David Marc Jannik Krengel, Nico Graw, Regine Herbst-Irmer, Dietmar Stalke, Oliver Townrow, Malte Fischer
Heteroleptic stannylenes, featuring pendant hemilabile iminophosphorane functionalities and kinetically stabilizing terphenyl ligands, were synthesized straightforwardly through formal C–H activation. Subsequently, they were investigated for their ability to activate ammonia through N–H bond scission. By combining synthetic modifications of the ancillary ligand framework and computational analyses, detailed insights into the mechanism of NH3 activation by these systems were obtained, highlighting an activation pathway at tin without a change in oxidation state. Additionally, an observed by-product during these studies underscores the non-innocence of a lithium salt in the synthesis of the stannylene starting materials, providing access to a novel lithium stannylenoid.
{"title":"Ammonia activation using a heteroleptic stannylene and lithium stannylenoid formation facilitated by hemilabile iminophosphorane-based ligands","authors":"David Marc Jannik Krengel, Nico Graw, Regine Herbst-Irmer, Dietmar Stalke, Oliver Townrow, Malte Fischer","doi":"10.1039/d4qi02202e","DOIUrl":"https://doi.org/10.1039/d4qi02202e","url":null,"abstract":"Heteroleptic stannylenes, featuring pendant hemilabile iminophosphorane functionalities and kinetically stabilizing terphenyl ligands, were synthesized straightforwardly through formal C–H activation. Subsequently, they were investigated for their ability to activate ammonia through N–H bond scission. By combining synthetic modifications of the ancillary ligand framework and computational analyses, detailed insights into the mechanism of NH<small><sub>3</sub></small> activation by these systems were obtained, highlighting an activation pathway at tin without a change in oxidation state. Additionally, an observed by-product during these studies underscores the non-innocence of a lithium salt in the synthesis of the stannylene starting materials, providing access to a novel lithium stannylenoid.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142330149","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}
Yunli Wang, Rizhao Zhang, Xue Jinpeng, Yuqiao Chai, Bao Li, Jia Li
In the activation process of MOF materials, the formation of open metal sites (OMSs) generally enhances the binding force between the framework and C2H2/C2H4, while it can also lead to co-adsorption and significantly reduce separation efficiency. In actual working environments, OMSs are susceptible to water attacks, rendering the material more prone to damage. Herein, a heptanuclear cluster-based MOF material denoted as Ni7-MOF is reported, which is constructed using extremely inexpensive organic linkers under pure water conditions. Two guest-free materials, Ni7-100 with coordinated water and Ni7-250 with OMSs were obtained to investigate the C2H2/C2H4 separation properties and mechanisms. The enhanced adsorption and separation performance of Ni7-250 compared to Ni7-100 is primarily attributed to the appropriate pore environment within the framework, leading to the dense packing of guest molecules, and is independent of OMSs. This conclusion is further supported by grand canonical Monte Carlo (GCMC) calculations. Due to the stability of nickel ions in the pentagonal pyramid structure, Ni7-250 with OMSs exhibits high stability and can achieve structural restoration under water vapor conditions. Although environmental factors can disrupt MOF materials through OMSs, such disruption can be avoided by selecting metal ions for MOF materials based on the stability of metal ion coordination geometry. Concurrently, the regeneration of material through the adsorption of water vapor by OMSs in the air can achieve a longer service life.
{"title":"Significant Adsorption Enhancements Driven by Pore Microenvironment Tuning for Efficient C2H2/C2H4 Separation in a Chemically Stable Ni7-Cluster-based framework","authors":"Yunli Wang, Rizhao Zhang, Xue Jinpeng, Yuqiao Chai, Bao Li, Jia Li","doi":"10.1039/d4qi01856g","DOIUrl":"https://doi.org/10.1039/d4qi01856g","url":null,"abstract":"In the activation process of MOF materials, the formation of open metal sites (OMSs) generally enhances the binding force between the framework and C2H2/C2H4, while it can also lead to co-adsorption and significantly reduce separation efficiency. In actual working environments, OMSs are susceptible to water attacks, rendering the material more prone to damage. Herein, a heptanuclear cluster-based MOF material denoted as Ni7-MOF is reported, which is constructed using extremely inexpensive organic linkers under pure water conditions. Two guest-free materials, Ni7-100 with coordinated water and Ni7-250 with OMSs were obtained to investigate the C2H2/C2H4 separation properties and mechanisms. The enhanced adsorption and separation performance of Ni7-250 compared to Ni7-100 is primarily attributed to the appropriate pore environment within the framework, leading to the dense packing of guest molecules, and is independent of OMSs. This conclusion is further supported by grand canonical Monte Carlo (GCMC) calculations. Due to the stability of nickel ions in the pentagonal pyramid structure, Ni7-250 with OMSs exhibits high stability and can achieve structural restoration under water vapor conditions. Although environmental factors can disrupt MOF materials through OMSs, such disruption can be avoided by selecting metal ions for MOF materials based on the stability of metal ion coordination geometry. Concurrently, the regeneration of material through the adsorption of water vapor by OMSs in the air can achieve a longer service life.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142328882","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}
