Iron carbides assisted Fe-N-C electrocatalysts have attracted significant attention as promising candidates to enhance intrinsic activity in the oxygen reduction reaction (ORR), offering a viable alternative for Pt-based catalysts. However, their widespread development is impeded by challenges such as uncontrolled aggregation, the formation of large nanoparticles, and inefficient synthesis processes. Herein, we report a multiligand coordination self-assembly strategy to synthesize a novel metal-organic framework (MOF) precursor (FeZn-PBMI) with dual ligands and dual metals, followed by a thermal polymerization self-assembly process that successfully prepared the coexistence of FeNx sites and FexC atomic clusters decorate N-doped carbon nanotubes (FexC@FeNCNTs) in gram-scale quantities. The ordered distribution of Zn and Fe within the FeZn-PBMI effectively prevents Fe aggregation during high-temperature pyrolysis, resulting in uniformly dispersed approximately 10 nm FexC nanoparticles. As expected, the FexC@FeNCNTs composite exhibits superior ORR performance with a half-wave potential of 0.87 V, surpassing commercial Pt/C (0.85 V), and demonstrates excellent long-term stability in Zn-air batteries with 1000 cycles. This synthetic approach may facilitate the development of highly active catalysts, advancing the practical application of Fe-N-C catalysts in various energy-related technologies.
{"title":"Multiligand Coordination Self-Assembly Bimetallic Complex Derived Fexc Decorate Fe and N Co-doped Carbon Nanotube for Highly Efficient Oxygen Reduction Reaction","authors":"Qiulin Li, Zhiqin Deng, Yan-Dong Ma, Yangyang Tan, Ruilin He, Qianwei Chen, Shu-Juan Bao, Heng Liu","doi":"10.1039/d5qi00130g","DOIUrl":"https://doi.org/10.1039/d5qi00130g","url":null,"abstract":"Iron carbides assisted Fe-N-C electrocatalysts have attracted significant attention as promising candidates to enhance intrinsic activity in the oxygen reduction reaction (ORR), offering a viable alternative for Pt-based catalysts. However, their widespread development is impeded by challenges such as uncontrolled aggregation, the formation of large nanoparticles, and inefficient synthesis processes. Herein, we report a multiligand coordination self-assembly strategy to synthesize a novel metal-organic framework (MOF) precursor (FeZn-PBMI) with dual ligands and dual metals, followed by a thermal polymerization self-assembly process that successfully prepared the coexistence of FeNx sites and FexC atomic clusters decorate N-doped carbon nanotubes (FexC@FeNCNTs) in gram-scale quantities. The ordered distribution of Zn and Fe within the FeZn-PBMI effectively prevents Fe aggregation during high-temperature pyrolysis, resulting in uniformly dispersed approximately 10 nm FexC nanoparticles. As expected, the FexC@FeNCNTs composite exhibits superior ORR performance with a half-wave potential of 0.87 V, surpassing commercial Pt/C (0.85 V), and demonstrates excellent long-term stability in Zn-air batteries with 1000 cycles. This synthetic approach may facilitate the development of highly active catalysts, advancing the practical application of Fe-N-C catalysts in various energy-related technologies.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"128 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495736","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 synthesized centimeter-scale type-I Weyl semimetal layered trigonal PtBi2 (t-PtBi2) crystals, including intrinsic and doped with diverse elements. Electrocatalytic hydrogen evolution tests were conducted in acidic solutions, allowing for a comparative analysis of their performance against commercial Pt/C electrodes. The results demonstrated that the hydrogen evolution activity of the synthesized topological semimetal crystals significantly surpassed that of the commercial Pt/C electrodes. Furthermore, the introduction of various dopants further enhanced the hydrogen evolution performance of the crystals. Besides, the first principle calculations confirmed these findings and were consistent with the experimental data. This research contributes valuable insights into the potential applications of topological semimetals in electrocatalytic hydrogen evolution.
