Electrochemical water splitting produces "green hydrogen" a clean, sustainable fuel that can eventually contribute towards carbon neutrality. However, the big challenge to the widespread adoption of water-splitting technology is the complex synthesis routes that involve harmful or expensive chemicals and sluggish reaction kinetics. This work presents a scalable and environmentally friendly solvent-free strategy for the in-situ synthesis of highly dispersed CeO2/CoFe nanoparticles encapsulated within 3D hierarchically porous carbon heterostructures (CeO2/CoFe@C) via a simple pyrolysis process. The optimized Ce20/CoFe@C/750 catalyst shows a low overpotential of 114 and 191 mV at 10 mA cm-2 toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, in 1.0 M KOH. Two-electrode systems achieve a cell voltage of 1.508@10 mA cm-2 with robust stability over 500 h in 1.0 M KOH. This notable performance is attributed to hierarchically porous nanosheet architecture with a superhydrophilic surface that facilitates mass transport, rapid H2/O2 gas bubble escape, synergistically coupled CeO2/CoFe heterointerface, and abundant oxygen vacancies boost overall activity, particularly for OER. Additionally, results indicate that the optimum performance depends critically on the effect of changing Ce concentration. Density functional theory (DFT) calculations suggest that optimizing the CeO2/CoFe interface triggered CeO2 reconstruction, where oxygen migration to CoFe created vacancies. Also, this reduction of the Ce site at the interface and the availability of d and f orbitals contribute to bonding and antibonding adsorbates, thereby moderating their adsorption energy and boosting OER activity. This study demonstrates the significance of rational design concepts in catalyst structure optimization, resulting in noticeably improved overall water-splitting performance.
电化学水分离技术可以产生 "绿色氢气"，这是一种清洁、可持续的燃料，最终可实现碳中和。然而，水分离技术的广泛应用所面临的巨大挑战是复杂的合成路线，其中涉及有害或昂贵的化学品以及缓慢的反应动力学。本研究提出了一种可扩展且环保的无溶剂策略，通过简单的热解过程，在三维分层多孔碳异质结构（CeO2/CoFe@C）中原位合成高度分散的 CeO2/CoFe 纳米颗粒。优化后的 Ce20/CoFe@C/750 催化剂在 1.0 M KOH 溶液中进行氢进化反应（HER）和氧进化反应（OER）时，在 10 mA cm-2 电流条件下的过电位分别为 114 mV 和 191 mV。双电极系统在 1.0 M KOH 中的电池电压达到 1.508@10 mA cm-2，并在 500 小时内保持稳定。这种显著的性能归功于具有超亲水性表面的分层多孔纳米片结构，这种结构有利于质量传输、H2/O2 气泡的快速逸出、协同耦合的 CeO2/CoFe 异质表面，以及丰富的氧空位提高了整体活性，尤其是对 OER 而言。此外，研究结果表明，最佳性能主要取决于 Ce 浓度变化的影响。密度泛函理论（DFT）计算表明，优化 CeO2/CoFe 界面会引发 CeO2 重构，氧迁移到 CoFe 会产生空位。此外，界面上 Ce 位点的减少以及 d 和 f 轨道的可用性有助于吸附物的成键和反键，从而缓和了它们的吸附能并提高了 OER 活性。这项研究证明了合理的设计理念在催化剂结构优化中的重要意义，从而显著提高了催化剂的整体分水性能。
{"title":"Interface Engineering of Highly Stable CeO2/CoFe@C Electrocatalysts for Synergistically Boosting Overall Alkaline Water Splitting Performance","authors":"Waleed Yaseen, Karim Harrath, Guangya Li, Yusuf Bashir Bashir Adegbemiga, Suci Meng, Meng Xie, Iltaf Khan, Jimin Xie, Changkun Xia, Yuanguo Xu","doi":"10.1039/d4qi02487g","DOIUrl":"https://doi.org/10.1039/d4qi02487g","url":null,"abstract":"Electrochemical water splitting produces \"green hydrogen\" a clean, sustainable fuel that can eventually contribute towards carbon neutrality. However, the big challenge to the widespread adoption of water-splitting technology is the complex synthesis routes that involve harmful or expensive chemicals and sluggish reaction kinetics. This work presents a scalable and environmentally friendly solvent-free strategy for the in-situ synthesis of highly dispersed CeO2/CoFe nanoparticles encapsulated within 3D hierarchically porous carbon heterostructures (CeO2/CoFe@C) via a simple pyrolysis process. The optimized Ce20/CoFe@C/750 catalyst shows a low overpotential of 114 and 191 mV at 10 mA cm-2 toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, in 1.0 M KOH. Two-electrode systems achieve a cell voltage of 1.508@10 mA cm-2 with robust stability over 500 h in 1.0 M KOH. This notable performance is attributed to hierarchically porous nanosheet architecture with a superhydrophilic surface that facilitates mass transport, rapid H2/O2 gas bubble escape, synergistically coupled CeO2/CoFe heterointerface, and abundant oxygen vacancies boost overall activity, particularly for OER. Additionally, results indicate that the optimum performance depends critically on the effect of changing Ce concentration. Density functional theory (DFT) calculations suggest that optimizing the CeO2/CoFe interface triggered CeO2 reconstruction, where oxygen migration to CoFe created vacancies. Also, this reduction of the Ce site at the interface and the availability of d and f orbitals contribute to bonding and antibonding adsorbates, thereby moderating their adsorption energy and boosting OER activity. This study demonstrates the significance of rational design concepts in catalyst structure optimization, resulting in noticeably improved overall water-splitting performance.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"166 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642694","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}