Iron oxide-based heterojunctions have garnered widespread interest in the field of photocatalysis due to their outstanding photoelectric properties. However, an in-depth understanding of the relationship between the interfacial structure and electronic properties of these heterojunctions at the atomic scale remains unclear. Access to such knowledge is critical for guiding the design and enhancing the efficiency of novel photocatalyst classes. Herein, a first-principles computational investigation focuses on the interfacial geometry, electronic structure and electron transfer mechanisms of MAPbI3/α-Fe2O3, MAPbI3/γ-Fe2O3 and MAPbI3/TiO2 heterojunctions. Compared to the classical MAPbI3/TiO2 system, the influence of iron coordination at the two octahedral iron sites of α-Fe2O3 and at both tetrahedral and octahedral iron sites of γ-Fe2O3 is investigated. It indicates that the stability of the interface on the γ-Fe2O3 (111) surface is enhanced by the octahedrally coordinated iron, whereas the subsurface Feo2 plays a pivotal role in stabilizing the interface with PbI on the α-Fe2O3-Feo1 surface. Furthermore, a notable modulation by different iron coordination of the valence band maximum charge distribution at the the α-Fe2O3/PbI and γ-Fe2O3/PbI interfaces is observed, which is pivotal for the separation and transfer of photogenerated electrons and holes. Combined with the comprehensive analysis of the band structure, electrostatic potential and average plane charge density of the heterojunction, the MAPbI3/iron oxides heterojunction is consistent with the S-scheme heterojunction mechanism. Molecular adsorption simulations of CO2, O2 and H2O show that the α-Fe2O3-Feo1/PbI interface stands out with the lowest adsorption energy, indicating its superior photocatalytic potential for CO2 reduction and dye degradation. These findings provide valuable insights into the design principles of photocatalytic materials, emphasizing the strategic manipulation of iron coordination to optimize iron-based heterojunction performance.
{"title":"Insights into the role of iron coordination in the enhanced photoactivity of MAPbI3/iron oxides heterojunctions","authors":"Wei Jian","doi":"10.1039/d4qi02039a","DOIUrl":"https://doi.org/10.1039/d4qi02039a","url":null,"abstract":"Iron oxide-based heterojunctions have garnered widespread interest in the field of photocatalysis due to their outstanding photoelectric properties. However, an in-depth understanding of the relationship between the interfacial structure and electronic properties of these heterojunctions at the atomic scale remains unclear. Access to such knowledge is critical for guiding the design and enhancing the efficiency of novel photocatalyst classes. Herein, a first-principles computational investigation focuses on the interfacial geometry, electronic structure and electron transfer mechanisms of MAPbI<small><sub>3</sub></small>/α-Fe<small><sub>2</sub></small>O<small><sub>3</sub></small>, MAPbI<small><sub>3</sub></small>/γ-Fe<small><sub>2</sub></small>O<small><sub>3</sub></small> and MAPbI<small><sub>3</sub></small>/TiO<small><sub>2</sub></small> heterojunctions. Compared to the classical MAPbI<small><sub>3</sub></small>/TiO<small><sub>2</sub></small> system, the influence of iron coordination at the two octahedral iron sites of α-Fe<small><sub>2</sub></small>O<small><sub>3</sub></small> and at both tetrahedral and octahedral iron sites of γ-Fe<small><sub>2</sub></small>O<small><sub>3</sub></small> is investigated. It indicates that the stability of the interface on the γ-Fe<small><sub>2</sub></small>O<small><sub>3</sub></small> (111) surface is enhanced by the octahedrally coordinated iron, whereas the subsurface Fe<small><sub>o2</sub></small> plays a pivotal role in stabilizing the interface with PbI on the α-Fe<small><sub>2</sub></small>O<small><sub>3</sub></small>-Fe<small><sub>o1</sub></small> surface. Furthermore, a notable modulation by different iron coordination of the valence band maximum charge distribution at the the α-Fe<small><sub>2</sub></small>O<small><sub>3</sub></small>/PbI and γ-Fe<small><sub>2</sub></small>O<small><sub>3</sub></small>/PbI interfaces is observed, which is pivotal for the separation and transfer of photogenerated electrons and holes. Combined with the comprehensive analysis of the band structure, electrostatic potential and average plane charge density of the heterojunction, the MAPbI<small><sub>3</sub></small>/iron oxides heterojunction is consistent with the S-scheme heterojunction mechanism. Molecular adsorption simulations of CO<small><sub>2</sub></small>, O<small><sub>2</sub></small> and H<small><sub>2</sub></small>O show that the α-Fe<small><sub>2</sub></small>O<small><sub>3</sub></small>-Fe<small><sub>o1</sub></small>/PbI interface stands out with the lowest adsorption energy, indicating its superior photocatalytic potential for CO<small><sub>2</sub></small> reduction and dye degradation. These findings provide valuable insights into the design principles of photocatalytic materials, emphasizing the strategic manipulation of iron coordination to optimize iron-based heterojunction performance.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329243","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}