{"title":"Electrocatalytic Hydrogen Evolution and Doping Modification of Weyl Semimetal PtBi2 Acidic Solution","authors":"Yinghui Liu, Qiubo Chen, Yukai An, Hailong Qiu, Shihui Ma, Hongjun Liu, Zhanggui Hu, Yicheng Wu","doi":"10.1039/d5qi00022j","DOIUrl":"https://doi.org/10.1039/d5qi00022j","url":null,"abstract":"We synthesized centimeter-scale type-I Weyl semimetal layered trigonal PtBi2 (t-PtBi2) crystals, including intrinsic and doped with diverse elements. Electrocatalytic hydrogen evolution tests were conducted in acidic solutions, allowing for a comparative analysis of their performance against commercial Pt/C electrodes. The results demonstrated that the hydrogen evolution activity of the synthesized topological semimetal crystals significantly surpassed that of the commercial Pt/C electrodes. Furthermore, the introduction of various dopants further enhanced the hydrogen evolution performance of the crystals. Besides, the first principle calculations confirmed these findings and were consistent with the experimental data. This research contributes valuable insights into the potential applications of topological semimetals in electrocatalytic hydrogen evolution.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"51 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495737","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 photoreaction of an osmium(VI) nitrido complex, [OsVI(N)(L)(CN)3]‒ (OsN), with various phenols has been investigated. Upon irradiation of OsN with visible light, the excited state (OsN*) is generated which reacts readily with a variety of phenols. OsN* reacts with mono- and di-substituted phenols, including 2,6-dimethylphenol, 2,6-dichlorophenol and 4-methylphenol to afford the corresponding osmium(II) benzoquinone monoimine and osmium(IV) benzoquinone monoiminato complexes. On the other hand, in the reactions of OsN* with bulky tri-substituted phenol such as 2,4,6-tri-tert-butylphenol (tBu3PhOH), C-C bond cleavage occurred and [OsIV(L)(CN)3(N=tBu2Ph(-2H)O)]‒ was formed as the major product. The electronic effects of various para-substituents (X) on the oxidation of phenols were investigated by the method of initial rates (Rx). A Hammett plot of log(Rx/RH) versus σp is linear with a ρ value of ‒0.54. A linear correlation of log(Rx) with the oxidation potentials (E) of phenols was also found with a slope of ‒0.80. On the other hand, no correlations were found between log(Rx) and O-H bond dissociation energy (BDE), as well as the pKa of phenols. The oxidation phenol by OsN* exhibits a negligible kinetic isotope effect (KIE), k(C6H5OH)/k(C6D5OD) ~1. These results are consistent with a mechanism that involves an initial 1e‒ oxidation of the phenol followed by rapid proton transfer (ET-PT) to generate a phenoxy radical, this is followed by a N-rebound step to give the osmium products.
{"title":"Oxidation of Phenols by the Excited State of an Osmium(VI) Nitrido Complex","authors":"yuzhong lu, Li-Xin Wang, Rui-Yue Qi, Jing Xiang, Jiyan Liu, Tai-Chu Lau","doi":"10.1039/d4qi03144j","DOIUrl":"https://doi.org/10.1039/d4qi03144j","url":null,"abstract":"The photoreaction of an osmium(VI) nitrido complex, [OsVI(N)(L)(CN)3]‒ (OsN), with various phenols has been investigated. Upon irradiation of OsN with visible light, the excited state (OsN*) is generated which reacts readily with a variety of phenols. OsN* reacts with mono- and di-substituted phenols, including 2,6-dimethylphenol, 2,6-dichlorophenol and 4-methylphenol to afford the corresponding osmium(II) benzoquinone monoimine and osmium(IV) benzoquinone monoiminato complexes. On the other hand, in the reactions of OsN* with bulky tri-substituted phenol such as 2,4,6-tri-tert-butylphenol (tBu3PhOH), C-C bond cleavage occurred and [OsIV(L)(CN)3(N=tBu2Ph(-2H)O)]‒ was formed as the major product. The electronic effects of various para-substituents (X) on the oxidation of phenols were investigated by the method of initial rates (Rx). A Hammett plot of log(Rx/RH) versus σp is linear with a ρ value of ‒0.54. A linear correlation of log(Rx) with the oxidation potentials (E) of phenols was also found with a slope of ‒0.80. On the other hand, no correlations were found between log(Rx) and O-H bond dissociation energy (BDE), as well as the pKa of phenols. The oxidation phenol by OsN* exhibits a negligible kinetic isotope effect (KIE), k(C6H5OH)/k(C6D5OD) ~1. These results are consistent with a mechanism that involves an initial 1e‒ oxidation of the phenol followed by rapid proton transfer (ET-PT) to generate a phenoxy radical, this is followed by a N-rebound step to give the osmium products.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"30 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495673","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}