Jie Yao, Zi-Jie Feng, Jinqi Hu, Guowei Du, Yu-An Xiong, Haoran Ji, Tai-Ting Sha, Xiangzhi Zhang, Zheng-Yin Jing, Qiang Pan, Huihui Hu, Yu-Meng You
Ferroelastic materials, as a significant category within the primary ferroic materials, have paved the way for the development of shape memory, superelasticity, tunable electronics, MEMS and actuators. The ferroic phase transition rules summarized by Aizu provides a theoretical guideline for material design. However, ferroelectrics and ferroelastics are to some extent intertwined with each other. Decoupling these properties is essential for optimizing material performance and developing better theoretical models. By modifying [(CH3)4N][FeCl4], a typical molecular ferroelectric that is not ferroelastic, we synthesized (Me2EtNCH3CH2Cl)FeCl4 (DMCE-FeCl4), an organic–inorganic hybrid compound that introduces ferroelasticity while maintaining ferroelectricity. DFT calculations reveal that the shape of the organic cations contributes to ferroelasticity, while their dipole moments contribute to ferroelectricity. This work advances the understanding of ferroic properties and their independent control, with implications for reconfigurable memory devices and intelligent actuators.
{"title":"Steric Effect Induced Modulation on Crystallographic Symmetry: Implementing Ferroelasticity in Molecular Ferroelectric","authors":"Jie Yao, Zi-Jie Feng, Jinqi Hu, Guowei Du, Yu-An Xiong, Haoran Ji, Tai-Ting Sha, Xiangzhi Zhang, Zheng-Yin Jing, Qiang Pan, Huihui Hu, Yu-Meng You","doi":"10.1039/d4qi02527j","DOIUrl":"https://doi.org/10.1039/d4qi02527j","url":null,"abstract":"Ferroelastic materials, as a significant category within the primary ferroic materials, have paved the way for the development of shape memory, superelasticity, tunable electronics, MEMS and actuators. The ferroic phase transition rules summarized by Aizu provides a theoretical guideline for material design. However, ferroelectrics and ferroelastics are to some extent intertwined with each other. Decoupling these properties is essential for optimizing material performance and developing better theoretical models. By modifying [(CH3)4N][FeCl4], a typical molecular ferroelectric that is not ferroelastic, we synthesized (Me2EtNCH3CH2Cl)FeCl4 (DMCE-FeCl4), an organic–inorganic hybrid compound that introduces ferroelasticity while maintaining ferroelectricity. DFT calculations reveal that the shape of the organic cations contributes to ferroelasticity, while their dipole moments contribute to ferroelectricity. This work advances the understanding of ferroic properties and their independent control, with implications for reconfigurable memory devices and intelligent actuators.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"109 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637482","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}
Due to metal halide perovskites (MHPs) possess excellent optoelectronic performances, constructing MHPs based photocatalysts is a promising strategy to promote photocatalytic uranium(VI) reduction. However, instability of MHPs in water limits their practical application, which is still a major issue and challenge. In this article, we constructed a perovskite nanotube array-based catalyst encapsulated by functionalized POMs, (HMTA)3Pb2Br7@STA-PW12, which can maintain stability in water for 10 hours under stirring conditions. It is noteworthy that, considering the “electron-sponge” property of POMs, STA-PW12 acting as electronic transfer medium not only increases the stability of the catalyst in water due to the hydrophobic long-chain STA, but also contributes to the separation of photogenerated carriers and enhances charges transfer from (HMTA)3Pb2Br7 to PW12, which enhance the photocatalytic activity significantly. The enhanced electrons carrier mobility (μe) (1.1 cm2 V-1 s-1) and carrier diffusion length (245 nm) of (HMTA)3Pb2Br7@STA-PW12 further illustrate its effective charge carriers’ transfer. DFT calculations further indicate the transition of electrons from (HMTA)3Pb2Br7 to PW12, which greatly inhibits the recombination of photogenerated carriers, thereby advancing electron transfer. Finally, the synthesized catalyst exhibits an excellent performance in the photocatalytic removal of U(VI) with removal ratio of 99.3% in the U(VI) concentration of 40 ppm after 40 min under simulated sunlight.