Angel Luciano Huamani, Gregorio Laucirica, Juan A Allegretto, Maria Eugenia Toimil-Molares, Aline Ribeiro Passos, Agustin Silvio Picco, Marcelo Ceolín, Omar Azzaroni, Waldemar Alejandro Marmisollé, Matias Rafti
We studied ionic transport properties of UiO-66 metal-organic framework-modified solid-state nanochannels (MOF@SSNs) embedded in polyethylene terephthalate (PET) membranes, focusing on the effect of calcium ions from chloride salt (CaCl2) acting as ionic response modulator. We observed a behavior known as ionic current saturation (ICS) regime in a broad pH range, which can be attributed to specific binding of divalent calcium ions to free-carboxylate moieties present in the MOF-filled nanochannels. Such binding provokes a surface charge increase and causes the ICS regime to dominate the response even in alkaline aqueous environments, which were previously shown to feature simple ohmic regimes. The primary ionic transport mechanism operating involves the presence of (mesoscopic) constructional porosity arising from defects and gaps generated during MOF formation within PET nanochannels, rather than intrinsic MOF microporosity also present. The hereby discussed example illustrates how, through straightforward chemical modification, ionic transport properties of the nanochannels can be modulated to feature specific responses necessary for high-impact applications such as ion selective transport, biosensing, or energy generation.
{"title":"Calcium Chloride as an Ionic Response Modulator in Metal Organic Framework-filled Nanopores (MOF@SSNs): Enhancing Ionic Current Saturation and Selectivity","authors":"Angel Luciano Huamani, Gregorio Laucirica, Juan A Allegretto, Maria Eugenia Toimil-Molares, Aline Ribeiro Passos, Agustin Silvio Picco, Marcelo Ceolín, Omar Azzaroni, Waldemar Alejandro Marmisollé, Matias Rafti","doi":"10.1039/d4qi01575d","DOIUrl":"https://doi.org/10.1039/d4qi01575d","url":null,"abstract":"We studied ionic transport properties of UiO-66 metal-organic framework-modified solid-state nanochannels (MOF@SSNs) embedded in polyethylene terephthalate (PET) membranes, focusing on the effect of calcium ions from chloride salt (CaCl2) acting as ionic response modulator. We observed a behavior known as ionic current saturation (ICS) regime in a broad pH range, which can be attributed to specific binding of divalent calcium ions to free-carboxylate moieties present in the MOF-filled nanochannels. Such binding provokes a surface charge increase and causes the ICS regime to dominate the response even in alkaline aqueous environments, which were previously shown to feature simple ohmic regimes. The primary ionic transport mechanism operating involves the presence of (mesoscopic) constructional porosity arising from defects and gaps generated during MOF formation within PET nanochannels, rather than intrinsic MOF microporosity also present. The hereby discussed example illustrates how, through straightforward chemical modification, ionic transport properties of the nanochannels can be modulated to feature specific responses necessary for high-impact applications such as ion selective transport, biosensing, or energy generation.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324888","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}
Developing non-noble metal efficient electrocatalysts with high activity and stability is extremely essential for the hydrogen generation by water electrolysis with low cost. Herein, we report a novel binder-free high-entropy self-standing electrode with unique three-dimensional structure and petunia-, needle- and fork-like morphology prepared by the hydrothermal and selenizing methods. Due to high-entropy, lattice distortion and high-curvature tip-enhancement effects, electrochemical tests demonstrated that the prepared FeCoMnCuNiSe2 with an ultralow overpotential of 71.6 mV at 100 mA cm-2 exhibited superior activity for the hydrogen evolution reaction (HER) in 1.0 M KOH solution, far outperforming almost all reported advanced non-noble metal HER catalysts. More impressively, the assembled FeCoMnCuNiSe2||FeCoMnCuNiSe2 overall-water splitting device with more than 45 h continuous operation stability at 10, 20 and 50 mA cm-2 in 1.0 M KOH required a remarkably low cell voltage of 1.30 V at 10 mA cm-2 as well, demonstrating a promising practical application prospect in future water electrolysis.
