Li3V2(PO4)3 (LVP)-coated with N and S co-doped carbon (NSC) is investigated by DFT calculation, suggesting that NSC significantly enhances electronic conductivity and lowers Li+ migration energy barrier in comparison to the LVP-embeded pristine carbon. To experimentally confirm the theoretical prediction, three types of LVP particles embedded N and S co-doped porous carbon (LVP@NSC) materials with various nitrogen and sulfur molar ratios (N:S=1:1, 1:2 and 2:1) were prepared by a facile freeze drying-assisted wet chemical route associated with a post-annealing process. When using as a cathode for lithium-ion battery (LIB), the designed LVP@NSC with N:S=1:2 exhibits outstanding high rate capacities of 124.4 and 107.85 mA h g-1 at 2 and 20 C in a voltage window of 3.0-4.3 V, respectively, and a ultralong cycle stability of 500 times at 20 C with remaining a reversible capacity of 100.22 mA h g−1 possibly due to its smallest charge transfer resistance and highest Li+ migration coefficiency, which is in good agreement with the theoretical rediction. This work not only reveals the critical role of interaction mechanism between NSC and LVP, but also offers great potentials for high energy density LIBs applications.
通过 DFT 计算研究了包覆有 N 和 S 共掺杂碳（NSC）的 Li3V2(PO4)3（LVP），结果表明，与嵌入 LVP 的原始碳相比，NSC 能显著增强电子导电性并降低 Li+ 迁移能垒。为了在实验中证实这一理论预测，研究人员采用一种简便的冷冻干燥辅助湿化学方法，并结合一种后退火工艺，制备了三种嵌入 N 和 S 共掺多孔碳（LVP@NSC）的 LVP 粒子材料，其氮、硫摩尔比各不相同（N:S=1:1、1:2 和 2:1）。当用作锂离子电池（LIB）正极时，所设计的 N:S=1:2 的 LVP@NSC 在 3.0-4.3 V 的电压窗口内，分别于 2 C 和 20 C 条件下表现出 124.4 和 107.85 mA h g-1 的出色高倍率容量，并且在 20 C 条件下具有 500 次的超长循环稳定性，剩余可逆容量为 100.22 mA h g-1，这可能是由于它具有最小的电荷转移电阻和最高的 Li+ 迁移系数，这与理论预测结果非常吻合。这项研究不仅揭示了 NSC 与 LVP 之间相互作用机制的关键作用，还为高能量密度锂离子电池的应用提供了巨大潜力。
{"title":"Li3V2(PO4)3 particles embedded in N and S Co-doped porous carbon cathode for high performance lithium storage：An experimental and DFT study","authors":"Jinggao Wu, Canyu Zhong, Xiaofan Chen, Jing Huang","doi":"10.1039/d4qi01916d","DOIUrl":"https://doi.org/10.1039/d4qi01916d","url":null,"abstract":"Li3V2(PO4)3 (LVP)-coated with N and S co-doped carbon (NSC) is investigated by DFT calculation, suggesting that NSC significantly enhances electronic conductivity and lowers Li+ migration energy barrier in comparison to the LVP-embeded pristine carbon. To experimentally confirm the theoretical prediction, three types of LVP particles embedded N and S co-doped porous carbon (LVP@NSC) materials with various nitrogen and sulfur molar ratios (N:S=1:1, 1:2 and 2:1) were prepared by a facile freeze drying-assisted wet chemical route associated with a post-annealing process. When using as a cathode for lithium-ion battery (LIB), the designed LVP@NSC with N:S=1:2 exhibits outstanding high rate capacities of 124.4 and 107.85 mA h g-1 at 2 and 20 C in a voltage window of 3.0-4.3 V, respectively, and a ultralong cycle stability of 500 times at 20 C with remaining a reversible capacity of 100.22 mA h g−1 possibly due to its smallest charge transfer resistance and highest Li+ migration coefficiency, which is in good agreement with the theoretical rediction. This work not only reveals the critical role of interaction mechanism between NSC and LVP, but also offers great potentials for high energy density LIBs applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"246 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598377","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}
Qixian Ren, Wangfei Che, Mengmeng Chen, Chen Cui, Yabo Wu, Zhi Su
Thioantimonates containing high oxidation state Sb5+ have proven to exhibit excellent performance in the design of new materials such as infrared optics crystals and lithium-ion batteries. However, as described by the “inert pair effect”, the preparation of P-block elements containing high oxidation states in sealed systems have been a challenge. In this study, an aliovalent cation substitution strategy was used to design and synthesize three novel thioantimonates (V), respectively A4BaSb2Se8 (A = Cs, Rb) and Rb2BaSbS4Cl (RBSSC), which all contain rare [SbS4] tetrahedral units. The introduction of Ba2+ ion leads to the distortion and high-density arrangement of [SbSe4] units, which is manifested as a significant 3.7 times enhancement of the birefringence compared to the parent compound Cs3SbSe4 (0.041→0.150@1064 nm). By further introducing highly electronegative halogen atoms, the first antimony-based thiohalides (V) RBSSC was synthesized. Theoretical calculations show that the band gap of RBSSC is up to 3.674 eV, lager than those of all known antimony-based thiohalides (III). This work provides a strong evidence that the aliovalent cation substitution strategy is an effective way to find new thioantimonates (V) families, and also indicates that the cation size effect introduced by elements substitution may lead to surprising performance improvements.
