Tao Shao, Xianmeng Song, Zongnan Wei, Shuaibing Yang, Siying Zhang, Rong Cao, Minna Cao
Electrochemical CO2 reduction reaction (CO2RR) offers a promising pathway to convert CO2 into value-added chemicals, with CO production being a primary target. While the conversion of CO2 to CO hinges on the delicate balance of *COOH and *CO binding energies, this study introduces a series of Pd-based hybrid catalysts, Me10CB[5]-M/Pd (M=Sr, Ca, Cd), to address this challenge. The catalysts were synthesized via thermal treatment of supramolecular precursors formed by Me10CB[5], M2+, and [PdCl4]2- ions. Notably, Me10CB[5]-Sr/Pd exhibited exceptional CO selectivity (91.3% FECO at -0.7 V vs. RHE) and long-term stability. The incorporation of Me10CB[5]-Sr into the Pd catalyst system enhanced CO2 adsorption, modulated the electronic structure of Pd, and optimized the adsorption/desorption energies of critical intermediates, ultimately leading to superior CO2RR performance. This work underscores the potential of supramolecular engineering in designing high-performance electrocatalysts for CO2 conversion.
电化学二氧化碳还原反应（CO2RR）为将二氧化碳转化为高附加值化学品提供了一条前景广阔的途径，而 CO 生产则是其中的一个主要目标。将 CO2 转化为 CO 取决于 *COOH 和 *CO 结合能的微妙平衡，本研究介绍了一系列钯基混合催化剂 Me10CB[5]-M/Pd（M=Sr、Ca、Cd），以应对这一挑战。这些催化剂是通过热处理由 Me10CB[5]、M2+ 和 [PdCl4]2- 离子形成的超分子前体而合成的。值得注意的是，Me10CB[5]-Sr/Pd 表现出优异的 CO 选择性（-0.7 V 对 RHE 时 FECO 为 91.3%）和长期稳定性。在钯催化剂体系中加入 Me10CB[5]-Sr 增强了对 CO2 的吸附，调节了钯的电子结构，优化了关键中间产物的吸附/解吸能，最终实现了卓越的 CO2RR 性能。这项研究强调了超分子工程在设计用于二氧化碳转化的高性能电催化剂方面的潜力。
{"title":"Enhancing CO2 Electroreduction with Decamethylcucurbit[5]uril-Alkaline Earth Metal Modified Pd Nanoparticles","authors":"Tao Shao, Xianmeng Song, Zongnan Wei, Shuaibing Yang, Siying Zhang, Rong Cao, Minna Cao","doi":"10.1039/d4qi02135e","DOIUrl":"https://doi.org/10.1039/d4qi02135e","url":null,"abstract":"Electrochemical CO2 reduction reaction (CO2RR) offers a promising pathway to convert CO2 into value-added chemicals, with CO production being a primary target. While the conversion of CO2 to CO hinges on the delicate balance of *COOH and *CO binding energies, this study introduces a series of Pd-based hybrid catalysts, Me10CB[5]-M/Pd (M=Sr, Ca, Cd), to address this challenge. The catalysts were synthesized via thermal treatment of supramolecular precursors formed by Me10CB[5], M2+, and [PdCl4]2- ions. Notably, Me10CB[5]-Sr/Pd exhibited exceptional CO selectivity (91.3% FECO at -0.7 V vs. RHE) and long-term stability. The incorporation of Me10CB[5]-Sr into the Pd catalyst system enhanced CO2 adsorption, modulated the electronic structure of Pd, and optimized the adsorption/desorption energies of critical intermediates, ultimately leading to superior CO2RR performance. This work underscores the potential of supramolecular engineering in designing high-performance electrocatalysts for CO2 conversion.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"5 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556006","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}
Meng-Jia Shang, Han-Han Lu, Qiang Liu, Ren-He Zhou, Hui-Ying Sun, Zhen Shao, Liang Zhao, Yin-Shan Meng, Tao Liu
The development of single-chain magnets with reversible and adjustable properties is of great significance for achieving high-density information storage and switching devices with multi-stimuli responsiveness whilst remains a challenging task. In this work, we synthesized a new cyano-bridged {Fe2Co}-based coordination polymer, {[(PzTp)Fe(CN)3]2Co(Ipi)2}·2MeOH·0.5H2O (1·solv; pzTp, tetra-kis(1-pyrazolyl)borate; Ipi, 1-(4-iodophenyl)-1H-imidazole). 1·solv displayed reversible metal-to-metal electron transfer (MMET) between FeIIILS(μ-CN)CoIIHS(μ-NC)FeIIILS (LS, low spin; HS, high spin) and FeIIILS(μ-CN)CoIIILS(μ-NC)FeIILS states under alternating irradiations with 808 and 532 nm lasers, respectively, as verified by photomagnetic and in-situ photo-monitored X-ray diffraction studies. The bidirectional light irradiations induced significant changes in magnetic anisotropy and intrachain exchange interactions, demonstrating the on/off switching of single-chain magnet (SCM) behavior by 808 and 532 nm light irradiations. 1·solv underwent a thermally induced single-crystal to single-crystal (SCSC) phase transition to a desolvated {[(PzTp)Fe(CN)3]2Co(Ipi)2} (1·desolv) phase, accompanying with the MMET. Magnetic susceptibilities measurements indicated that 1·desolv exhibited thermally induced incomplete MMET behavior and field-induced nanomagnet behavior. 1·desolv also displayed a substantial dielectric anomaly during the electron transfer process, presenting a new case showing the synergetic switching of dielectric and magnetic properties. Interestingly, 1·desolv can revert to the solvated phase 1·resolv after soaking in the mother liquor, whose SCM behavior was erased by the reversible SCSC transition. This study provides a new approach for the swift and reversible control of SCM behavior via both SCSC transition and light-induced MMET.