开发高活性、高稳定性的非贵金属高效电催化剂对于低成本电解水制氢至关重要。在此，我们报告了一种新型的无粘结剂高熵自立电极，它具有独特的三维结构和牵牛花状、针状和叉状形貌，由水热法和硒化法制备而成。由于高熵效应、晶格畸变和高曲率尖端增强效应，电化学测试表明，制备的 FeCoMnCuNiSe2 在 100 mA cm-2 条件下具有 71.6 mV 的超低过电位，在 1.0 M KOH 溶液中的氢进化反应（HER）中表现出卓越的活性，远远超过几乎所有已报道的先进非贵金属 HER 催化剂。更令人印象深刻的是，所组装的 FeCoMnCuNiSe2|||FeCoMnCuNiSe2整体水分离装置在 1.0 M KOH 溶液中以 10、20 和 50 mA cm-2 的电流持续稳定运行 45 小时以上，在 10 mA cm-2 的电流下所需的电池电压也非常低，仅为 1.30 V，这表明该装置在未来水电解领域具有广阔的实际应用前景。
{"title":"High-Entropy FeCoMnCuNi diselenide Self-Standing Electrode with Outstanding Water-Electrolysis Performance in Alkaline Medium","authors":"Xinxin Guo, Mengmeng Zhou, Ziwu Liu, Shiheng Mu, Kaijia Wang, Huanqiang Shi, Fang Wang, Shijian Lu, Zhong-Hai Ni, Guiqing Liu","doi":"10.1039/d4qi01835d","DOIUrl":"https://doi.org/10.1039/d4qi01835d","url":null,"abstract":"Developing non-noble metal efficient electrocatalysts with high activity and stability is extremely essential for the hydrogen generation by water electrolysis with low cost. Herein, we report a novel binder-free high-entropy self-standing electrode with unique three-dimensional structure and petunia-, needle- and fork-like morphology prepared by the hydrothermal and selenizing methods. Due to high-entropy, lattice distortion and high-curvature tip-enhancement effects, electrochemical tests demonstrated that the prepared FeCoMnCuNiSe2 with an ultralow overpotential of 71.6 mV at 100 mA cm-2 exhibited superior activity for the hydrogen evolution reaction (HER) in 1.0 M KOH solution, far outperforming almost all reported advanced non-noble metal HER catalysts. More impressively, the assembled FeCoMnCuNiSe2||FeCoMnCuNiSe2 overall-water splitting device with more than 45 h continuous operation stability at 10, 20 and 50 mA cm-2 in 1.0 M KOH required a remarkably low cell voltage of 1.30 V at 10 mA cm-2 as well, demonstrating a promising practical application prospect in future water electrolysis.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324887","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}
Matthew S. Chambers, Jue Liu, Olaf J. Borkiewicz, Kevin Llopart, Robert L. Sacci and Gabriel M. Veith
<p >Li<small><sub>1+<em>x</em></sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> (LATP) and Li<small><sub>3</sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> (<em>x</em> = 0, 0.3) are promising candidates in all-solid-state batteries due to their high room temperature conductivity of 10<small><sup>−3</sup></small> S cm<small><sup>−1</sup></small> and air- and moisture-stability. They also exhibit unusual thermal expansion properties, with Li<small><sub>1+<em>x</em></sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> showing near-zero thermal expansion along the <em>a</em> axis while Li<small><sub>3</sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> exhibits polynomial positive thermal expansion along the <em>a</em> axis and polynomial negative thermal expansion along the <em>c</em> axis. A crucial component to understanding these properties is understanding the local structure. Total scattering is a powerful analytical technique as it provides information on the long-range, average structure as well as the local structure. Here, we report the first X-ray and neutron total scattering experiments performed on Li<small><sub>1+<em>x</em></sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> and Li<small><sub>3</sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> (<em>x</em> = 0, 0.3). We show that the PO<small><sub>4</sub></small> and TiO<small><sub>6</sub></small> polyhedra experience very little expansion of the P/Ti–O bonds up to 800 °C, nor is there much expansion when the Li content increases significantly. The minor thermal expansion of the nearest-neighbor bonds of the polyhedra is revealed to be the reason behind the unusual thermal expansion properties, causing the near-zero thermal expansion along <em>a</em> in Li<small><sub>1+<em>x</em></sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> and moving as whole units in Li<small><sub>3</sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small>. The structural robustness of the framework is also the reason for the increased conductivity as Li content increases, as the framework remains undistorted as Li content increases, permitting Li-ion mobility as the number of charge carriers increases. This suggests that phosphate-based fram