{"title":"Simple Aliovalent Cation Substitution to Induce Strong Optical Anisotropy Enhancement in Rare Thioantimonates (V) Family","authors":"Qixian Ren, Wangfei Che, Mengmeng Chen, Chen Cui, Yabo Wu, Zhi Su","doi":"10.1039/d4qi02280g","DOIUrl":"https://doi.org/10.1039/d4qi02280g","url":null,"abstract":"Thioantimonates containing high oxidation state Sb5+ have proven to exhibit excellent performance in the design of new materials such as infrared optics crystals and lithium-ion batteries. However, as described by the “inert pair effect”, the preparation of P-block elements containing high oxidation states in sealed systems have been a challenge. In this study, an aliovalent cation substitution strategy was used to design and synthesize three novel thioantimonates (V), respectively A4BaSb2Se8 (A = Cs, Rb) and Rb2BaSbS4Cl (RBSSC), which all contain rare [SbS4] tetrahedral units. The introduction of Ba2+ ion leads to the distortion and high-density arrangement of [SbSe4] units, which is manifested as a significant 3.7 times enhancement of the birefringence compared to the parent compound Cs3SbSe4 (0.041→0.150@1064 nm). By further introducing highly electronegative halogen atoms, the first antimony-based thiohalides (V) RBSSC was synthesized. Theoretical calculations show that the band gap of RBSSC is up to 3.674 eV, lager than those of all known antimony-based thiohalides (III). This work provides a strong evidence that the aliovalent cation substitution strategy is an effective way to find new thioantimonates (V) families, and also indicates that the cation size effect introduced by elements substitution may lead to surprising performance improvements.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598209","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}
Nitrate–methanol co-electrolysis involving the cathodic nitrate reduction reaction (NO3RR) combined with the anodic methanol oxidation reaction (MOR) is a viable way to synchronously produce ammonia (NH3) and formate via gentle, sustainable and energy-saving “E-refining” and “E-reforming” means. An efficient bifunctional catalyst for the NO3RR and MOR is pivotal to achieve such a goal. In this work, a nitrogen-doped carbon-encapsulated nickel iron phosphide hybrid (Ni2FeP@NC) was prepared as a bifunctional catalyst for the NO3RR and MOR, and its electrochemical performance for nitrate–methanol co-electrolysis was investigated. The Ni2FeP@NC catalyst exhibited a high NH3 yield (0.47 mmol h−1 cm−2 at −0.35 V) and faradaic efficiency (FE, 93% at −0.15 V) for the NO3RR and simultaneously demonstrated high MOR efficiency for formate production (yield of 1.62 mmol h−1 cm−2 at 1.7 V and FE of around 95%). The bifunctional catalytic features of the nitrate–methanol co-electrolysis system enabled the concurrent production of NH3 and formate at low input voltage. This work provides a viable paradigm for pairwise electrosynthesis of valuable chemicals via “E-refining” and “E-reforming” through the rational design of bifunctional catalysts.