{"title":"Water-stable perovskite nanotube array with enhanced transport of charge carriers induced by functionalized polyoxometalate for highly-efficient photoreduction of uranium(VI)","authors":"Yan-Li Yang, Keke Guo, Xue Bai, Maochun Zhu, Siyue Wang, Shuxia Liu","doi":"10.1039/d4qi02393e","DOIUrl":"https://doi.org/10.1039/d4qi02393e","url":null,"abstract":"Due to metal halide perovskites (MHPs) possess excellent optoelectronic performances, constructing MHPs based photocatalysts is a promising strategy to promote photocatalytic uranium(VI) reduction. However, instability of MHPs in water limits their practical application, which is still a major issue and challenge. In this article, we constructed a perovskite nanotube array-based catalyst encapsulated by functionalized POMs, (HMTA)3Pb2Br7@STA-PW12, which can maintain stability in water for 10 hours under stirring conditions. It is noteworthy that, considering the “electron-sponge” property of POMs, STA-PW12 acting as electronic transfer medium not only increases the stability of the catalyst in water due to the hydrophobic long-chain STA, but also contributes to the separation of photogenerated carriers and enhances charges transfer from (HMTA)3Pb2Br7 to PW12, which enhance the photocatalytic activity significantly. The enhanced electrons carrier mobility (μe) (1.1 cm2 V-1 s-1) and carrier diffusion length (245 nm) of (HMTA)3Pb2Br7@STA-PW12 further illustrate its effective charge carriers’ transfer. DFT calculations further indicate the transition of electrons from (HMTA)3Pb2Br7 to PW12, which greatly inhibits the recombination of photogenerated carriers, thereby advancing electron transfer. Finally, the synthesized catalyst exhibits an excellent performance in the photocatalytic removal of U(VI) with removal ratio of 99.3% in the U(VI) concentration of 40 ppm after 40 min under simulated sunlight.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"6 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142609916","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}
polymeric carbon nitrides (PCN), as an emerging class of metal-free photocatalysts, have demonstrated significant potential in the field of solar energy conversion, particularly in the areas of water splitting. But the utilization of it is restricted by high carrier recombination rate and low charge transfer efficiency. In order to address these challenges, this work chooses pyridyl organic small molecules nicotinic acid and melamine to construct donor-acceptor (D-A) structured carbon nitride nanotubes. Pyridine heterocyclic rings are converged at the edge of the PCN structure via supramolecular self-assembly, facilitating the fabrication of donor-acceptor structured g-C3N4 nanotubes. Strong electronic ability of the pyridine heterocyclic rings establishes a preferential electronic transfer pathway within the D-A composite material, effectively mitigating carrier recombination within the plane. In addition, the unique hollow tubular structure of carbon nitride nanotubes enhances the visible light absorption ability, expands the surface area of the catalyst, and then increases the catalytically active sites, consequently enhancing photocatalytic performance. The photocatalytic activity of one-dimensional tubular carbon nitride doped with 100 mg nicotinic acid (designated as NA100-CN) is 2584.2 µmol g-1 h-1, which is 4.7 times that of the single PCN. This investigation elucidates the mechanism of charge transfer from D to A, describing the response mechanism of photocatalysis, with profound implications for advancing clean energy, environmental preservation, and sustainable development.