Li1+xAlxTi2-x(PO4)3（LATP）和 Li3AlxTi2-x(PO4)3（x = 0，0.3）具有 10-3 S cm-1 的高室温电导率以及空气和湿气稳定性，是全固态电池的理想候选材料。它们还表现出不同寻常的热膨胀特性，Li1+xAlxTi2-x(PO4)3 沿 a 轴表现出近乎零的热膨胀，而 Li3AlxTi2-x(PO4)3沿 a 轴表现出多项式正热膨胀，沿 c 轴表现出多项式负热膨胀。要了解这些性质，关键在于了解局部结构。全散射是一种强大的分析技术，因为它提供了长程平均结构和局部结构的信息。在此，我们首次报告了对 Li1+xAlxTi2-x(PO4)3 和 Li3AlxTi2-x(PO4)3 (x = 0, 0.3) 进行的 X 射线和中子全散射实验。实验结果表明，PO4 和 TiO6 多面体的 P/Ti-O 键在 800 °C 以下几乎没有膨胀，而当锂含量显著增加时，膨胀也不大。多面体近邻键的微小热膨胀被揭示为非同寻常的热膨胀特性背后的原因，导致 Li1+xAlxTi2-x(PO4)3 中沿 a 的热膨胀接近零，而 Li3AlxTi2-x(PO4)3 中则作为整体单元移动。 框架结构的稳健性也是随着锂含量的增加而增加导电性的原因，因为随着锂含量的增加，框架保持不变形，允许锂离子随着电荷载体数量的增加而移动。这表明，除了 LATP 之外，磷酸盐基框架材料也是探索新型锂离子（和其他离子）导电材料的良好材料空间。
{"title":"Elucidating the local structure of Li1+xAlxTi2−x(PO4)3 and Li3AlxTi2−x(PO4)3 (x = 0, 0.3) via total scattering†","authors":"Matthew S. Chambers, Jue Liu, Olaf J. Borkiewicz, Kevin Llopart, Robert L. Sacci and Gabriel M. Veith","doi":"10.1039/D4QI01545B","DOIUrl":"10.1039/D4QI01545B","url":null,"abstract":"<p >Li<small><sub>1+<em>x</em></sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> (LATP) and Li<small><sub>3</sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> (<em>x</em> = 0, 0.3) are promising candidates in all-solid-state batteries due to their high room temperature conductivity of 10<small><sup>−3</sup></small> S cm<small><sup>−1</sup></small> and air- and moisture-stability. They also exhibit unusual thermal expansion properties, with Li<small><sub>1+<em>x</em></sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> showing near-zero thermal expansion along the <em>a</em> axis while Li<small><sub>3</sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> exhibits polynomial positive thermal expansion along the <em>a</em> axis and polynomial negative thermal expansion along the <em>c</em> axis. A crucial component to understanding these properties is understanding the local structure. Total scattering is a powerful analytical technique as it provides information on the long-range, average structure as well as the local structure. Here, we report the first X-ray and neutron total scattering experiments performed on Li<small><sub>1+<em>x</em></sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> and Li<small><sub>3</sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> (<em>x</em> = 0, 0.3). We show that the PO<small><sub>4</sub></small> and TiO<small><sub>6</sub></small> polyhedra experience very little expansion of the P/Ti–O bonds up to 800 °C, nor is there much expansion when the Li content increases significantly. The minor thermal expansion of the nearest-neighbor bonds of the polyhedra is revealed to be the reason behind the unusual thermal expansion properties, causing the near-zero thermal expansion along <em>a</em> in Li<small><sub>1+<em>x</em></sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small> and moving as whole units in Li<small><sub>3</sub></small>Al<small><sub><em>x</em></sub></small>Ti<small><sub>2−<em>x</em></sub></small>(PO<small><sub>4</sub></small>)<small><sub>3</sub></small>. The structural robustness of the framework is also the reason for the increased conductivity as Li content increases, as the framework remains undistorted as Li content increases, permitting Li-ion mobility as the number of charge carriers increases. This suggests that phosphate-based fram","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":6.1,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324908","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 perovskite solar cells (PSCs), chemical bath deposition (CBD) is promising to be the core technique for preparing commercial electron transport layer (ETL) because the film prepared by CBD exhibits excellent uniform and conformal coverage of the substrate. However, metal oxide (MOx) films prepared through CBD often have defects on the surface like oxygen vacancies and hydroxyl that limit the PSCs efficiency and degrade the long-term stability. To address this obstacle to the scaled PSCs application, we here reconstructed the surface microstructure of CBD tin dioxide (SnO2) ETL by post-treatment with dilute H2SO4 solution to terminate the oxygen vacancies from the MOx surface while effectively removing the hydroxyl groups. Concurrently, the potent oxidizing property of H2SO4 facilitates the transformation from Sn (II) to Sn (IV), thereby enhancing the alignment of energy level between SnO2 and perovskite (PVK) layer within the ETL architecture. Moreover, the interaction between SO42- and perovskite precursor mitigates the difference in crystallization velocity between the perovskite upper and buried surfaces, enabling films with homogeneous phase distribution and good crystallization. Ultimately, with the assistance of this facile surface microstructure reconstruction, the power conversion efficiency (PCE) is improved from 22.48% to 24.29%.