{"title":"Reversible on–off switching of a single-chain magnet via single-crystal-to- single-crystal transition- and light-induced metal-to-metal electron transfer","authors":"Meng-Jia Shang, Han-Han Lu, Qiang Liu, Ren-He Zhou, Hui-Ying Sun, Zhen Shao, Liang Zhao, Yin-Shan Meng, Tao Liu","doi":"10.1039/d4qi01691b","DOIUrl":"https://doi.org/10.1039/d4qi01691b","url":null,"abstract":"The development of single-chain magnets with reversible and adjustable properties is of great significance for achieving high-density information storage and switching devices with multi-stimuli responsiveness whilst remains a challenging task. In this work, we synthesized a new cyano-bridged {Fe<small><sub>2</sub></small>Co}-based coordination polymer, {[(<small><sup>Pz</sup></small>Tp)Fe(CN)<small><sub>3</sub></small>]<small><sub>2</sub></small>Co(Ipi)<small><sub>2</sub></small>}·2MeOH·0.5H<small><sub>2</sub></small>O (<strong>1·solv</strong>; <small><sup>pz</sup></small>Tp, tetra-kis(1-pyrazolyl)borate; Ipi, 1-(4-iodophenyl)-1H-imidazole). <strong>1·solv</strong> displayed reversible metal-to-metal electron transfer (MMET) between Fe<small><sup>III</sup></small><small><sub>LS</sub></small>(<em>μ</em>-CN)Co<small><sup>II</sup></small><small><sub>HS</sub></small>(<em>μ</em>-NC)Fe<small><sup>III</sup></small><small><sub>LS</sub></small> (LS, low spin; HS, high spin) and Fe<small><sup>III</sup></small><small><sub>LS</sub></small>(<em>μ</em>-CN)Co<small><sup>III</sup></small><small><sub>LS</sub></small>(<em>μ</em>-NC)Fe<small><sup>II</sup></small><small><sub>LS</sub></small> states under alternating irradiations with 808 and 532 nm lasers, respectively, as verified by photomagnetic and <em>in-situ</em> photo-monitored X-ray diffraction studies. The bidirectional light irradiations induced significant changes in magnetic anisotropy and intrachain exchange interactions, demonstrating the on/off switching of single-chain magnet (SCM) behavior by 808 and 532 nm light irradiations. <strong>1·solv</strong> underwent a thermally induced single-crystal to single-crystal (SCSC) phase transition to a desolvated {[(<small><sup>Pz</sup></small>Tp)Fe(CN)<small><sub>3</sub></small>]<small><sub>2</sub></small>Co(Ipi)<small><sub>2</sub></small>} (<strong>1·desolv</strong>) phase, accompanying with the MMET. Magnetic susceptibilities measurements indicated that <strong>1·desolv</strong> exhibited thermally induced incomplete MMET behavior and field-induced nanomagnet behavior. <strong>1·desolv</strong> also displayed a substantial dielectric anomaly during the electron transfer process, presenting a new case showing the synergetic switching of dielectric and magnetic properties. Interestingly, <strong>1·desolv</strong> can revert to the solvated phase <strong>1·resolv</strong> after soaking in the mother liquor, whose SCM behavior was erased by the reversible SCSC transition. This study provides a new approach for the swift and reversible control of SCM behavior via both SCSC transition and light-induced MMET.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"238 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541124","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}
In recent years, great efforts have been devoted to develop low or intermediate temperature solid oxide fuel cells (SOFCs) operating at 500–800 °C. Lowering the operating temperature can suppress degradation of components and extend the range of acceptable material selection. Moreover, this is also favorable for improving cell durability and reducing the system cost. However, reducing the operating temperature decreases the electrode kinetics and leads to large interfacial polarization resistances, especially prominent for the oxygen reduction reaction (ORR) at the cathode. This review introduces the research progress of nanoengineering of electrodes employed for SOFCs operating at low and intermediate temperatures, including nanofiber-, nanotube- and nanowire-based cathodes, nanocoatings fabricated by atomic layer deposition (ALD) and pulsed laser deposition (PLD), in situ exsolution nanoparticles from perovskite materials, infiltration nanoparticles, single-atom based cathode catalysts, triple-conducting oxide cathodes, etc. Finally, we also provide future research directions on nanoengineering of cathodes for next-generation SOFCs.