{"title":"In-situ construction of donor-acceptor structured g-C3N4 nanotubes incorporated with pyridine heterocyclic rings for efficient photocatalytic water splitting","authors":"Bo Zhang, Wenjing Luo, Luye Pan, Chenhuan Tian, Peipei Sun, Pengcheng Yan, Xianglin Zhu, Haibo Wang, Zhao Mo, Hui Xu","doi":"10.1039/d4qi02452d","DOIUrl":"https://doi.org/10.1039/d4qi02452d","url":null,"abstract":"polymeric carbon nitrides (PCN), as an emerging class of metal-free photocatalysts, have demonstrated significant potential in the field of solar energy conversion, particularly in the areas of water splitting. But the utilization of it is restricted by high carrier recombination rate and low charge transfer efficiency. In order to address these challenges, this work chooses pyridyl organic small molecules nicotinic acid and melamine to construct donor-acceptor (D-A) structured carbon nitride nanotubes. Pyridine heterocyclic rings are converged at the edge of the PCN structure via supramolecular self-assembly, facilitating the fabrication of donor-acceptor structured g-C3N4 nanotubes. Strong electronic ability of the pyridine heterocyclic rings establishes a preferential electronic transfer pathway within the D-A composite material, effectively mitigating carrier recombination within the plane. In addition, the unique hollow tubular structure of carbon nitride nanotubes enhances the visible light absorption ability, expands the surface area of the catalyst, and then increases the catalytically active sites, consequently enhancing photocatalytic performance. The photocatalytic activity of one-dimensional tubular carbon nitride doped with 100 mg nicotinic acid (designated as NA100-CN) is 2584.2 µmol g-1 h-1, which is 4.7 times that of the single PCN. This investigation elucidates the mechanism of charge transfer from D to A, describing the response mechanism of photocatalysis, with profound implications for advancing clean energy, environmental preservation, and sustainable development.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"19 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601373","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}
Dynamic luminescence materials overcome the disadvantage of traditional static anti-counterfeiting materials that are easy to imitate, but the repeated display of dynamic luminescence is still a challenge. In this work, the dynamic luminescence material Sr3Ga4O9: Sm3+ was synthesized. It was found that under 254 nm irradiation, the color of PL gradually changed from purple to pink in tens of seconds. More importantly, the dynamic luminescence intensity and self-recovery performance of the phosphor were improved by doping Zn2+. The experimental results show that this is achieved by Zn2+ acting as a new dynamic luminescence center and enhancing the density of the shallow trap. In addition, multi-color secondary dynamic luminescence, which used in the field of anti-counterfeiting, was experimentally demonstrated. This study provides a new perspective on the synergistic enhancement of dynamic luminescence intensity and rapid self-recovery.
{"title":"Enhancement of the dynamic luminescence and self-recovery performance in Zn2+ co-doped Sr3Ga4O9: Sm3+","authors":"Jingjing Li, Zhangwen Long, Xiaqing Jiang, Junyi Yang, Dacheng Zhou, Yong Yang, Qi Wang, Hao Wu, Jianbei Qiu","doi":"10.1039/d4qi02564d","DOIUrl":"https://doi.org/10.1039/d4qi02564d","url":null,"abstract":"Dynamic luminescence materials overcome the disadvantage of traditional static anti-counterfeiting materials that are easy to imitate, but the repeated display of dynamic luminescence is still a challenge. In this work, the dynamic luminescence material Sr3Ga4O9: Sm3+ was synthesized. It was found that under 254 nm irradiation, the color of PL gradually changed from purple to pink in tens of seconds. More importantly, the dynamic luminescence intensity and self-recovery performance of the phosphor were improved by doping Zn2+. The experimental results show that this is achieved by Zn2+ acting as a new dynamic luminescence center and enhancing the density of the shallow trap. In addition, multi-color secondary dynamic luminescence, which used in the field of anti-counterfeiting, was experimentally demonstrated. This study provides a new perspective on the synergistic enhancement of dynamic luminescence intensity and rapid self-recovery.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601643","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}
Gengxin Wu, Yong-Kang Zhu, Dongxia Li, Jia-Rui Wu, Yan Wang, Zhiquan Zhang, Ying-Wei Yang
Engineering ideal functional coordination polymers (CPs) via post-synthetic modification has emerged as a powerful synthetic strategy to achieve desirable functionalities and superior properties. In this work, we report a versatile ligand-strain modulation strategy that harnesses ligand strain to modify the skeleton conformation of CPs by metal node exchange. A one-dimensional (1D) crystalline CP, Ag(I)-L, featuring a curved ligand geometry, is prepared through a direct synthesis route. Exploiting polarization differences between different metal ions, we successfully regulate the ligand strain, enabling a metal node exchange process that yields another crystalline CP, Cu(I)-L, exhibiting a distinct linear parallel ligand orientation. Significantly, the complete exchange of AgNO3 to CuI is achieved via solid-liquid contact, while only partial exchange occurs under grinding. This ligand-strain engineering strategy will open new avenues in constructing functional systems and supramolecular materials through dynamic metal exchange and ligand-strain control.
