Inorganic Chemistry Frontiers最新文献_第5页

Facet-engineered CeO2 with Cu single atom drives photocatalytic selective oxidation of 5-hydroxymethylfurfural 含有单个铜原子的刻面工程 CeO2 推动了 5-羟甲基糠醛的光催化选择性氧化作用

IF 7 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers

Pub Date : 2024-11-04 DOI: 10.1039/d4qi02230k

Yifei Li, Senyao Meng, Ping Wang, Miao He, Jiasai Yao, Cheng Yang, Fangzhou Mo, Jiang Li, Zhenxing Li

The crystal facet of CeO2 is crucial in governing the catalytic performance. However, studies on the relationship between the photocatalytic oxidation performance of CeO2 and its crystal facets are scarce. Herein, we synthesized a series of CeO2. Through loading Cu single atom (Cu/CeO2), the facet effects of crystal facets on the photocatalytic selective oxidation were studied systematically via employing the selective oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran as a model. Because the (110) facet's superior electron transfer efficiency, are feasible for absorbing 5-hydroxymethylfurfural, eliminating α-H, and desorbing 2,5-diformylfuran, the selectivity of Cu/CeO2-nanorod (Cu/CeO2-R) with (110) facet (93.34%) is much higher than that of Cu/CeO2-nanocube (Cu/CeO2-C) with (100) facet (32.22%) and Cu/CeO2-nanooctahedra (Cu/CeO2-O) with (111) facet (15.20%). The DFT calculation shows that the Cu 3d has orbital hybridization with Ce 5d and 4f, which provides a favorable pathway for electron transfer. This work delves into the facet-performance relationship during the photocatalytic process.

CeO2 的晶面是影响催化性能的关键。然而，有关 CeO2 的光催化氧化性能与其晶面之间关系的研究却很少。在此，我们合成了一系列 CeO2。以 5-hydroxymethylfurfural 对 2,5-二甲酰基呋喃的选择性氧化为模型，通过负载 Cu 单原子（Cu/CeO2），系统研究了晶面对光催化选择性氧化的影响。由于（110）面具有优异的电子传递效率，可以吸收 5-羟甲基糠醛、消除 α-H 并解吸 2,5-二甲酰基呋喃，因此具有（110）面的 Cu/CeO2-nanorod (Cu/CeO2-R) 的选择性（93.34%）远高于具有（100）面的Cu/CeO2-纳米立方体（Cu/CeO2-C）（32.22%）和具有（111）面的Cu/CeO2-纳米八面体（Cu/CeO2-O）（15.20%）。DFT 计算表明，Cu 3d 与 Ce 5d 和 4f 存在轨道杂化，这为电子转移提供了有利途径。这项研究深入探讨了光催化过程中的面-性能关系。

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引用次数: 0

Multistage construction of Gd-Doped g-C3N4/Mo15S19 Composites Enabled Both N2 activation and multiple electron transfer for Enhanced Photocatalytic Nitrogen Reduction Reaction 多级构建掺杂钆的 g-C3N4/Mo15S19 复合材料，实现氮气活化和多重电子转移，从而增强光催化氮还原反应

IF 7 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers

Pub Date : 2024-11-04 DOI: 10.1039/d4qi02016b

Xiaoyu Jiang, Boran Tao, Hongda Li

The efficiency of photocatalytic nitrogen reduction reactions (NRR) faces significant challenges due to the need for effective activation of the N≡N bond and efficient multi-electron/proton transfer. A novel Gd-doped and Mo15S19-loaded g-C3N4 nanorods (GdC3N4/Mo15S19) was promoted in this work. Experimental results show that the GdC3N4/Mo15S19 composite exhibits remarkable visible-light-driven photocatalytic ammonia production (407.51 μmol g⁻1 h⁻1, 33 times that of g-C3N4), which attributed to the promoted multiple electron transfer by in-built Gd3+ redox centers and increased Mo active sites by loading of Mo15S19. Calculations using Density Functional Theory (DFT) show that Mo15S19 loading also helps to effectively activate the N≡N bond, which quickens the NRR's start. The synergistic effect of Gd doping and Mo15S19 loading lowers the Gibbs free energy of intermediates, enhancing the overall photocatalytic efficiency. This work provides a viable approach to the construction of multistage structures in the photocatalytic NRR that incorporates multiple electron transfer and N2 activation effects.