涉及阴极硝酸盐还原反应（NO3RR）和阳极甲醇氧化反应（MOR）的硝酸盐-甲醇共电解是通过温和、可持续和节能的 "E-精制 "和 "E-重整 "方式同步生产氨（NH3）和甲酸盐的可行方法。要实现这一目标，高效的 NO3RR 和 MOR 双功能催化剂至关重要。本研究制备了掺氮碳包封磷化镍铁杂化物（Ni2FeP@NC），作为 NO3RR 和 MOR 的双功能催化剂，并研究了其在硝酸-甲醇共电解中的电化学性能。Ni2FeP@NC 催化剂在 NO3RR 中表现出较高的 NH3 产率（-0.35 V 时为 0.47 mmol h-1 cm-2）和法拉第效率（FE，-0.15 V 时为 93%），同时在甲酸生产中表现出较高的 MOR 效率（1.7 V 时产率为 1.62 mmol h-1 cm-2，FE 约为 95%）。硝酸-甲醇共电解系统的双功能催化特性使其能够在低输入电压下同时生产 NH3 和甲酸盐。这项研究通过合理设计双功能催化剂，为通过 "电精制 "和 "电重整 "成对电合成有价值的化学品提供了可行的范例。
{"title":"Ammonia and formate cosynthesis via nitrate electroreduction combined with methanol electrooxidation over nitrogen-doped carbon-encapsulated nickel iron phosphide","authors":"Zongyi Wang, Jiuli Chang, Zhiyong Gao","doi":"10.1039/d4qi02350a","DOIUrl":"https://doi.org/10.1039/d4qi02350a","url":null,"abstract":"Nitrate–methanol co-electrolysis involving the cathodic nitrate reduction reaction (NO<small><sub>3</sub></small>RR) combined with the anodic methanol oxidation reaction (MOR) is a viable way to synchronously produce ammonia (NH<small><sub>3</sub></small>) and formate <em>via</em> gentle, sustainable and energy-saving “E-refining” and “E-reforming” means. An efficient bifunctional catalyst for the NO<small><sub>3</sub></small>RR and MOR is pivotal to achieve such a goal. In this work, a nitrogen-doped carbon-encapsulated nickel iron phosphide hybrid (Ni<small><sub>2</sub></small>FeP@NC) was prepared as a bifunctional catalyst for the NO<small><sub>3</sub></small>RR and MOR, and its electrochemical performance for nitrate–methanol co-electrolysis was investigated. The Ni<small><sub>2</sub></small>FeP@NC catalyst exhibited a high NH<small><sub>3</sub></small> yield (0.47 mmol h<small><sup>−1</sup></small> cm<small><sup>−2</sup></small> at −0.35 V) and faradaic efficiency (FE, 93% at −0.15 V) for the NO<small><sub>3</sub></small>RR and simultaneously demonstrated high MOR efficiency for formate production (yield of 1.62 mmol h<small><sup>−1</sup></small> cm<small><sup>−2</sup></small> at 1.7 V and FE of around 95%). The bifunctional catalytic features of the nitrate–methanol co-electrolysis system enabled the concurrent production of NH<small><sub>3</sub></small> and formate at low input voltage. This work provides a viable paradigm for pairwise electrosynthesis of valuable chemicals <em>via</em> “E-refining” and “E-reforming” through the rational design of bifunctional catalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"36 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598212","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}
Xiaowei Zhang, Dashuai Sun, Pengcheng Luo, Luhui Zhou, Zheng Lu, Jia Liu, Congcong Fan, Xinyu Ye, Hongpeng You
For efficient near-infrared (NIR) emitters, tuning their luminescence properties is important for their extended optical applications. A fundamental study of garnet-type inorganics has led to the development of a new NIR phosphor Y3ScAl4O12:Cr3+ (YSAO:Cr3+), exhibiting emission in the range of 600 to 950 nm, an internal quantum efficiency (IQE) of 84.01%, and good thermal stability at 423 K (89.7% of that at room temperature). Doping with Yb3+/Nd3+ ions helps achieve an efficient energy transfer from the Cr3+ to Yb3+/Nd3+ ions with excellent thermal stability. NIR pc-LED devices prepared using YSAO:Cr3+,Yb3+ and YSAO:Cr3+,Nd3+ can achieve high NIR output powers of 46.37 and 42.82 mW at 100 mA and photoconversion efficiencies of 20.27 and 18.84% at a driving current of 20 mA, respectively. Furthermore, the NIR pc-LED package demonstrated excellent capability for penetrating biological tissues, effectively distinguishing between pork, chicken, and beef. These results suggest that the phosphors can be utilized for non-destructive monitoring applications.