在过氧化物太阳能电池（PSCs）中，化学沉积法（CBD）有望成为制备商用电子传输层（ETL）的核心技术，因为通过 CBD 制备的薄膜能够很好地均匀、保形地覆盖基底。然而，通过化学气相沉积制备的金属氧化物（MOx）薄膜表面往往存在氧空位和羟基等缺陷，从而限制了 PSC 的效率并降低了其长期稳定性。为了解决这一影响 PSCs 大规模应用的障碍，我们用稀 H2SO4 溶液对 CBD 二氧化锡（SnO2）ETL 进行后处理，以终止 MOx 表面的氧空位，同时有效去除羟基，从而重建了其表面微观结构。同时，H2SO4 的强氧化特性促进了 Sn (II) 向 Sn (IV) 的转化，从而增强了 ETL 结构中 SnO2 和过氧化物层 (PVK) 之间的能级排列。此外，SO42- 和包晶体前驱体之间的相互作用还能缓解包晶体上表面和埋藏表面之间的结晶速度差异，从而使薄膜具有均匀的相分布和良好的结晶性。最终，在这种简便的表面微结构重建技术的帮助下，功率转换效率（PCE）从 22.48% 提高到了 24.29%。
{"title":"Rationally reconstructing the surface microstructure of chemical bath deposited electron transport layer for efficient and stable perovskite solar cells","authors":"Xianxuan Yang, Lexin Wang, Meihan Liu, Jiahui Jin, Lili Yang, Lin Fan, Maobin Wei, Huilian Liu, Haoran Chen, Jinghai Yang, Yulei Chang, Fengyou Wang","doi":"10.1039/d4qi01808g","DOIUrl":"https://doi.org/10.1039/d4qi01808g","url":null,"abstract":"In perovskite solar cells (PSCs), chemical bath deposition (CBD) is promising to be the core technique for preparing commercial electron transport layer (ETL) because the film prepared by CBD exhibits excellent uniform and conformal coverage of the substrate. However, metal oxide (MOx) films prepared through CBD often have defects on the surface like oxygen vacancies and hydroxyl that limit the PSCs efficiency and degrade the long-term stability. To address this obstacle to the scaled PSCs application, we here reconstructed the surface microstructure of CBD tin dioxide (SnO2) ETL by post-treatment with dilute H2SO4 solution to terminate the oxygen vacancies from the MOx surface while effectively removing the hydroxyl groups. Concurrently, the potent oxidizing property of H2SO4 facilitates the transformation from Sn (II) to Sn (IV), thereby enhancing the alignment of energy level between SnO2 and perovskite (PVK) layer within the ETL architecture. Moreover, the interaction between SO42- and perovskite precursor mitigates the difference in crystallization velocity between the perovskite upper and buried surfaces, enabling films with homogeneous phase distribution and good crystallization. Ultimately, with the assistance of this facile surface microstructure reconstruction, the power conversion efficiency (PCE) is improved from 22.48% to 24.29%.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324890","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}
Yu He, Kefan Shi, Xueqin Wang, Xingzi Zheng, Lanke Luo, Liu Lin, Zemin Sun and Genban Sun
The development of low-cost, efficient, and stable electrocatalysts is critical for the anodic oxygen evolution reaction (OER). Ni3S2 not only has the advantages of low cost, easy preparation, and environmental friendliness, but also attracts attention for its structure throughout the Ni–Ni bond, which provides metal-like electrical conductivity. In this work, the Fe and Ce double-doped Ni3S2 nanoneedle array catalyst (Fe,Ce-Ni3S2@NF) was prepared by a one-step hydrothermal method. The synergistic doping of Fe and Ce optimized the microscopic morphology and the electronic structure of Ni3S2, which increased the exposure of catalytically active sites, enhanced the electron transfer rate in the OER process, and improved the intrinsic activity of the catalyst. The catalyst has an overpotential of 254 mV at 10 mA cm−2 and a Tafel slope of 55.56 mV dec−1, and exhibits good electrocatalytic performance under alkaline conditions (1 M KOH). Compared with the original Ni3S2 (363 mV at 10 mA cm−2), the overpotential of Fe,Ce-Ni3S2@NF is reduced by 109 mV. This provides a new feasible direction for the preparation of transition metal and lanthanide metal double-doped catalysts and their application in electrocatalysis.