{"title":"Advances in nanoengineering of cathodes for next-generation solid oxide fuel cells","authors":"Chunwen Sun","doi":"10.1039/D4QI02451F","DOIUrl":"10.1039/D4QI02451F","url":null,"abstract":"<p >In recent years, great efforts have been devoted to develop low or intermediate temperature solid oxide fuel cells (SOFCs) operating at 500–800 °C. Lowering the operating temperature can suppress degradation of components and extend the range of acceptable material selection. Moreover, this is also favorable for improving cell durability and reducing the system cost. However, reducing the operating temperature decreases the electrode kinetics and leads to large interfacial polarization resistances, especially prominent for the oxygen reduction reaction (ORR) at the cathode. This review introduces the research progress of nanoengineering of electrodes employed for SOFCs operating at low and intermediate temperatures, including nanofiber-, nanotube- and nanowire-based cathodes, nanocoatings fabricated by atomic layer deposition (ALD) and pulsed laser deposition (PLD), <em>in situ</em> exsolution nanoparticles from perovskite materials, infiltration nanoparticles, single-atom based cathode catalysts, triple-conducting oxide cathodes, <em>etc</em>. Finally, we also provide future research directions on nanoengineering of cathodes for next-generation SOFCs.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 23","pages":" 8164-8182"},"PeriodicalIF":6.1,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542061","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}
Dalma Gál, Daniel Buzsaki, Balázs Szathmári, Tamas Holczbauer, Antal Udvardy, Júlia Kertész Szilágyiné, Denis Kargin, Clemens Bruhn, Rudolf Pietschnig, Zsolt Kelemen
The special C-C bond in the icosahedral closo-dicarbadodecaboranes and its high plasticity have been highlighted several times, which is reflected in the ease of tuning the C-C bond distance with different substituents. Apart from this special case, the other bonds within the carborane clusters have not been investigated yet. DFT calculations demonstrated that the elongation of C-B and B-B bonds is ruled by the same effects as the well investigated C-C bond; however, stretching of B-B requires more energy. These results indicate that the bonds of the carborane clusters do not differ significantly; in fact they possess similar properties. The promising computational results encouraged us to synthetize the most promising derivatives. The distinct tuning was achieved by the variation of π-donor substituents. In the case of the disulfanide derivative of meta-carborane derivative, the B9-B10 bond distance is elongated up to 1.92(2) Å.