{"title":"Tunable luminescence via Cr3+–Yb3+/Nd3+ energy transfer in Cr3+ and Yb3+/Nd3+ coactivated NIR phosphors for non-destructive analysis","authors":"Xiaowei Zhang, Dashuai Sun, Pengcheng Luo, Luhui Zhou, Zheng Lu, Jia Liu, Congcong Fan, Xinyu Ye, Hongpeng You","doi":"10.1039/d4qi02260b","DOIUrl":"https://doi.org/10.1039/d4qi02260b","url":null,"abstract":"For efficient near-infrared (NIR) emitters, tuning their luminescence properties is important for their extended optical applications. A fundamental study of garnet-type inorganics has led to the development of a new NIR phosphor Y<small><sub>3</sub></small>ScAl<small><sub>4</sub></small>O<small><sub>12</sub></small>:Cr<small><sup>3+</sup></small> (YSAO:Cr<small><sup>3+</sup></small>), exhibiting emission in the range of 600 to 950 nm, an internal quantum efficiency (IQE) of 84.01%, and good thermal stability at 423 K (89.7% of that at room temperature). Doping with Yb<small><sup>3+</sup></small>/Nd<small><sup>3+</sup></small> ions helps achieve an efficient energy transfer from the Cr<small><sup>3+</sup></small> to Yb<small><sup>3+</sup></small>/Nd<small><sup>3+</sup></small> ions with excellent thermal stability. NIR pc-LED devices prepared using YSAO:Cr<small><sup>3+</sup></small>,Yb<small><sup>3+</sup></small> and YSAO:Cr<small><sup>3+</sup></small>,Nd<small><sup>3+</sup></small> can achieve high NIR output powers of 46.37 and 42.82 mW at 100 mA and photoconversion efficiencies of 20.27 and 18.84% at a driving current of 20 mA, respectively. Furthermore, the NIR pc-LED package demonstrated excellent capability for penetrating biological tissues, effectively distinguishing between pork, chicken, and beef. These results suggest that the phosphors can be utilized for non-destructive monitoring applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"37 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598211","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}
Sustainable hydrogen production by electrocatalytic water splitting is a promising energy storage technology yet challenging due to the sluggish kinetics of the oxygen evolution reaction (OER). Rationally designed robust and high-efficiency non-noble metal electrocatalysts for large-current-density OER is highly desirable for industrial-grade hydrogen production. Herein, a unique hiereachical heterostructure electrocatalyst composed of FeCo layered double hydroxides nanosheets and NiSe nanowires array grown on Ni foam (FeCo LDH/NiSe@NF) is demonstrated. The optimized FeCo LDH/NiSe@NF exhibits an excellent OER activity with low overpotentials of 230, 266 and 298 mV at current densities of 100, 500 and 1000 mA cm-2 in an alkaline solution. Especially, it can deliver 1000 mA cm-2 without much decay after the long-term stability test for 100 h. Both the experimental results and theoretical calculations reveal that reasonable construction of hiereachical heterostructure, as well as the strong interaction at the heterointerface between NiSe and FeCo LDH not only can offer sufficient exposure of the surface active sites, better electrochemical conductivity and structural stability, but also effectively optimize electronic configurations, lower the reaction energy barriers, consequently facilitating the reaction kinetics especially in large-current-density alkaline water electrolysis. Moreover, a two-electrode electrolyzer using FeCo LDH/NiSe@NF and NiCoP/NiCoSx@NF as anode and cathode only needs a cell voltage of 1.849 V to reach 1000 mA cm-2 in 30wt% KOH solution at 80 °C. The high catalytic activity and long-term stability of the catalyst at large current densities have exceeded most electrocatalysts reported, highlighting its great potential in large-scale applications.
通过电催化水分裂实现可持续制氢是一项前景广阔的储能技术，但由于氧进化反应（OER）的动力学缓慢，这项技术具有挑战性。合理设计用于大电流密度氧进化反应的坚固高效非贵金属电催化剂是工业级制氢的理想选择。本文展示了一种由生长在镍泡沫上的铁钴层状双氢氧化物纳米片和镍硒纳米线阵列（FeCo LDH/NiSe@NF）组成的独特的 "hiereachical "异质结构电催化剂。优化后的 FeCo LDH/NiSe@NF 在碱性溶液中的电流密度分别为 100、500 和 1000 mA cm-2 时，具有 230、266 和 298 mV 的低过电位，表现出卓越的 OER 活性。实验结果和理论计算均表明，合理地构建异质结构，以及 NiSe 和 FeCo LDH 在异质界面上的强相互作用，不仅能提供充分的表面活性位点暴露、更好的电化学传导性和结构稳定性，还能有效优化电子构型、降低反应能垒，从而促进反应动力学，尤其是在大电流密度碱性水电解中。此外，以 FeCo LDH/NiSe@NF 和 NiCoP/NiCoSx@NF 作为阳极和阴极的双电极电解槽在 80 °C 的 30wt% KOH 溶液中只需 1.849 V 的电池电压就能达到 1000 mA cm-2。该催化剂在大电流密度下的高催化活性和长期稳定性超过了大多数已报道的电催化剂，凸显了其在大规模应用中的巨大潜力。