通过合成后修饰来设计理想的功能配位聚合物（CPs）已成为一种实现理想功能和优异性能的强大合成策略。在这项工作中，我们报告了一种多功能配体应变调控策略，该策略利用配体应变通过金属节点交换来改变配位聚合物的骨架构象。我们通过直接合成路线制备了具有弯曲配体几何形状的一维（1D）结晶 CP--Ag(I)-L。利用不同金属离子之间的极化差异，我们成功地调节了配体应变，从而实现了金属节点交换过程，制备出了另一种结晶 CP--Cu(I)-L，其配体取向呈现出明显的线性平行。值得注意的是，AgNO3 与 CuI 的完全交换是通过固液接触实现的，而在研磨过程中只发生了部分交换。这种配体应变工程策略将为通过动态金属交换和配体应变控制构建功能系统和超分子材料开辟新的途径。
{"title":"Metal Node Exchange-Driven Ligand-Strain Modulation Strategy for One-Dimensional Crystalline Coordination Polymers","authors":"Gengxin Wu, Yong-Kang Zhu, Dongxia Li, Jia-Rui Wu, Yan Wang, Zhiquan Zhang, Ying-Wei Yang","doi":"10.1039/d4qi02422b","DOIUrl":"https://doi.org/10.1039/d4qi02422b","url":null,"abstract":"Engineering ideal functional coordination polymers (CPs) via post-synthetic modification has emerged as a powerful synthetic strategy to achieve desirable functionalities and superior properties. In this work, we report a versatile ligand-strain modulation strategy that harnesses ligand strain to modify the skeleton conformation of CPs by metal node exchange. A one-dimensional (1D) crystalline CP, Ag(I)-L, featuring a curved ligand geometry, is prepared through a direct synthesis route. Exploiting polarization differences between different metal ions, we successfully regulate the ligand strain, enabling a metal node exchange process that yields another crystalline CP, Cu(I)-L, exhibiting a distinct linear parallel ligand orientation. Significantly, the complete exchange of AgNO3 to CuI is achieved via solid-liquid contact, while only partial exchange occurs under grinding. This ligand-strain engineering strategy will open new avenues in constructing functional systems and supramolecular materials through dynamic metal exchange and ligand-strain control.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"35 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600065","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}
Tamara A. Bazhenova, Vyacheslav Kopotkov, Denis V. Korchagin, Elena Yureva, Michael V. Zhidkov, Alexey I Dmitriev, Ilya Yakushev, N. N. Efimov, Konstantin Andreevich Babeshkin, Vladimir Sergeevich Mironov, Eduard B. Yagubskii
A series of three new seven-coordinate pentagonal-bipyramidal (PBPY-7) Dy(III) complexes [Dy(L<small><sup>CH3</sup></small>)(Cy<small><sub>3</sub></small>PO)<small><sub>2</sub></small>]ClO<small><sub>4</sub></small>∙CH<small><sub>3</sub></small>CN (<strong>1</strong>), [Dy(L<small><sup>2(t-Bu)</sup></small>)(Ph<small><sub>3</sub></small>PO)<small><sub>2</sub></small>]ClO<small><sub>4</sub></small>∙0.63C<small><sub>2</sub></small>H<small><sub>5</sub></small>OH (<strong>2</strong>), [Dy(L<small><sup>OCH3</sup></small>)(Ph<small><sub>3</sub></small>PO)<small><sub>2</sub></small>]ClO<small><sub>4</sub></small>∙2H<small><sub>2</sub></small>O (<strong>3</strong>) including various chelating pentadentate ligands with a [N<small><sub>3</sub></small>O<small><sub>2</sub></small>]<small><sup>2−</sup></small> binding node in the equatorial plane, L<small><sup>CH3</sup></small> = [2,6-diacetylpyridine bis(acetylhydrazone)]<small><sup>2-</sup></small>, L<small><sup>2(t-Bu)</sup></small> = [2,6-diacetylpyridine bis(3,5di-tert-butylbenzoylhydrazone)]<small><sup>2-</sup></small>, L<small><sup>CH3</sup></small> = [2,6-diacetylpyridine bis(4-methoxybenzoylhydrazone)]<small><sup>2-</sup></small>, and two apical Cy<small><sub>3</sub></small>PO and Ph<small><sub>3</sub></small>PO ligands was synthesized and characterized structurally and magnetically. AC magnetic measurements indicated a single-molecule-magnet (SMM) behavior of <strong>1</strong>− <strong>3</strong> with energy barriers of <em>U<small><sub>eff</sub></small></em> ≈ 318−350 K. <em>Ab initio</em> calculations and crystal-field (CF) analysis showed that the ground state of <strong>1</strong>− <strong>3</strong> is a nearly pure Ising type Kramers doublet (KD<small><sub>0</sub></small>) |±15/2> <small><sub>eq</sub></small> with the long magnetic axis lying in the equatorial plane N<small><sub>3</sub></small>O<small><sub>2</sub></small>, as opposite to high-performance PBPY-7 Dy(III) SMMs (<em>U<small><sub>eff</sub></small></em> > 1000 K), where long magnetic axis of KD<small><sub>0</sub></small> |±15/2> invariably points toward apical ligands. This difference is due to competition between the apical and equatorial CFs, which has been quantitatevely examined with CF calculations. We show that the turning of the long magnetic axis (<em>g<small><sub>z</sub></small></em> ~ 19.6) from apical ligands (<em>z</em>) to the equatorial plane (<em>xy</em>) is due to crossover between the oblate |±15/2> and prolate |±1/2> ground states of Dy(III) ion, that occurs at the negative ratio <em>B<small><sub>20</sub></small>/B<small><sub>40</sub></small></em> < –0.07 of two axial CF parameters <em>B<small><sub>20</sub></small></em> and <em>B<small><sub>40</sub></small></em>. Complexes <strong>1</strong>−<strong>3</strong> refer to this case due to strong equatorial CF of the negatively charged chelate node [N<small><sub>3</sub></small>O<small><sub>2</sub></small>]<small><sup>2–</sup></small>producing large p