{"title":"The „chemical tug-of-war” in carborane clusters: distinct tuning on different sides of the cluster","authors":"Dalma Gál, Daniel Buzsaki, Balázs Szathmári, Tamas Holczbauer, Antal Udvardy, Júlia Kertész Szilágyiné, Denis Kargin, Clemens Bruhn, Rudolf Pietschnig, Zsolt Kelemen","doi":"10.1039/d4qi02566k","DOIUrl":"https://doi.org/10.1039/d4qi02566k","url":null,"abstract":"The special C-C bond in the icosahedral closo-dicarbadodecaboranes and its high plasticity have been highlighted several times, which is reflected in the ease of tuning the C-C bond distance with different substituents. Apart from this special case, the other bonds within the carborane clusters have not been investigated yet. DFT calculations demonstrated that the elongation of C-B and B-B bonds is ruled by the same effects as the well investigated C-C bond; however, stretching of B-B requires more energy. These results indicate that the bonds of the carborane clusters do not differ significantly; in fact they possess similar properties. The promising computational results encouraged us to synthetize the most promising derivatives. The distinct tuning was achieved by the variation of π-donor substituents. In the case of the disulfanide derivative of meta-carborane derivative, the B9-B10 bond distance is elongated up to 1.92(2) Å.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"239 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542060","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}
Zhou Fang, Yi Tong, Yue Yang, Anjun Hu, Jianping Long, Yan Zhao, Xin Lai, Daojiang Gao, Mengjiao Liu
Recently, aqueous zinc ion batteries (AZIBs) emerge as novel energy storage devices for their low cost, favorable safety and high theoretical capacity. However, the layered ammonium vanadates, as the promising cathode materials, suffer from the slow Zn2+ diffusion kinetics due to the strong electrostatic interactions between Zn2+ and [VOn] layer, irreversible deammoniation and poor conductivity. In this work, Ag+ intercalated NH4V4O10 (ANVO) was synthesized as high-performance cathodes for AZIBs. The pre-intercalated Ag+ interacts with the lattice oxygen to form strong Ag-O bonds, acting as "pillar" to stabilize the layered structure in electrochemical reactions. Moreover, the in-situ generated Ag0 during the discharge process favors enhancement in electronic conductivity of the material. The dual effects of Ag+ intercalation endow the AVNO with high structure stability and fast electron/Zn2+ diffusion kinetics, leading to the superior electrochemical performance. Specially, it exhibits ultralong cycling life (with 95% capacity retention after 1000 cycles at 5 A g–1) as well as competitive rate performance (473.6 mAh g−1 at 0.2 A g−1 and 286.6 mAh g–1 at 10 A g–1). This research provides valuable insights for designing high capacity and long-life cathode materials.
近来，锌离子水电池（AZIBs）以其低成本、良好的安全性和高理论容量成为新型储能设备。然而，层状钒酸铵作为一种前景广阔的阴极材料，却因 Zn2+ 与 [VOn] 层之间强烈的静电作用而导致 Zn2+ 扩散动力学缓慢、不可逆脱氨和导电性差等问题。在这项工作中，合成了作为 AZIBs 高性能阴极的 Ag+ 插层 NH4V4O10（ANVO）。预插层的 Ag+ 与晶格氧相互作用形成强 Ag-O 键，在电化学反应中起到稳定层状结构的 "支柱 "作用。此外，放电过程中原位生成的 Ag0 有利于增强材料的电子导电性。Ag+ 插层的双重效应赋予了 AVNO 材料高度的结构稳定性和快速的电子/Zn2+ 扩散动力学，从而使其具有优异的电化学性能。特别是，它具有超长的循环寿命（在 5 A g-1 条件下循环 1000 次后容量保持率为 95%）和极具竞争力的速率性能（在 0.2 A g-1 条件下为 473.6 mAh g-1，在 10 A g-1 条件下为 286.6 mAh g-1）。这项研究为设计高容量、长寿命阴极材料提供了宝贵的见解。
{"title":"Dual effects of Ag+ intercalation boosting kineties and stability of NH4V4O10 cathodes for enhanced zinc ion storage","authors":"Zhou Fang, Yi Tong, Yue Yang, Anjun Hu, Jianping Long, Yan Zhao, Xin Lai, Daojiang Gao, Mengjiao Liu","doi":"10.1039/d4qi01942c","DOIUrl":"https://doi.org/10.1039/d4qi01942c","url":null,"abstract":"Recently, aqueous zinc ion batteries (AZIBs) emerge as novel energy storage devices for their low cost, favorable safety and high theoretical capacity. However, the layered ammonium vanadates, as the promising cathode materials, suffer from the slow Zn2+ diffusion kinetics due to the strong electrostatic interactions between Zn2+ and [VOn] layer, irreversible deammoniation and poor conductivity. In this work, Ag+ intercalated NH4V4O10 (ANVO) was synthesized as high-performance cathodes for AZIBs. The pre-intercalated Ag+ interacts with the lattice oxygen to form strong Ag-O bonds, acting as \"pillar\" to stabilize the