Inseo Kim, Sora Yun, Hyun Jae Kim, Jung Yup Yang, Kyu Hyoung Lee, Min Suk Oh, Kimoon Lee
Authors report the fabrication of heterostructure diode adopting p-Ni0.8Cu0.2WO4 oxide/n-Si junction, and its demonstration toward high speed rectifier circuit upto 1 MHz. Newly developed p-type Cu-doped NiWO4 was synthesized by solid-state reaction, and its thin-film form was successfully deposited by e-beam evaporation method. From X-ray diffraction and Raman spectroscopy, it is confirmed that all the deposited Cu-doped NiWO4 films showed amorphous phases independent from substrate heating temperature. UV-visible transmittance and electrical resistivity value decreases, as increasing substrate heating temperature from 100 to 300 oC, revealing that optical transparency and electrical conductivity were in the trade-off relation in Cu-doped NiWO4 film. By fabricating p-Ni0.8Cu0.2WO4/n-Si heterostructure diodes, a highly rectifying behaviour can be attained with an ideality factor and an on/off current ratio of 1.23 and ~104, respectively. When we configure the AC to DC converting half-wave rectifier circuit with p-Ni0.8Cu0.2WO4/n-Si diode, a high-speed operation upto 1 MHz was demonstrated, as strongly supporting that our newly developed p-type oxide can be utilized as a key component in practical oxide-based electronics such as radio frequency identification.
{"title":"Fabrication of p-Ni0.8Cu0.2WO4/n-Si heterojunction diode and 1 MHz rectifier operation","authors":"Inseo Kim, Sora Yun, Hyun Jae Kim, Jung Yup Yang, Kyu Hyoung Lee, Min Suk Oh, Kimoon Lee","doi":"10.1039/d4qi03223c","DOIUrl":"https://doi.org/10.1039/d4qi03223c","url":null,"abstract":"Authors report the fabrication of heterostructure diode adopting <em>p</em>-Ni<small><sub>0.8</sub></small>Cu<small><sub>0.2</sub></small>WO<small><sub>4</sub></small> oxide/<em>n</em>-Si junction, and its demonstration toward high speed rectifier circuit upto 1 MHz. Newly developed <em>p</em>-type Cu-doped NiWO<small><sub>4</sub></small> was synthesized by solid-state reaction, and its thin-film form was successfully deposited by e-beam evaporation method. From X-ray diffraction and Raman spectroscopy, it is confirmed that all the deposited Cu-doped NiWO<small><sub>4</sub></small> films showed amorphous phases independent from substrate heating temperature. UV-visible transmittance and electrical resistivity value decreases, as increasing substrate heating temperature from 100 to 300 <small><sup>o</sup></small>C, revealing that optical transparency and electrical conductivity were in the trade-off relation in Cu-doped NiWO<small><sub>4</sub></small> film. By fabricating <em>p</em>-Ni<small><sub>0.8</sub></small>Cu<small><sub>0.2</sub></small>WO<small><sub>4</sub></small>/<em>n</em>-Si heterostructure diodes, a highly rectifying behaviour can be attained with an ideality factor and an on/off current ratio of 1.23 and ~10<small><sup>4</sup></small>, respectively. When we configure the AC to DC converting half-wave rectifier circuit with <em>p</em>-Ni<small><sub>0.8</sub></small>Cu<small><sub>0.2</sub></small>WO<small><sub>4</sub></small>/<em>n</em>-Si diode, a high-speed operation upto 1 MHz was demonstrated, as strongly supporting that our newly developed <em>p</em>-type oxide can be utilized as a key component in practical oxide-based electronics such as radio frequency identification.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"51 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486533","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}
Yuye Chou, Tao Zheng, Rui Liu, Jingjing Liu, Xiangdong Xue, Wengang Liu, Jian Liu
Electrochemical CO₂ reduction to syngas (CO + H₂) offers a promising way to produce valuable chemicals and fuels from renewable electricity and captured CO₂, but developing efficient, tunable catalysts to control the syngas ratio remains challenging. Herein, we demonstrated the rational design of bimetallic Ni/Co single-atom catalysts for efficient, tunable CO₂ electroreduction to syngas. Adsorption energy descriptor was introduced to identify optimal Metal-N4 sites for CO₂ electroreduction, highlighting Ni-N4 and Co-N4 as promising candidates. Isolated Ni and Co atoms were precisely an-chored into nitrogen-doped carbon supports, forming Ni/Co-N4 active sites. Mechanistic insights revealed that atomic Ni-N4 sites selectively adsorbed and activated CO₂ to form CO, while Co-N4 sites bound H₂O to facilitate hydrogen evolution. This synergy between Co/Ni single-atom sites enabled high Faradaic efficiency and a tunable CO/H₂ ratio from 1:2.3 to 2.8:1. This research offers strategies for designing single-atom catalysts to achieve precise product selectivity control over energy-related applications.