开发低成本、高效和稳定的电催化剂对于阳极氧进化反应（OER）至关重要。Ni3S2 不仅具有低成本、易制备、环保等优点，而且其贯穿 Ni-Ni 键的结构可提供类似金属的导电性，因此备受关注。本研究采用一步水热法制备了Fe和Ce双掺杂Ni3S2纳米针状阵列催化剂（Fe,Ce-Ni3S2@NF）。Fe和Ce的协同掺杂优化了Ni3S2的微观形貌和电子结构，增加了催化活性位点的暴露，提高了OER过程中的电子转移率，提高了催化剂的内在活性。该催化剂在 10 mA cm-2 时的过电位为 254 mV，Tafel 斜率为 55.56 mV dec-1，在碱性条件（1 M KOH）下表现出良好的电催化性能。与原来的 Ni3S2（10 mA cm-2 时为 363 mV）相比，Fe,Ce-Ni3S2@NF 的过电位降低了 109 mV。这为制备过渡金属和镧系金属双掺杂催化剂及其在电催化中的应用提供了一个新的可行方向。
{"title":"Synergistic Fe,Ce doping of Ni3S2 for enhancing oxygen evolution reaction performance†","authors":"Yu He, Kefan Shi, Xueqin Wang, Xingzi Zheng, Lanke Luo, Liu Lin, Zemin Sun and Genban Sun","doi":"10.1039/D4QI02187H","DOIUrl":"10.1039/D4QI02187H","url":null,"abstract":"<p >The development of low-cost, efficient, and stable electrocatalysts is critical for the anodic oxygen evolution reaction (OER). Ni<small><sub>3</sub></small>S<small><sub>2</sub></small> not only has the advantages of low cost, easy preparation, and environmental friendliness, but also attracts attention for its structure throughout the Ni–Ni bond, which provides metal-like electrical conductivity. In this work, the Fe and Ce double-doped Ni<small><sub>3</sub></small>S<small><sub>2</sub></small> nanoneedle array catalyst (Fe,Ce-Ni<small><sub>3</sub></small>S<small><sub>2</sub></small>@NF) was prepared by a one-step hydrothermal method. The synergistic doping of Fe and Ce optimized the microscopic morphology and the electronic structure of Ni<small><sub>3</sub></small>S<small><sub>2</sub></small>, which increased the exposure of catalytically active sites, enhanced the electron transfer rate in the OER process, and improved the intrinsic activity of the catalyst. The catalyst has an overpotential of 254 mV at 10 mA cm<small><sup>−2</sup></small> and a Tafel slope of 55.56 mV dec<small><sup>−1</sup></small>, and exhibits good electrocatalytic performance under alkaline conditions (1 M KOH). Compared with the original Ni<small><sub>3</sub></small>S<small><sub>2</sub></small> (363 mV at 10 mA cm<small><sup>−2</sup></small>), the overpotential of Fe,Ce-Ni<small><sub>3</sub></small>S<small><sub>2</sub></small>@NF is reduced by 109 mV. This provides a new feasible direction for the preparation of transition metal and lanthanide metal double-doped catalysts and their application in electrocatalysis.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":6.1,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142325324","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}
Yan Li, Fei Zhang, Miaomiao Wu, Yong Guo, Yuanyuan Liang, Reyihanguli Ababaikeri, Luyang Wang, Qiao Liu, Xingchao Wang
Manganese dioxide (MnO2) has been extensively studied in aqueous zinc ion batteries (AZIBs) due to its high redox potential, high theoretical capacity and low cost. However, its low capacity and poor structural stability result in poor performance. In this study, we propose a novel approach where δ-MnO2 is grown in situ on carbon fibers derived from coal (δ-MnO2@CCFs). The unform anchoring of δ-MnO2 on the carbon fibers allow for good flexibility and keep structural stability during cycling. The doping of heteroatoms (N) directly forms chemical bonds with δ-MnO2 and reduces electrostatic repulsion within the δ-MnO2@CCFs material, while facilitating the insertion and extraction of Zn2+ and H+ ions. Moreover, the flexible AZIBs exhibit excellent electrochemical reversibility even under bending and folding conditions. The δ-MnO2@CCFs electrode material exhibits a capacity of 352 mAh g-1 at a current density of 0.5 A g-1 after 100 cycles. Furthermore, the assembled flexible Zn//δ-MnO2@CCFs AZIBs maintain a capacity of 293.7 mAh g-1 after 50 cycles at a current density of 0.1 A g-1.