layered structure in electrochemical reactions. Moreover, the in-situ generated Ag0 during the discharge process favors enhancement in electronic conductivity of the material. The dual effects of Ag+ intercalation endow the AVNO with high structure stability and fast electron/Zn2+ diffusion kinetics, leading to the superior electrochemical performance. Specially, it exhibits ultralong cycling life (with 95% capacity retention after 1000 cycles at 5 A g–1) as well as competitive rate performance (473.6 mAh g−1 at 0.2 A g−1 and 286.6 mAh g–1 at 10 A g–1). This research provides valuable insights for designing high capacity and long-life cathode materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"33 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541365","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}
Hyeonggeun Choi, Seunghwan Jo, Ki Hoon Shin, HeeYoung Lim, Liting Zhang, Keon Beom Lee, Young-Woo Lee, Jung Inn Sohn
Nonprecious NiMo composites are promising hydrogen evolution reaction electrocatalysts due to their Pt-like catalytic surface. However, because of hydroxide adsorption in alkaline media, the oxidative elution of Mo deteriorates structural and catalytic stability. Herein, Cu and Co incorporated NiMo composite (NiMoCuCo) is prepared as an active and durable hydrogen evolution reaction (HER) electrocatalyst by direct electrochemical deposition. The low electronegativities of Cu and Co effectively reduce the charge valence state of metals and the zeta potential of electrocatalysts, ameliorating the surface electronegativity. NiMoCuCo shows a low overpotential of 53 mV at a current density of 10 mA cm−2 and a slight overpotential increase of 0.01 mV h−1 (1.8 %) after long-term stability test for 100 h at a current density of 100 mA cm−2, outperforming the NiMo and NiMoCu. Ex-situ analyses demonstrate that the NiMoCuCo exhibits a reduced charge valence state of Mo without significant degradation after the long-term stability test. Furthermore, Co in the NiMoCuCo acts as the OH adsorption site on behalf of Mo, owing to the reduced surface electronegativity of Mo and strong OH affinity. This results in the balance between the water dissociation and HER kinetics of NiMo composites, leading to excellent HER activity and stability.
非贵金属镍钼复合材料具有类似铂的催化表面，是一种很有前途的氢进化反应电催化剂。然而，由于氢氧化物在碱性介质中的吸附作用，钼的氧化洗脱会降低其结构和催化稳定性。在此，通过直接电化学沉积法制备了铜和钴结合的镍钼复合材料（NiMoCuCo），作为一种活性持久的氢进化反应（HER）电催化剂。Cu 和 Co 的低电负性有效降低了金属的电荷价态和电催化剂的 Zeta 电位，改善了表面电负性。在电流密度为 10 mA cm-2 时，NiMoCuCo 的过电位较低，仅为 53 mV；在电流密度为 100 mA cm-2 时，经过 100 小时的长期稳定性测试后，过电位略有增加，仅为 0.01 mV h-1 （1.8%），优于 NiMo 和 NiMoCu。原位分析表明，NiMoCuCo 在长期稳定性测试后，钼的电荷价态有所降低，但没有出现明显的降解。此外，由于 Mo 的表面电负性降低，且与 OH 有很强的亲和力，NiMoCuCo 中的 Co 代替 Mo 成为 OH 的吸附位点。这使得 NiMo 复合材料的水解离和 HER 动力学之间达到了平衡，从而获得了优异的 HER 活性和稳定性。
{"title":"Highly active and durable NiMoCuCo catalyst with moderated hydroxide adsorption energy for efficient hydrogen evolution reaction","authors":"Hyeonggeun Choi, Seunghwan Jo, Ki Hoon Shin, HeeYoung Lim, Liting Zhang, Keon Beom Lee, Young-Woo Lee, Jung Inn Sohn","doi":"10.1039/d4qi01947d","DOIUrl":"https://doi.org/10.1039/d4qi01947d","url":null,"abstract":"Nonprecious NiMo composites are promising hydrogen evolution reaction electrocatalysts due to their Pt-like catalytic surface. However, because of hydroxide adsorption in alkaline media, the oxidative elution of Mo deteriorates structural and catalytic stability. Herein, Cu and Co incorporated NiMo composite (NiMoCuCo) is prepared as an active and durable hydrogen evolution reaction (HER) electrocatalyst by direct electrochemical deposition. The low electronegativities of Cu and Co effectively reduce the charge valence state of metals and the zeta potential of electrocatalysts, ameliorating the surface electronegativity. NiMoCuCo shows a low overpotential of 53 mV at a current density of 10 mA cm−2 and a slight overpotential increase of 0.01 mV h−1 (1.8 %) after long-term stability test for 100 h at a current density of 100 mA cm−2, outperforming the NiMo and NiMoCu. Ex-situ analyses demonstrate that the NiMoCuCo exhibits a reduced charge valence state of Mo without significant degradation after the long-term stability test. Furthermore, Co in the NiMoCuCo acts as the OH adsorption site on behalf of Mo, owing to the reduced surface electronegativity of Mo and strong OH affinity. This results in the balance between the water dissociation and HER kinetics of NiMo composites, leading to excellent HER activity and stability.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"5 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519865","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}