{"title":"Bimetallic Ni/Co Single-Atom Catalysts Guided by Energy Descriptor for Efficient CO2 Electroreduction to Syngas","authors":"Yuye Chou, Tao Zheng, Rui Liu, Jingjing Liu, Xiangdong Xue, Wengang Liu, Jian Liu","doi":"10.1039/d4qi03138e","DOIUrl":"https://doi.org/10.1039/d4qi03138e","url":null,"abstract":"Electrochemical CO₂ reduction to syngas (CO + H₂) offers a promising way to produce valuable chemicals and fuels from renewable electricity and captured CO₂, but developing efficient, tunable catalysts to control the syngas ratio remains challenging. Herein, we demonstrated the rational design of bimetallic Ni/Co single-atom catalysts for efficient, tunable CO₂ electroreduction to syngas. Adsorption energy descriptor was introduced to identify optimal Metal-N4 sites for CO₂ electroreduction, highlighting Ni-N4 and Co-N4 as promising candidates. Isolated Ni and Co atoms were precisely an-chored into nitrogen-doped carbon supports, forming Ni/Co-N4 active sites. Mechanistic insights revealed that atomic Ni-N4 sites selectively adsorbed and activated CO₂ to form CO, while Co-N4 sites bound H₂O to facilitate hydrogen evolution. This synergy between Co/Ni single-atom sites enabled high Faradaic efficiency and a tunable CO/H₂ ratio from 1:2.3 to 2.8:1. This research offers strategies for designing single-atom catalysts to achieve precise product selectivity control over energy-related applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"49 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486536","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 phosphides (TMPs) have gained widespread applications in the field of electrochemical energy storage. However, controlled morphology and multi-site dynamic activation remain challenging. Herein, a thin-walled, hollow, and porous ternary Co-Ni-Mn metal phosphide was synthesized on carbon cloth (CC/CoNiMn-P) via a mixed-solvent-assisted etching method combined with gas-phase phosphidation, using Co-MOF and CoNiMn(OH)2 triangular nanosheet arrays as templates. The mild phosphating process maintained the hollow porous structure of the master plate. The DFT calculation further proved that the insertion of P improved the adsorption of the electrode to OH-, thus improving the conductivity and thermal stability. Combined with the synergistic effect of ternary metals, the electrode showed a high specific capacity 2247 F•g-1 at a current density of 1 A•g-1, and excellent rate performance (with 90.2% retention at 8 A•g⁻¹). When used in hybrid supercapacitors (HSCs), the CC/CoNiMn-P-500//AC HSC achieves a high energy density of 45.7 Wh•kg⁻¹ at a power density of 344.8 W•kg⁻¹, with a capacitance retention of 84.3% after 10,000 cycles. This work provides a novel approach for constructing electrode materials with well-defined hierarchical structures for supercapacitor and energy storage applications.