{"title":"Hierarchical FeCo LDH/NiSe heterostructure electrocatalysts with rich heterointerfaces for robust water splitting at industrial-level current density","authors":"Weiwei Han, Wenyi Wang, Jiahong Liao, Yi He, Xingwang Zhang, Chunlin Yu","doi":"10.1039/d4qi02426e","DOIUrl":"https://doi.org/10.1039/d4qi02426e","url":null,"abstract":"Sustainable hydrogen production by electrocatalytic water splitting is a promising energy storage technology yet challenging due to the sluggish kinetics of the oxygen evolution reaction (OER). Rationally designed robust and high-efficiency non-noble metal electrocatalysts for large-current-density OER is highly desirable for industrial-grade hydrogen production. Herein, a unique hiereachical heterostructure electrocatalyst composed of FeCo layered double hydroxides nanosheets and NiSe nanowires array grown on Ni foam (FeCo LDH/NiSe@NF) is demonstrated. The optimized FeCo LDH/NiSe@NF exhibits an excellent OER activity with low overpotentials of 230, 266 and 298 mV at current densities of 100, 500 and 1000 mA cm-2 in an alkaline solution. Especially, it can deliver 1000 mA cm-2 without much decay after the long-term stability test for 100 h. Both the experimental results and theoretical calculations reveal that reasonable construction of hiereachical heterostructure, as well as the strong interaction at the heterointerface between NiSe and FeCo LDH not only can offer sufficient exposure of the surface active sites, better electrochemical conductivity and structural stability, but also effectively optimize electronic configurations, lower the reaction energy barriers, consequently facilitating the reaction kinetics especially in large-current-density alkaline water electrolysis. Moreover, a two-electrode electrolyzer using FeCo LDH/NiSe@NF and NiCoP/NiCoSx@NF as anode and cathode only needs a cell voltage of 1.849 V to reach 1000 mA cm-2 in 30wt% KOH solution at 80 °C. The high catalytic activity and long-term stability of the catalyst at large current densities have exceeded most electrocatalysts reported, highlighting its great potential in large-scale applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"242 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580726","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}
Exploration of non-noble-metal-based catalysts with high catalytic activity and selectivity is significant for driving innovation in green chemistry and technology. Herein, we report a facile synthesis of two-dimensional (2D) NiCo-MOF bimetallic nanosheets, which exhibited excellent catalytic performance, in terms of high conversion rate (99.9%), high selectivity (98.0-99.9%), rapid reduction kinetics (1-10 min) and mild reaction conditions (room temperature), for the catalytic hydrogenation of various nitroarenes and aldehyde compounds. These excellent catalytic performances were distinctly superior to those of other catalysts, and it can be stemmed from the unique structure of 2D NiCo-MOF bimetallic catalyst. The bimetallic system could effectively enhance the reaction selectivity with considerable reactivity, and the maximized utilization of the dispersed catalytic sites in the 2D MOF-based single-atom catalyst system could efficiently enhance the overall catalytic activity. Thus, the co-action of the synergistic effect of the bimetallic system and the maximal utilization of the catalytic sites endowed the 2D bimetallic MOF catalytic system with rapid, efficient, and highly selective catalysis under extremely gentle conditions. The reaction mechanism of the hydrogenation was investigated by using density functional theory calculations and X-ray photoelectron spectroscopy. Our study provides an appealing strategy for constructing highly efficient and selective catalysts and demonstrates the significance of 2D ultrathin MOF nanosheets in the catalysis field.