{"title":"Pentagonal-bipyramidal Dysprosium(III) complexes with two apical phosphine oxide ligands and equatorial pentadentate N3O2 Schiff-base ligands: Breakdown of the apical magnetic axiality by strong equatorial crystal field†","authors":"Tamara A. Bazhenova, Vyacheslav Kopotkov, Denis V. Korchagin, Elena Yureva, Michael V. Zhidkov, Alexey I Dmitriev, Ilya Yakushev, N. N. Efimov, Konstantin Andreevich Babeshkin, Vladimir Sergeevich Mironov, Eduard B. Yagubskii","doi":"10.1039/d4qi02262a","DOIUrl":"https://doi.org/10.1039/d4qi02262a","url":null,"abstract":"A series of three new seven-coordinate pentagonal-bipyramidal (PBPY-7) Dy(III) complexes [Dy(L<small><sup>CH3</sup></small>)(Cy<small><sub>3</sub></small>PO)<small><sub>2</sub></small>]ClO<small><sub>4</sub></small>∙CH<small><sub>3</sub></small>CN (<strong>1</strong>), [Dy(L<small><sup>2(t-Bu)</sup></small>)(Ph<small><sub>3</sub></small>PO)<small><sub>2</sub></small>]ClO<small><sub>4</sub></small>∙0.63C<small><sub>2</sub></small>H<small><sub>5</sub></small>OH (<strong>2</strong>), [Dy(L<small><sup>OCH3</sup></small>)(Ph<small><sub>3</sub></small>PO)<small><sub>2</sub></small>]ClO<small><sub>4</sub></small>∙2H<small><sub>2</sub></small>O (<strong>3</strong>) including various chelating pentadentate ligands with a [N<small><sub>3</sub></small>O<small><sub>2</sub></small>]<small><sup>2−</sup></small> binding node in the equatorial plane, L<small><sup>CH3</sup></small> = [2,6-diacetylpyridine bis(acetylhydrazone)]<small><sup>2-</sup></small>, L<small><sup>2(t-Bu)</sup></small> = [2,6-diacetylpyridine bis(3,5di-tert-butylbenzoylhydrazone)]<small><sup>2-</sup></small>, L<small><sup>CH3</sup></small> = [2,6-diacetylpyridine bis(4-methoxybenzoylhydrazone)]<small><sup>2-</sup></small>, and two apical Cy<small><sub>3</sub></small>PO and Ph<small><sub>3</sub></small>PO ligands was synthesized and characterized structurally and magnetically. AC magnetic measurements indicated a single-molecule-magnet (SMM) behavior of <strong>1</strong>− <strong>3</strong> with energy barriers of <em>U<small><sub>eff</sub></small></em> ≈ 318−350 K. <em>Ab initio</em> calculations and crystal-field (CF) analysis showed that the ground state of <strong>1</strong>− <strong>3</strong> is a nearly pure Ising type Kramers doublet (KD<small><sub>0</sub></small>) |±15/2> <small><sub>eq</sub></small> with the long magnetic axis lying in the equatorial plane N<small><sub>3</sub></small>O<small><sub>2</sub></small>, as opposite to high-performance PBPY-7 Dy(III) SMMs (<em>U<small><sub>eff</sub></small></em> > 1000 K), where long magnetic axis of KD<small><sub>0</sub></small> |±15/2> invariably points toward apical ligands. This difference is due to competition between the apical and equatorial CFs, which has been quantitatevely examined with CF calculations. We show that the turning of the long magnetic axis (<em>g<small><sub>z</sub></small></em> ~ 19.6) from apical ligands (<em>z</em>) to the equatorial plane (<em>xy</em>) is due to crossover between the oblate |±15/2> and prolate |±1/2> ground states of Dy(III) ion, that occurs at the negative ratio <em>B<small><sub>20</sub></small>/B<small><sub>40</sub></small></em> < –0.07 of two axial CF parameters <em>B<small><sub>20</sub></small></em> and <em>B<small><sub>40</sub></small></em>. Complexes <strong>1</strong>−<strong>3</strong> refer to this case due to strong equatorial CF of the negatively charged chelate node [N<small><sub>3</sub></small>O<small><sub>2</sub></small>]<small><sup>2–</sup></small>producing large p","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"43 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600018","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}
ASAD ULLAH, Imran Khan, Yangke Cun, Yue Liu, Zhiguo Song, Jianbei Qiu, Tatiana Grigorievna Cherkasova, Anjun Huang, Asif Ali Haider, Zhengwen Yang