{"title":"Conformal phosphating hierarchical interface of CC/CoNiMn-P for hybrid supercapacitors with high rate stable cycling","authors":"Dongxu Wang, Feng Zhu, Yupeng Dang, JingZe Luan, MingQuan Li, Zexiang Shen, Dandan Han","doi":"10.1039/d5qi00123d","DOIUrl":"https://doi.org/10.1039/d5qi00123d","url":null,"abstract":"Transition metal phosphides (TMPs) have gained widespread applications in the field of electrochemical energy storage. However, controlled morphology and multi-site dynamic activation remain challenging. Herein, a thin-walled, hollow, and porous ternary Co-Ni-Mn metal phosphide was synthesized on carbon cloth (CC/CoNiMn-P) via a mixed-solvent-assisted etching method combined with gas-phase phosphidation, using Co-MOF and CoNiMn(OH)2 triangular nanosheet arrays as templates. The mild phosphating process maintained the hollow porous structure of the master plate. The DFT calculation further proved that the insertion of P improved the adsorption of the electrode to OH-, thus improving the conductivity and thermal stability. Combined with the synergistic effect of ternary metals, the electrode showed a high specific capacity 2247 F•g-1 at a current density of 1 A•g-1, and excellent rate performance (with 90.2% retention at 8 A•g⁻¹). When used in hybrid supercapacitors (HSCs), the CC/CoNiMn-P-500//AC HSC achieves a high energy density of 45.7 Wh•kg⁻¹ at a power density of 344.8 W•kg⁻¹, with a capacitance retention of 84.3% after 10,000 cycles. This work provides a novel approach for constructing electrode materials with well-defined hierarchical structures for supercapacitor and energy storage applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"422 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486532","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}
Polyoxometalate (POMs), as a class of structurally well-defined compounds with excellent charge trapping and releasing capabilities, are ideal candidates for high-performance memory devices. However, their performance optimization in conventional environments remains limited. Here, three water-soluble organic-inorganic hybridized POMs-based nonvolatile memory devices are proposed. Pure inorganic POM clusters are assembled with organic ligands by electrostatic and covalent interactions. This approach that modulates the hydrophilicity and stability of the resulting compounds. Structural analysis and two-dimensional correlation infrared spectroscopy (2D-COS-IR) reveal that hydrogen bonding and π-conjugation interactions may influence the performance of POMs-based memristors. The resistive switching (RS) mechanism could be controlled by the synergistic effect of space-charge-limited current and oxygen vacancies. Notably, the FTO/VB3/Ag, modified with hydrogen bonding and constructed with Li+, exhibits rewritable RS behavior and a high ON/OFF current ratio of 2.62 × 104, even at 270 °C and various harsh environments. Additionally, this study is the first example of investigating the dynamics of weak forces in the structure of the device during heating using 2D-COS-IR, and elucidating the mechanisms that memristors enable stable operation at high temperatures. This work explores the relationship between structure and RS performance of the material, proposes a method for designing and enhancing memristor performance at the molecular level, and offers a theoretical foundation for the development of high-performance memory devices for extreme environments.
{"title":"Enhancing the performance of polyoxometalate-based memristors in harsh environments based on hydrogen bonding cooperative π-conjugation interaction","authors":"Mingze Meng, Yiqun Gao, Yi-Ping Chen, Hao-Hong Li, Xiaohui Huang","doi":"10.1039/d5qi00030k","DOIUrl":"https://doi.org/10.1039/d5qi00030k","url":null,"abstract":"Polyoxometalate (POMs), as a class of structurally well-defined compounds with excellent charge trapping and releasing capabilities, are ideal candidates for high-performance memory devices. However, their performance optimization in conventional environments remains limited. Here, three water-soluble organic-inorganic hybridized POMs-based nonvolatile memory devices are proposed. Pure inorganic POM clusters are assembled with organic ligands by electrostatic and covalent interactions. This approach that modulates the hydrophilicity and stability of the resulting compounds. Structural analysis and two-dimensional correlation infrared spectroscopy (2D-COS-IR) reveal that hydrogen bonding and π-conjugation interactions may influence the performance of POMs-based memristors. The resistive switching (RS) mechanism could be controlled by the synergistic effect of space-charge-limited current and oxygen vacancies. Notably, the FTO/VB3/Ag, modified with hydrogen bonding and constructed with Li+, exhibits rewritable RS behavior and a high ON/OFF current ratio of 2.62 × 104, even at 270 °C and various harsh environments. Additionally, this study is the first example of investigating the dynamics of weak forces in the structure of the device during heating using 2D-COS-IR, and elucidating the mechanisms that memristors enable stable operation at high temperatures. This work explores the relationship between structure and RS performance of the material, proposes a method for designing and enhancing memristor performance at the molecular level, and offers a theoretical foundation for the development of high-performance memory devices for extreme environments.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"53 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486520","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}
Mao He, Xiaoying Peng, Suqin Wu, Bin Lei, Shuai Xiong, Qin Luo, Zongxing Tu, Xiaoxue Lin, Guiming Peng
The photocatalytic two-electron oxygen reduction offers a sustainable method to produce hydrogen peroxide (H2O2). The efficiency of carbon nitride (CN) in this process is hindered by the serious charge recombination and slow diffusion of oxygen. This work reports the thermal vapor-assisted surface chemical modification of CN by 4-aminobenzoyl groups (PABA/CN), which alters the conjugation system, extends the light absorption range, and enhances the charge separation and electron transfer. Besides, it tunes the CN surface to be hydrophobic, which forms a gas/solid/liquid triphase interface in photocatalytic H2O2 production, thus significantly improves O2 diffusion and proton supply for photosynthesis of H2O2. Photocatalytic experiments revealed that PABA/CN delivered a H2O2 yield of up to 745 μmol/g/h in pure water, 8 times as that of pristine CN, ranking among the top performances by CN-based photocatalysts. The selectivity reached 70%. Mechanism studies identified a two-step 1-electron oxygen reduction reaction pathway for H2O2 photoproduction. Overall, this work simultaneously addresses the issues of mass transfer of O2, light harvesting, and charge separation of CN in photosynthesis of H2O2 by surface chemical modification with 4-aminobenzoyl moieties which extends the π-conjugation and imparts the hydrophobic surface.