二氧化锰（MnO2）具有高氧化还原电位、高理论容量和低成本的特点，因此在锌离子水电池（AZIBs）中得到了广泛的研究。然而，二氧化锰容量低、结构稳定性差，导致性能不佳。在本研究中，我们提出了一种新方法，即在煤（δ-MnO2@CCFs）衍生的碳纤维上原位生长 δ-MnO2。δ-MnO2在碳纤维上的非形式锚定使其具有良好的柔韧性，并在循环过程中保持结构稳定。杂原子（N）的掺杂直接与 δ-MnO2 形成化学键，减少了 δ-MnO2@CCFs 材料内部的静电排斥，同时有利于 Zn2+ 和 H+ 离子的插入和提取。此外，柔性 AZIB 即使在弯曲和折叠条件下也能表现出优异的电化学可逆性。经过 100 次循环后，δ-MnO2@CCFs 电极材料在 0.5 A g-1 的电流密度下显示出 352 mAh g-1 的容量。此外，组装好的柔性 Zn//δ-MnO2@CCFs AZIB 在 0.1 A g-1 的电流密度下，循环 50 次后仍能保持 293.7 mAh g-1 的容量。
{"title":"In situ growth of δ-MnO2/C fibers as binder-free and free-standing cathode for advanced aqueous Zn-ions batteries","authors":"Yan Li, Fei Zhang, Miaomiao Wu, Yong Guo, Yuanyuan Liang, Reyihanguli Ababaikeri, Luyang Wang, Qiao Liu, Xingchao Wang","doi":"10.1039/d4qi01661k","DOIUrl":"https://doi.org/10.1039/d4qi01661k","url":null,"abstract":"Manganese dioxide (MnO2) has been extensively studied in aqueous zinc ion batteries (AZIBs) due to its high redox potential, high theoretical capacity and low cost. However, its low capacity and poor structural stability result in poor performance. In this study, we propose a novel approach where δ-MnO2 is grown in situ on carbon fibers derived from coal (δ-MnO2@CCFs). The unform anchoring of δ-MnO2 on the carbon fibers allow for good flexibility and keep structural stability during cycling. The doping of heteroatoms (N) directly forms chemical bonds with δ-MnO2 and reduces electrostatic repulsion within the δ-MnO2@CCFs material, while facilitating the insertion and extraction of Zn2+ and H+ ions. Moreover, the flexible AZIBs exhibit excellent electrochemical reversibility even under bending and folding conditions. The δ-MnO2@CCFs electrode material exhibits a capacity of 352 mAh g-1 at a current density of 0.5 A g-1 after 100 cycles. Furthermore, the assembled flexible Zn//δ-MnO2@CCFs AZIBs maintain a capacity of 293.7 mAh g-1 after 50 cycles at a current density of 0.1 A g-1.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":null,"pages":null},"PeriodicalIF":7.0,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321758","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}
Photocatalytic CO2 reduction into highly-valued chemical fuels holds great promises for resolving the energy shortage and mitigating the greenhouse gas. But the current CO2 conversion efficiency is hampered by the undesirable charge transfer and deficient reactive sites of photocatalysts. Herein, we synthesize Bi2MoO6 doped by monovalence Cu with accompanying O vacancies (Ov) to accelerate the bulk and surface charge separation and transfer. Moreover, the Cu dopants serving as the reactive sites improve the adsorption and activation of CO2 molecules on catalyst’s surface. As a result, the Cu-doped Bi2MoO6 catalysts exhibit remarkedly boosted CO2 reduction activity to the pristine Bi2MoO6, and the peak activity reaches at Bi2MoO6-10% Cu with a CO evolution rate of 11.40 μmol g-1 h-1 under 300 W Xenon lamp irradiation, without any cocatalyst or sacrificial agent. This photoactivity surpasses most of the previously reported catalysts, and it is about 6-fold higher than that of Bi2MoO6 (1.94 μmol g-1 h-1). Moreover, even under natural sunlight illumination, the Bi2MoO6-10% Cu also exhibits considerable activity for CO2 photocatalytic conversion to CO. This study may inspire an efficient strategy for designing and developing high performance photocatalysts toward CO2 conversion.
光催化将二氧化碳还原成高价值的化学燃料，为解决能源短缺和减少温室气体带来了巨大希望。但目前的二氧化碳转化效率受到光催化剂不良电荷转移和反应位点不足的影响。在此，我们合成了掺杂了单价Cu和伴生O空位（Ov）的Bi2MoO6，以加速块体和表面电荷的分离和转移。此外，作为反应位点的掺杂铜还能改善催化剂表面对二氧化碳分子的吸附和活化。因此，与原始 Bi2MoO6 相比，掺杂铜的 Bi2MoO6 催化剂的二氧化碳还原活性显著提高，在 300 W 氙灯辐照下，达到峰值活性的 Bi2MoO6-10% Cu 催化剂的二氧化碳进化速率为 11.40 μmol g-1 h-1，而无需任何助催化剂或牺牲剂。这一光活性超过了之前报道的大多数催化剂，是 Bi2MoO6（1.94 μmol g-1 h-1）的 6 倍。此外，即使在自然日光照射下，Bi2MoO6-10% Cu 在 CO2 光催化转化为 CO 方面也表现出相当高的活性。这项研究为设计和开发高性能光催化剂提供了一种有效的策略。
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