Photochromic luminescent phosphor has attracted considerable attention owing to its excellent optical properties, which face the problem of limited applications. Herein, the reversible photochromic and photo-/thermal bleaching phenomenon of BiNbO4 ceramic was reported, exhibiting a color change between ivory and grey by alternating stimuli between 365/405 nm light illumination and 808 nm laser irradiation (or thermal treatment at 400 ℃). Their potential coloration mechanisms are explained by the color center model, providing a comprehensive framework for understanding the original processes. Through Er3+ ion doping, the maximum coloration contrast decreases from 24% to 20%, while simultaneously enabling the observation of bright green upconversion luminescence. Relying on the combination of re-absorption and energy transfer process, the upconversion luminescence intensity of the Er3+ ions can be effectively modulated, respectively showing a maximum regulation and recovery rate of 88.0% and 98.1%. The cycle measurements demonstrate the excellent anti-fatigue properties and reproducibility of BiNbO4: Er3+ ceramics, confirming their potential multi-functional applications in anti-counterfeiting and fingerprint acquisition.
{"title":"Dual-functional Applications of Photochromic BiNbO4: Er3+ Ceramics Based on Reversible Upconversion Luminescence Modulation","authors":"ASAD ULLAH, Imran Khan, Yangke Cun, Yue Liu, Zhiguo Song, Jianbei Qiu, Tatiana Grigorievna Cherkasova, Anjun Huang, Asif Ali Haider, Zhengwen Yang","doi":"10.1039/d4qi02440k","DOIUrl":"https://doi.org/10.1039/d4qi02440k","url":null,"abstract":"Photochromic luminescent phosphor has attracted considerable attention owing to its excellent optical properties, which face the problem of limited applications. Herein, the reversible photochromic and photo-/thermal bleaching phenomenon of BiNbO4 ceramic was reported, exhibiting a color change between ivory and grey by alternating stimuli between 365/405 nm light illumination and 808 nm laser irradiation (or thermal treatment at 400 ℃). Their potential coloration mechanisms are explained by the color center model, providing a comprehensive framework for understanding the original processes. Through Er3+ ion doping, the maximum coloration contrast decreases from 24% to 20%, while simultaneously enabling the observation of bright green upconversion luminescence. Relying on the combination of re-absorption and energy transfer process, the upconversion luminescence intensity of the Er3+ ions can be effectively modulated, respectively showing a maximum regulation and recovery rate of 88.0% and 98.1%. The cycle measurements demonstrate the excellent anti-fatigue properties and reproducibility of BiNbO4: Er3+ ceramics, confirming their potential multi-functional applications in anti-counterfeiting and fingerprint acquisition.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"20 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600019","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}
Ping Zhang, Yongchong Yu, Reyila Tuerhong, Xinyu Du, Keyi Chai, Xiaoping Su, Qiong Su, Shujuan Meng, Lijuan Han
The conventional synthetic ammonia industry is characterized by its high energy consumption, necessitating the exploration of a new environmentally sustainable method for NH3 synthesis. A prospective alternative to the Haber-Bosch process is the photocatalytic reduction nitrogen (pNRR), allowing NH3 production under room conditions. The optimization of photocatalysts, particularly through the use of single metal atom catalysts, plays a significant role in enhancing the performance of pNRR. Single metal atom catalysts offer adjustable catalytic performance and improved selectivity, making them a viable strategy for pNRR. Research has demonstrated that carbon-based and metal-based matrices effectively disperse highly active single atoms, enhancing pNRR efficiency. This review delves into utilizing atomically dispersed single atoms in pNRR on various supporters, examining theoretical frameworks and experimental findings. The review is structured into 4 sections: elucidating the mechanism and pathway of pNRR, highlighting the use of single metal atom catalysts (SMACs) where metal atoms are dispersed on carbon substrates for pNRR, showcasing SMACs with metal atoms dispersed on non-carbon substrates for pNRR, and concluding with an overview of the existing challenges and prospects of pNRR for sustainable ammonia production.