{"title":"Gas/solid/liquid triphase interface of carbon nitride for efficient photocatalytic H2O2 production","authors":"Mao He, Xiaoying Peng, Suqin Wu, Bin Lei, Shuai Xiong, Qin Luo, Zongxing Tu, Xiaoxue Lin, Guiming Peng","doi":"10.1039/d4qi03352c","DOIUrl":"https://doi.org/10.1039/d4qi03352c","url":null,"abstract":"The photocatalytic two-electron oxygen reduction offers a sustainable method to produce hydrogen peroxide (H2O2). The efficiency of carbon nitride (CN) in this process is hindered by the serious charge recombination and slow diffusion of oxygen. This work reports the thermal vapor-assisted surface chemical modification of CN by 4-aminobenzoyl groups (PABA/CN), which alters the conjugation system, extends the light absorption range, and enhances the charge separation and electron transfer. Besides, it tunes the CN surface to be hydrophobic, which forms a gas/solid/liquid triphase interface in photocatalytic H2O2 production, thus significantly improves O2 diffusion and proton supply for photosynthesis of H2O2. Photocatalytic experiments revealed that PABA/CN delivered a H2O2 yield of up to 745 μmol/g/h in pure water, 8 times as that of pristine CN, ranking among the top performances by CN-based photocatalysts. The selectivity reached 70%. Mechanism studies identified a two-step 1-electron oxygen reduction reaction pathway for H2O2 photoproduction. Overall, this work simultaneously addresses the issues of mass transfer of O2, light harvesting, and charge separation of CN in photosynthesis of H2O2 by surface chemical modification with 4-aminobenzoyl moieties which extends the π-conjugation and imparts the hydrophobic surface.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"15 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486534","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}
Kelly A. Peterson, Mark E. Bowden, Bavan P. Rajan, Tenley E. Webb, Bridgette N. Carven, Libor Kovarik, Zsombor Molnár, Mark H. Engelhard, Sandra D. Taylor, Elsa A. Cordova, Thomas W. Wietsma, Sebastian T. Mergelsberg, Christopher J. Thompson, Sebastien N. Kerisit, John S. Loring
A synthesis method for nanosized forsterite (Mg2SiO4) doped with varying concentrations of Ni and Co has been developed to support studies of carbonation-based extraction and separation of Ni and Co from mafic and ultramafic rocks. The protocol expands upon an existing sol–gel/surfactant method and is demonstrated for doping levels of 5% and 25% of Ni or Co. Variables such as metal reagents, surfactant ratios, and calcination procedures were optimized to achieve high specific surface areas and small particle sizes while minimizing secondary phase formation. Particle sizes ranged from 29 to 83 nm, and specific surface areas were between 11 and 32 m2 g−1. Metal oxide impurities were minimal, appearing only in undoped and 25% Ni-doped samples at 0.6 wt% or less. Ni and Co were only detected in the +II oxidation state and partitioned predominantly in the M1 cation site of the forsterite crystal structure. Doped nanosized forsterites prepared with this method will enable in situ experiments that can track, at the molecular scale, the fate of Ni and Co during carbonation reactions and thus provide a knowledge base for improving metal extraction and separation technologies.
