)2Hg)2+]∞ units and isolated NO3− anions. Notably, it has an enhanced experimental birefringence (Δn = 0.32@546 nm), which is excellent among all metal nitrates. Structural analysis and theoretical calculations show that for Hg3O2(NO3)2·H2O, HgO2 and nitrate play a crucial role in optical anisotropy. For (CH5N3S)2Hg(NO3)2, the interaction between CH5N3S molecules and cations as well as nitrate play a crucial role in optical anisotropy. The research shows that the introduction of π-conjugated organic molecules is an effective strategy for developing high-performance birefringent materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"6 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837384","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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