Jing-Xuan Sun, Ting-Ting Zou, Yi-Chun Zhang, Yu-Li Liu, Li Dang, Shun-Ze Zhan, Hong Cai and Dan Li
Achieving exohedral metallofullerenes (ExMFs) with metal atoms selectively binding at specific spatial positions on the surface of a C60 molecule remains a considerable challenge. In this study, we report the synthesis of two decanuclear, regioisomeric cuprofullerenes with polar and tropical coordination patterns. Complex 1 features 10 CuI atoms coordinated to the CC bonds of two polar zones, stabilized by Cl− anions and protonated 4-methoxybenzylamine countercations. Complex 2 involves coordination of 10 CuI atoms in the tropical zone, utilizing trifluoroacetate (LF) and 5-methylpicolinate (Lmpic) as auxiliary ligands. Notably, complex 2 forms a typical pcu topology MOF, linking tropical cuprofullerenes through CuII(Lmpic)2 units. Theoretical calculations reveal intricate charge transfer processes that significantly influence the electronic properties of these cuprofullerenes.
{"title":"Polar and tropical regioisomeric decanuclear cuprofullerenes†","authors":"Jing-Xuan Sun, Ting-Ting Zou, Yi-Chun Zhang, Yu-Li Liu, Li Dang, Shun-Ze Zhan, Hong Cai and Dan Li","doi":"10.1039/D4QI02261K","DOIUrl":"10.1039/D4QI02261K","url":null,"abstract":"<p >Achieving exohedral metallofullerenes (ExMFs) with metal atoms selectively binding at specific spatial positions on the surface of a C<small><sub>60</sub></small> molecule remains a considerable challenge. In this study, we report the synthesis of two decanuclear, regioisomeric cuprofullerenes with polar and tropical coordination patterns. Complex <strong>1</strong> features 10 Cu<small><sup>I</sup></small> atoms coordinated to the C<img>C bonds of two polar zones, stabilized by Cl<small><sup>−</sup></small> anions and protonated 4-methoxybenzylamine countercations. Complex <strong>2</strong> involves coordination of 10 Cu<small><sup>I</sup></small> atoms in the tropical zone, utilizing trifluoroacetate (<strong>L<small><sub>F</sub></small></strong>) and 5-methylpicolinate (<strong>L<small><sub>mpic</sub></small></strong>) as auxiliary ligands. Notably, complex <strong>2</strong> forms a typical <em>pcu</em> topology MOF, linking tropical cuprofullerenes through Cu<small><sup>II</sup></small>(<strong>L<small><sub>mpic</sub></small></strong>)<small><sub>2</sub></small> units. Theoretical calculations reveal intricate charge transfer processes that significantly influence the electronic properties of these cuprofullerenes.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 23","pages":" 8324-8330"},"PeriodicalIF":6.1,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519890","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}
Anna A Mukhacheva, Vadim V. Yanshole, Mikhail V. Il’in, Alexander S. Novikov, Dmitrii Bolotin, Maksim Nailyevich Sokolov, Pavel A Abramov
The interactions of triple σ-(QIV)-hole donating chalconium cations ([Q(bPh)R]+, when Q = S, Se, Te) with nucleophilic beta-octamolybdate ([β-Mo8O26]4–) results in supramolecular association. The main focus of such assembling is on σ-(QIV)-holes recognition by the molybdate in cations with a biphenyl aromatic fragment. This leads to a remarkable diversity of the association patterns producing: i) neutral 4:1 {[Q(bPh)R]4[β-Mo8O26]} complexes with cations stacked by π-π interactions; ii) (Bu4N)+, [Q(bPh)R]+ and [β-Mo8O26]4– complexes of 2:2:1 stoichiometry with π-π interactions; iii) (Bu4N)+, [Q(bPh)R]+ and [β-Mo8O26]4– complexes of 2:2:1 stoichiometry without π-π interactions; iv) {[Q(bPh)R]2}2[β-Mo8O26] salts with π-π stacked cations but lacking any (QIV)∙∙∙O interactions. Moreover, interactions in the system can drive the reorganization of [β-Mo8O26]4– into [α-Mo8O26]4–. The halogen-bonded (QIV)∙∙∙O {(Q(bPh)R)x[β-Mo8O26]4–} (x = 2, 4) assemblies, π-π stacked cationic dimers {(Q(bPh)R)2}2+ and complicated associates based on both types interactions have been the subjects of crystallographic and computational studies.