{"title":"Nanometer-sized nickel and cobalt doped forsterite synthesis for investigating critical element recovery from mafic and ultramafic rocks","authors":"Kelly A. Peterson, Mark E. Bowden, Bavan P. Rajan, Tenley E. Webb, Bridgette N. Carven, Libor Kovarik, Zsombor Molnár, Mark H. Engelhard, Sandra D. Taylor, Elsa A. Cordova, Thomas W. Wietsma, Sebastian T. Mergelsberg, Christopher J. Thompson, Sebastien N. Kerisit, John S. Loring","doi":"10.1039/d4qi02586e","DOIUrl":"https://doi.org/10.1039/d4qi02586e","url":null,"abstract":"A synthesis method for nanosized forsterite (Mg<small><sub>2</sub></small>SiO<small><sub>4</sub></small>) doped with varying concentrations of Ni and Co has been developed to support studies of carbonation-based extraction and separation of Ni and Co from mafic and ultramafic rocks. The protocol expands upon an existing sol–gel/surfactant method and is demonstrated for doping levels of 5% and 25% of Ni or Co. Variables such as metal reagents, surfactant ratios, and calcination procedures were optimized to achieve high specific surface areas and small particle sizes while minimizing secondary phase formation. Particle sizes ranged from 29 to 83 nm, and specific surface areas were between 11 and 32 m<small><sup>2</sup></small> g<small><sup>−1</sup></small>. Metal oxide impurities were minimal, appearing only in undoped and 25% Ni-doped samples at 0.6 wt% or less. Ni and Co were only detected in the +<small>II</small> oxidation state and partitioned predominantly in the M1 cation site of the forsterite crystal structure. Doped nanosized forsterites prepared with this method will enable <em>in situ</em> experiments that can track, at the molecular scale, the fate of Ni and Co during carbonation reactions and thus provide a knowledge base for improving metal extraction and separation technologies.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"53 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486521","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}
Yanping Dong, Xiqiang Tian, Enxin Liu, Shoulei Huang, Muhammad Zahid
Incorporating a suitable promoter or co-catalyst is an effective strategy to improving the catalytic properties of low-content Pd catalysts. Herein, we report a straightforward method for synthesizing WN-TiO2, characterized by uniformly dispersed WN nanoparticles (NPs), which involves utilizing the evaporation induced self-assembly (EISA) process followed by nitridation. A polyol reduction method was employed to homogeneously anchor the Pd NPs on WN-TiO2 for the superior hydrogenation of lethal 4-nitrophenol (4-NP) to important fine chemicals. In our set of catalysts, the 1.0 wt% Pd@WN-TiO2 exhibited remarkable catalytic conversions rate for the 4-NP hydrogenation. Comprehensive characterization techniques were utilized to examine the impact of the synthesis technique on the interfacial properties of Pd species and their catalytic activities. The exceptional conversion rates of the 1.0wt%Pd@WN-TiO2 catalyst are attributable to its unique nanostructural characteristics and the durable synergetic interaction arises between Pd NPs and WN, which improve the distribution of Pd NPs and develop the availability of surface exposed Pd (Pd0) entities.
{"title":"Improving Hydrogenation of 4-Nitrophenol using Pd catalysts homogenously anchored on WN-TiO2: A synergistic interaction between WN and Pd nanoparticles","authors":"Yanping Dong, Xiqiang Tian, Enxin Liu, Shoulei Huang, Muhammad Zahid","doi":"10.1039/d5qi00050e","DOIUrl":"https://doi.org/10.1039/d5qi00050e","url":null,"abstract":"Incorporating a suitable promoter or co-catalyst is an effective strategy to improving the catalytic properties of low-content Pd catalysts. Herein, we report a straightforward method for synthesizing WN-TiO2, characterized by uniformly dispersed WN nanoparticles (NPs), which involves utilizing the evaporation induced self-assembly (EISA) process followed by nitridation. A polyol reduction method was employed to homogeneously anchor the Pd NPs on WN-TiO2 for the superior hydrogenation of lethal 4-nitrophenol (4-NP) to important fine chemicals. In our set of catalysts, the 1.0 wt% Pd@WN-TiO2 exhibited remarkable catalytic conversions rate for the 4-NP hydrogenation. Comprehensive characterization techniques were utilized to examine the impact of the synthesis technique on the interfacial properties of Pd species and their catalytic activities. The exceptional conversion rates of the 1.0wt%Pd@WN-TiO2 catalyst are attributable to its unique nanostructural characteristics and the durable synergetic interaction arises between Pd NPs and WN, which improve the distribution of Pd NPs and develop the availability of surface exposed Pd (Pd0) entities.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"26 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486537","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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