{"title":"The use of single metal atoms-based photocatalysts for the production of ammonia through photocatalytic nitrogen fixation","authors":"Ping Zhang, Yongchong Yu, Reyila Tuerhong, Xinyu Du, Keyi Chai, Xiaoping Su, Qiong Su, Shujuan Meng, Lijuan Han","doi":"10.1039/d4qi02449d","DOIUrl":"https://doi.org/10.1039/d4qi02449d","url":null,"abstract":"The conventional synthetic ammonia industry is characterized by its high energy consumption, necessitating the exploration of a new environmentally sustainable method for NH3 synthesis. A prospective alternative to the Haber-Bosch process is the photocatalytic reduction nitrogen (pNRR), allowing NH3 production under room conditions. The optimization of photocatalysts, particularly through the use of single metal atom catalysts, plays a significant role in enhancing the performance of pNRR. Single metal atom catalysts offer adjustable catalytic performance and improved selectivity, making them a viable strategy for pNRR. Research has demonstrated that carbon-based and metal-based matrices effectively disperse highly active single atoms, enhancing pNRR efficiency. This review delves into utilizing atomically dispersed single atoms in pNRR on various supporters, examining theoretical frameworks and experimental findings. The review is structured into 4 sections: elucidating the mechanism and pathway of pNRR, highlighting the use of single metal atom catalysts (SMACs) where metal atoms are dispersed on carbon substrates for pNRR, showcasing SMACs with metal atoms dispersed on non-carbon substrates for pNRR, and concluding with an overview of the existing challenges and prospects of pNRR for sustainable ammonia production.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"69 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600015","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}
Katarzyna Zakret-Drozdowska, Bożena Szermer-Olearnik, Waldemar Goldeman, Michalina Gos, Dawid Drozdowski, Anna Gągor, Tomasz M. Goszczyński
Over the past decade, considerable scientific attention has been given to adapting cobalt bis(dicarbollides) as innovative agents with various biomedical applications. Although the studied compounds show great potential in this field, only a few reports have explored broad, well-thought-out libraries of derivatives to correlate their structure with biological activity. In this study, we investigate a panel of [CoSAN]- derivatives substituted with fluorine, chlorine, bromine, and iodine in order to elucidate the impact of the halogen presence on antimicrobial action and selectivity over mammalian cells. We present the first evidence that increasing the atomic mass of a substituent improves the biological activity of a derivative. Our results demonstrate that the addition of a single iodine atom to the [CoSAN]- core results in the most selective antibacterial outcome,especially toward Staphylococcus aureus ATCC 6538. The described correlation between the lipophilicity parameter and the activity of the compounds toward both bacteria and human cell lines highlights the importance of a conscious design method to obtain the most desirable [CoSAN]--based derivatives.
{"title":"Unraveling the Correlation between Biological Effects and Halogen Substituents in Cobalt bis(dicarbollide)","authors":"Katarzyna Zakret-Drozdowska, Bożena Szermer-Olearnik, Waldemar Goldeman, Michalina Gos, Dawid Drozdowski, Anna Gągor, Tomasz M. Goszczyński","doi":"10.1039/d4qi02296c","DOIUrl":"https://doi.org/10.1039/d4qi02296c","url":null,"abstract":"Over the past decade, considerable scientific attention has been given to adapting cobalt bis(dicarbollides) as innovative agents with various biomedical applications. Although the studied compounds show great potential in this field, only a few reports have explored broad, well-thought-out libraries of derivatives to correlate their structure with biological activity. In this study, we investigate a panel of [CoSAN]<small><sup>-</sup></small> derivatives substituted with fluorine, chlorine, bromine, and iodine in order to elucidate the impact of the halogen presence on antimicrobial action and selectivity over mammalian cells. We present the first evidence that increasing the atomic mass of a substituent improves the biological activity of a derivative. Our results demonstrate that the addition of a single iodine atom to the [CoSAN]<small><sup>-</sup></small> core results in the most selective antibacterial outcome,especially toward <em>Staphylococcus aureus </em>ATCC 6538. The described correlation between the lipophilicity parameter and the activity of the compounds toward both bacteria and human cell lines highlights the importance of a conscious design method to obtain the most desirable [CoSAN]-<small><sup></sup></small>-based derivatives.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"4 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600016","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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