{"title":"Chalcogen bond provided supramolecular association of beta-octamolybdate and chalconium cations","authors":"Anna A Mukhacheva, Vadim V. Yanshole, Mikhail V. Il’in, Alexander S. Novikov, Dmitrii Bolotin, Maksim Nailyevich Sokolov, Pavel A Abramov","doi":"10.1039/d4qi02258k","DOIUrl":"https://doi.org/10.1039/d4qi02258k","url":null,"abstract":"The interactions of triple σ-(QIV)-hole donating chalconium cations ([Q(bPh)R]+, when Q = S, Se, Te) with nucleophilic beta-octamolybdate ([β-Mo8O26]4–) results in supramolecular association. The main focus of such assembling is on σ-(QIV)-holes recognition by the molybdate in cations with a biphenyl aromatic fragment. This leads to a remarkable diversity of the association patterns producing: i) neutral 4:1 {[Q(bPh)R]4[β-Mo8O26]} complexes with cations stacked by π-π interactions; ii) (Bu4N)+, [Q(bPh)R]+ and [β-Mo8O26]4– complexes of 2:2:1 stoichiometry with π-π interactions; iii) (Bu4N)+, [Q(bPh)R]+ and [β-Mo8O26]4– complexes of 2:2:1 stoichiometry without π-π interactions; iv) {[Q(bPh)R]2}2[β-Mo8O26] salts with π-π stacked cations but lacking any (QIV)∙∙∙O interactions. Moreover, interactions in the system can drive the reorganization of [β-Mo8O26]4– into [α-Mo8O26]4–. The halogen-bonded (QIV)∙∙∙O {(Q(bPh)R)x[β-Mo8O26]4–} (x = 2, 4) assemblies, π-π stacked cationic dimers {(Q(bPh)R)2}2+ and complicated associates based on both types interactions have been the subjects of crystallographic and computational studies.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"52 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536573","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}
Alexander Artem'ev, Maxim Rogovoy, Ilia Odud, Maria Davydova, Marianna I Rakhmanova, Pavel A. Petrov, Valery K Brel, Oleg I. Artyushin, Konstantin Brylev, Denis G. Samsonenko, Alexey S. Berezin, Dmitry Gorbunov, Nina P. Gritsan
Coinage metal(I) complexes exhibiting thermally activated delayed fluorescence (TADF) have attracted worldwide attention as emitters for OLEDs. Reducing the decay times and increasing the quantum efficiency of such emitters is the current challenge in this hot field. To address this issue, a symmetry-based design strategy has been applied herein to obtain pseudo-symmetric complexes [M2-(tpbz)(NHC)2¬]2+ (M = Cu, Ag, Au) scaffolded by 1,2,4,5-tetrakis(diphenylphosphino)benzene (tpbz) and N-heterocyclic carbene (NHC) ligands. In the solid state, these compounds exhibit cyan-to-yellow TADF of the metal-to-ligand charge transfer type with excellent quantum yields (58–89%) and short decay times (2.5–15 µs). It has been shown that the Davydov model underlying the symmetry-based design strategy significantly increases the radiative constants of the “dimers” [M2¬(tpbz)(NHC)2¬]2+ compared to the “monomers” [M(dppb)(NHC)]+ based on 1,2-bis(diphenylphosphino)benzene (dppb). The practical potential of the designed TADF emitters has been demonstrated through their application as innovative thermo- and vapor-chromic emissive inks for advanced anti-counterfeiting labels.