{"title":"Ultrathin 2D NiCo-MOF bimetallic nanosheets as single-atom catalysts for chemoselective hydrogenation of nitroarenes","authors":"Yu-Xuan Zhang, Yi-Jie Ma, Yu-Jia Zhao, Zi-Yan Wang, Cai-Xia Yu, Xiaoqiang Li, Lei-Lei Liu","doi":"10.1039/d4qi02343a","DOIUrl":"https://doi.org/10.1039/d4qi02343a","url":null,"abstract":"Exploration of non-noble-metal-based catalysts with high catalytic activity and selectivity is significant for driving innovation in green chemistry and technology. Herein, we report a facile synthesis of two-dimensional (2D) NiCo-MOF bimetallic nanosheets, which exhibited excellent catalytic performance, in terms of high conversion rate (99.9%), high selectivity (98.0-99.9%), rapid reduction kinetics (1-10 min) and mild reaction conditions (room temperature), for the catalytic hydrogenation of various nitroarenes and aldehyde compounds. These excellent catalytic performances were distinctly superior to those of other catalysts, and it can be stemmed from the unique structure of 2D NiCo-MOF bimetallic catalyst. The bimetallic system could effectively enhance the reaction selectivity with considerable reactivity, and the maximized utilization of the dispersed catalytic sites in the 2D MOF-based single-atom catalyst system could efficiently enhance the overall catalytic activity. Thus, the co-action of the synergistic effect of the bimetallic system and the maximal utilization of the catalytic sites endowed the 2D bimetallic MOF catalytic system with rapid, efficient, and highly selective catalysis under extremely gentle conditions. The reaction mechanism of the hydrogenation was investigated by using density functional theory calculations and X-ray photoelectron spectroscopy. Our study provides an appealing strategy for constructing highly efficient and selective catalysts and demonstrates the significance of 2D ultrathin MOF nanosheets in the catalysis field.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"35 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588604","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}
Ionic liquids (ILs) as emerging solvents have demonstrated a significant prospective in green chemistry, which can be used as green solvent, high efficiency catalyst, electrolyte, and so on. Metal–organic frameworks (MOFs), also called coordination polymers, are crystalline solids comprising of metal ions and organic linkers through coordination bonds, which are characterized by high porosity. Both ILs and MOFs have been extensively investigated by many groups all over the world, and their applications cover a wide range of fields, including but not limited to separations, catalysis to energy devices. IL/MOF composites, integrating the advantages of ILs and MOFs in one moiety, are a new class of functional materials, which have attracted increasing attention during the past decades. This paper offers an extensive overview on the design, synthesis and sustainable applications of IL/MOF composites and provides some critical viewpoints on the present challenges and future development directions. Firstly, we briefly introduced the background of ILs, MOFs, and the combination of ILs and MOFs. Afterwards, a system discussion on design and synthetic methodology for preparing IL/MOF composite. For each method, the basic chemical or operation principle and benefits/drawbacks are elaborated. Later, an overview on the sustainable applications of IL/MOF composites is provided by highlighting numerous recent representative literatures, covering carbon capture and conversion, chemical catalysis, adsorptive removal of pollutants, and acting as electrolytes and membranes in energy storage devices. Finally, research trends and insights into IL/MOF composites are outlined to extend the family of IL/MOF composites as well as their application scope. This paper is ended with challenges and future opportunities in this emerging area.
{"title":"Ionic-liquid/metal-organic-framework composites: Synthesis and emerging sustainable applications","authors":"Maiyong Zhu","doi":"10.1039/d4qi02383h","DOIUrl":"https://doi.org/10.1039/d4qi02383h","url":null,"abstract":"Ionic liquids (ILs) as emerging solvents have demonstrated a significant prospective in green chemistry, which can be used as green solvent, high efficiency catalyst, electrolyte, and so on. Metal–organic frameworks (MOFs), also called coordination polymers, are crystalline solids comprising of metal ions and organic linkers through coordination bonds, which are characterized by high porosity. Both ILs and MOFs have been extensively investigated by many groups all over the world, and their applications cover a wide range of fields, including but not limited to separations, catalysis to energy devices. IL/MOF composites, integrating the advantages of ILs and MOFs in one moiety, are a new class of functional materials, which have attracted increasing attention during the past decades. This paper offers an extensive overview on the design, synthesis and sustainable applications of IL/MOF composites and provides some critical viewpoints on the present challenges and future development directions. Firstly, we briefly introduced the background of ILs, MOFs, and the combination of ILs and MOFs. Afterwards, a system discussion on design and synthetic methodology for preparing IL/MOF composite. For each method, the basic chemical or operation principle and benefits/drawbacks are elaborated. Later, an overview on the sustainable applications of IL/MOF composites is provided by highlighting numerous recent representative literatures, covering carbon capture and conversion, chemical catalysis, adsorptive removal of pollutants, and acting as electrolytes and membranes in energy storage devices. Finally, research trends and insights into IL/MOF composites are outlined to extend the family of IL/MOF composites as well as their application scope. This paper is ended with challenges and future opportunities in this emerging area.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"45 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588787","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}
Li Li, Jian-Ge Zeng, Ning-Ning Zhang, Yu Yang-Tao, Shu-Hao Li, Yang Hua
The multifunctional stimuli-responsive photochromic materials significantly expand their application fields, including molecular switching, information storage and encryption, detection and sensing, etc. 1,4,5,8-naphthalenediimides (NDIs) have been widely used for the construction photochromic material because of their excellent modification and high redox activity. Due to single organic NDIs materials exhibit poor fatigue resistance and relatively simple functions, the increasing interest in this field focuses on constructing multifunctional crystalline hybrid photochromic materials and exploring applications based on the electron-deficient features of NDIs. Nevertheless, the development of multifunctional naphthalene diimide-based crystalline hybrid photochromic materials (NCHPMs) remains a significant challenge. This paper summarizes structure design strategies of NCHPMs with different NDIs ligands, the photochromic mechanism, application, and future prospects. This article will provide a valuable reference for researchers studying NCHPMs.
{"title":"Naphthalene diimide-based crystalline hybrid photochromic materials: Structural types, photochromic mechanism, and applications","authors":"Li Li, Jian-Ge Zeng, Ning-Ning Zhang, Yu Yang-Tao, Shu-Hao Li, Yang Hua","doi":"10.1039/d4qi02653e","DOIUrl":"https://doi.org/10.1039/d4qi02653e","url":null,"abstract":"The multifunctional stimuli-responsive photochromic materials significantly expand their application fields, including molecular switching, information storage and encryption, detection and sensing, etc. 1,4,5,8-naphthalenediimides (NDIs) have been widely used for the construction photochromic material because of their excellent modification and high redox activity. Due to single organic NDIs materials exhibit poor fatigue resistance and relatively simple functions, the increasing interest in this field focuses on constructing multifunctional crystalline hybrid photochromic materials and exploring applications based on the electron-deficient features of NDIs. Nevertheless, the development of multifunctional naphthalene diimide-based crystalline hybrid photochromic materials (NCHPMs) remains a significant challenge. This paper summarizes structure design strategies of NCHPMs with different NDIs ligands, the photochromic mechanism, application, and future prospects. This article will provide a valuable reference for researchers studying NCHPMs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"63 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588783","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}
Solid-state potassium metal batteries have increasingly gained attention as promising alternatives in large-scale energy storage due to their safety and low cost. However, these batteries usually suffer from a lack of suitable K+ conducting solid electrolytes. Herein, a new KB11H14·2Me3NBH3 complex electrolyte with high ionic conductivity and relative stability against K metal is reported. The crystal structure was solved as a monoclinic P21/c lattice. The density functional theory (DFT) calculations confirm significantly enhanced K-ion diffusion in the structure. High K-ion conductivities of 2.63 × 10−6 S cm−1 at 25 °C and 3.25 × 10−4 S cm−1 at 75 °C are achieved, putting it among the leading K+ solid conductors. Moreover, it reveals favorable interfacial stability against the K metal anode precoated by NH3B3H7. Batteries coupling the TiS2 cathode deliver long-term cycling stability. This work opens a new group of K-ion solid-state electrolytes for safe potassium metal batteries.
固态钾金属电池因其安全性和低成本而日益受到人们的关注，成为大规模能源储存的理想替代品。然而，这些电池通常缺乏合适的 K+ 导电固体电解质。本文报告了一种新的 KB11H14-2Me3NBH3 复合物电解质，它具有高离子电导率和对 K 金属的相对稳定性。晶体结构为单斜 P21/c 晶格。密度泛函理论（DFT）计算证实，该结构中的 K 离子扩散显著增强。在 25 ℃ 和 75 ℃ 条件下，其 K 离子电导率分别达到 2.63 × 10-6 S cm-1 和 3.25 × 10-4 S cm-1，跻身领先的 K+ 固体导体行列。此外，它还显示出与预涂 NH3B3H7 的 K 金属阳极良好的界面稳定性。使用 TiS2 阴极的电池具有长期循环稳定性。这项研究为安全的钾金属电池开辟了一组新的钾离子固态电解质。
{"title":"Stable solid-state potassium metal batteries enabled by a KB11H14·2Me3NBH3 complex electrolyte","authors":"Guo-guo Zhang, Pengtao Qiu, Jiaxin Kang, Zhiwei Lu, An-qi Zhu, Xiaohu Yu, Xuenian Chen","doi":"10.1039/d4qi02372b","DOIUrl":"https://doi.org/10.1039/d4qi02372b","url":null,"abstract":"Solid-state potassium metal batteries have increasingly gained attention as promising alternatives in large-scale energy storage due to their safety and low cost. However, these batteries usually suffer from a lack of suitable K<small><sup>+</sup></small> conducting solid electrolytes. Herein, a new KB<small><sub>11</sub></small>H<small><sub>14</sub></small>·2Me<small><sub>3</sub></small>NBH<small><sub>3</sub></small> complex electrolyte with high ionic conductivity and relative stability against K metal is reported. The crystal structure was solved as a monoclinic <em>P</em>2<small><sub>1</sub></small>/<em>c</em> lattice. The density functional theory (DFT) calculations confirm significantly enhanced K-ion diffusion in the structure. High K-ion