{"title":"Toward highly efficient TADF-active Cu(I), Ag(I) and Au(I) carbene complexes using symmetry-based design strategy","authors":"Alexander Artem'ev, Maxim Rogovoy, Ilia Odud, Maria Davydova, Marianna I Rakhmanova, Pavel A. Petrov, Valery K Brel, Oleg I. Artyushin, Konstantin Brylev, Denis G. Samsonenko, Alexey S. Berezin, Dmitry Gorbunov, Nina P. Gritsan","doi":"10.1039/d4qi01996b","DOIUrl":"https://doi.org/10.1039/d4qi01996b","url":null,"abstract":"Coinage metal(I) complexes exhibiting thermally activated delayed fluorescence (TADF) have attracted worldwide attention as emitters for OLEDs. Reducing the decay times and increasing the quantum efficiency of such emitters is the current challenge in this hot field. To address this issue, a symmetry-based design strategy has been applied herein to obtain pseudo-symmetric complexes [M2-(tpbz)(NHC)2¬]2+ (M = Cu, Ag, Au) scaffolded by 1,2,4,5-tetrakis(diphenylphosphino)benzene (tpbz) and N-heterocyclic carbene (NHC) ligands. In the solid state, these compounds exhibit cyan-to-yellow TADF of the metal-to-ligand charge transfer type with excellent quantum yields (58–89%) and short decay times (2.5–15 µs). It has been shown that the Davydov model underlying the symmetry-based design strategy significantly increases the radiative constants of the “dimers” [M2¬(tpbz)(NHC)2¬]2+ compared to the “monomers” [M(dppb)(NHC)]+ based on 1,2-bis(diphenylphosphino)benzene (dppb). The practical potential of the designed TADF emitters has been demonstrated through their application as innovative thermo- and vapor-chromic emissive inks for advanced anti-counterfeiting labels.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"24 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541389","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}
Ruyi Bi, Jilu Zhao, Mei Yang, Jiangyan Wang, Ranbo Yu, Dan Wang
Lithium-sulfur battery has been considered as a promising next-generation energy storage device, due to its ultrahigh theoretical energy density and natural abundance of sulfur. However, the shuttle effect and sluggish redox kinetics of polysulfides hinder its commercial application. Herein, by combing the wise of material design and structure engineering, CoS2 hollow multishelled structure (HoMS) is developed to modify separator and also to establish a “vice electrode”, which effectively hinders shuttle effect and catalyzes the redox reactions. CoS2 HoMS can not only obstruct polysulfides through multiple shell barriers, but also provides a large available polar surface to effectively capture polysulfides. Additionally, CoS2 HoMS with a good conductivity could greatly accelerates the redox conversion of polysulfides and enhances the decomposition of Li2S. Moreover, these CoS2 HoMS can buffer the large volume change of sulfur during cycling and ensure good contact and stability of electrodes. As a result, lithium-sulfur battery with CoS2 HoMS modified separator exhibited a high discharge capacity of 873.1 mAh g−1 at a high rate of 1 C and delivered only 0.054% of capacity decay per cycle during 350 cycles.
{"title":"Multifunctional separator modified with catalytic multishelled structural CoS2 enables stable lithium-sulfur battery","authors":"Ruyi Bi, Jilu Zhao, Mei Yang, Jiangyan Wang, Ranbo Yu, Dan Wang","doi":"10.1039/d4qi02340d","DOIUrl":"https://doi.org/10.1039/d4qi02340d","url":null,"abstract":"Lithium-sulfur battery has been considered as a promising next-generation energy storage device, due to its ultrahigh theoretical energy density and natural abundance of sulfur. However, the shuttle effect and sluggish redox kinetics of polysulfides hinder its commercial application. Herein, by combing the wise of material design and structure engineering, CoS<small><sub>2</sub></small> hollow multishelled structure (HoMS) is developed to modify separator and also to establish a “vice electrode”, which effectively hinders shuttle effect and catalyzes the redox reactions. CoS<small><sub>2</sub></small> HoMS can not only obstruct polysulfides through multiple shell barriers, but also provides a large available polar surface to effectively capture polysulfides. Additionally, CoS<small><sub>2</sub></small> HoMS with a good conductivity could greatly accelerates the redox conversion of polysulfides and enhances the decomposition of Li<small><sub>2</sub></small>S. Moreover, these CoS<small><sub>2</sub></small> HoMS can buffer the large volume change of sulfur during cycling and ensure good contact and stability of electrodes. As a result, lithium-sulfur battery with CoS<small><sub>2</sub></small> HoMS modified separator exhibited a high discharge capacity of 873.1 mAh g<small><sub>−1</sub></small> at a high rate of 1 C and delivered only 0.054% of capacity decay per cycle during 350 cycles.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"15 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519869","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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