conductivities of 2.63 × 10<small><sup>−6</sup></small> S cm<small><sup>−1</sup></small> at 25 °C and 3.25 × 10<small><sup>−4</sup></small> S cm<small><sup>−1</sup></small> at 75 °C are achieved, putting it among the leading K<small><sup>+</sup></small> solid conductors. Moreover, it reveals favorable interfacial stability against the K metal anode precoated by NH<small><sub>3</sub></small>B<small><sub>3</sub></small>H<small><sub>7</sub></small>. Batteries coupling the TiS<small><sub>2</sub></small> cathode deliver long-term cycling stability. This work opens a new group of K-ion solid-state electrolytes for safe potassium metal batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580727","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 chalcogenides (TMCs) are a category of electrocatalysts with favorable catalytic activity, however, the impact of oxidation and the leaching of chalcogens on the urea oxidation reaction (UOR) is not clear. Herein, 3D nanostructures of Mo-Ni3S2 nanowire arrays densely grown on nickel foam (NF) were conceived and produced using a hydrothermal treatment. During the UOR process, S and Mo are electrooxidized to generate sulfite (SO32−) and molybdate (MoO42−), with SO32− further oxidized to sulfate (SO42−). Experiments proved that adding molybdate and sulfate actively improves the oxidation activity of Ni(OH)2 and optimizes the adsorption/desorption of the UOR intermediates. The well-conceived Mo-Ni3S2 bifunctional catalyst performs well in urea-aided hydrolysis at up to 82 mA cm−2 at a voltage of 1.57 V with little performance degradation over 50 h. A promising avenue for new insights into the mechanisms underlying anionic surface reconstruction in the UOR process is offered in this work.
过渡金属卤化物（TMC）是一类具有良好催化活性的电催化剂，但卤化物的氧化和浸出对尿素氧化反应（UOR）的影响尚不清楚。在此，我们利用水热处理方法构思并制备了在泡沫镍（NF）上密集生长的 Mo-Ni3S2 纳米线阵列的三维纳米结构。在 UOR 过程中，S 和 Mo 被电氧化生成亚硫酸盐 (SO32-) 和钼酸盐 (MoO42-)，其中 SO32- 进一步氧化为硫酸盐 (SO42-)。实验证明，添加钼酸盐和硫酸盐能有效提高 Ni(OH)2 的氧化活性，并优化 UOR 中间产物的吸附/解吸。构思巧妙的 Mo-Ni3S2 双功能催化剂在尿素辅助水解中表现良好，电压为 1.57 V 时，催化活性可达 82 mA cm-2，且在 50 小时内性能几乎没有下降。
{"title":"Dissecting the role of anions in surface reconstruction in urea oxidation to maximize assisted hydrogen production","authors":"Weiwei Bao, Mameng Yang, Taotao Ai, Jie Han, Zhifeng Deng, Xiangyu Zou, Peng Jiang, Junjun Zhang","doi":"10.1039/d4qi02333a","DOIUrl":"https://doi.org/10.1039/d4qi02333a","url":null,"abstract":"Transition metal chalcogenides (TMCs) are a category of electrocatalysts with favorable catalytic activity, however, the impact of oxidation and the leaching of chalcogens on the urea oxidation reaction (UOR) is not clear. Herein, 3D nanostructures of Mo-Ni<small><sub>3</sub></small>S<small><sub>2</sub></small> nanowire arrays densely grown on nickel foam (NF) were conceived and produced using a hydrothermal treatment. During the UOR process, S and Mo are electrooxidized to generate sulfite (SO<small><sub>3</sub></small><small><sup>2−</sup></small>) and molybdate (MoO<small><sub>4</sub></small><small><sup>2−</sup></small>), with SO<small><sub>3</sub></small><small><sup>2−</sup></small> further oxidized to sulfate (SO<small><sub>4</sub></small><small><sup>2−</sup></small>). Experiments proved that adding molybdate and sulfate actively improves the oxidation activity of Ni(OH)<small><sub>2</sub></small> and optimizes the adsorption/desorption of the UOR intermediates. The well-conceived Mo-Ni<small><sub>3</sub></small>S<small><sub>2</sub></small> bifunctional catalyst performs well in urea-aided hydrolysis at up to 82 mA cm<small><sup>−2</sup></small> at a voltage of 1.57 V with little performance degradation over 50 h. A promising avenue for new insights into the mechanisms underlying anionic surface reconstruction in the UOR process is offered in this work.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"29 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580728","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：