光催化氮还原反应（NRR）的效率面临重大挑战，因为需要有效激活 N≡N 键和高效的多电子/质子转移。本研究推广了一种掺杂钆和 Mo15S19 的新型 g-C3N4 纳米棒（GdC3N4/Mo15S19）。实验结果表明，GdC3N4/Mo15S19 复合材料在可见光驱动下表现出显著的光催化产氨能力（407.51 μmol g-1 h-1，是 g-C3N4 的 33 倍），这归功于内置 Gd3+ 氧化还原中心促进了多重电子转移，以及负载 Mo15S19 增加了 Mo 活性位点。利用密度泛函理论（DFT）进行的计算表明，Mo15S19 的负载还有助于有效激活 N≡N 键，从而加快 NRR 的启动。掺杂钆和添加 Mo15S19 的协同效应降低了中间产物的吉布斯自由能，从而提高了整体光催化效率。这项工作为在光催化 NRR 中构建多级结构提供了一种可行的方法，该方法结合了多重电子传递和 N2 激活效应。

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引用次数: 0

Reconstruction and immobilization of polymolybdate induced by metal-organic coordination units for enhanced electrocatalytic hydrogen generation 重构和固定金属有机配位单元诱导的聚钼酸盐，以增强电催化制氢能力

IF 7 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers

Pub Date : 2024-11-04 DOI: 10.1039/d4qi02311k

Jingyi Ma, Zhihan Chang, Xue Xi, Juju Liang, Yuchun Lin, Yaling Zhu, Xiuli Wang

Electrocatalytic water cracking for hydrogen evolution has drawn the concern from researchers owing to its high efficiency. Polymolybdate has excellent redox behaviors and O-rich surface, becoming attractive electrocatalytic materials. In this work, iso- and hetro-polymolybdate anions were introduced in the crystalline metal-organic coordination system as electrocatalytic electrode material for hydrogen evolution reaction. Semi-rigid bi-pyrazole bi-amide ligand was taken as the organic component, and four complexes were yielded under hydrothermal condition. The reconstruction and oriented immobilization of polymolybdate occur during the assembly of the architectures, owing to the potential template effect from the metal-organic units. This phenomenon influnce the distribution of active sites from polymolybdate. The discrete [AlMo6(OH)7O17]2- anions in complex 3 were immobilized among the directionally arranged metal-organic chains, and expose more active sites. The carbon cloth-based electrode modified by complex 3 possess obvious electrocatalytic activity by achieving a low overpotential of 17.0 mV at the current density of 10 mA cm-2 in 1 M KOH for hydrogen evolution reaction. Meanwhile, the overpotential can achieve 33.7 mV when the current density is 10 mA cm-2 in simulated seawater.

电催化水裂解制氢因其高效率而受到研究人员的关注。多聚钼酸盐具有优异的氧化还原行为和富含 O 的表面，成为极具吸引力的电催化材料。本研究在结晶金属有机配位体系中引入了异钼酸盐和正钼酸盐阴离子，作为氢气进化反应的电催化电极材料。以半刚性双吡唑双酰胺配体为有机组分，在水热条件下生成了四种配合物。由于金属有机单元的潜在模板效应，多钼酸盐在结构组装过程中发生了重构和定向固定。这种现象影响了聚钼酸盐活性位点的分布。复合物 3 中离散的[AlMo6(OH)7O17]2-阴离子被固定在定向排列的金属有机链中，并暴露出更多的活性位点。复合物 3 修饰的碳布基电极具有明显的电催化活性，在 1 M KOH 中进行氢气进化反应时，电流密度为 10 mA cm-2 时，过电位低至 17.0 mV。同时，在模拟海水中，当电流密度为 10 mA cm-2 时，过电位可达 33.7 mV。

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引用次数: 0

Lithium extraction by metal-organic frameworks 利用金属有机框架提取锂

IF 7 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers

Pub Date : 2024-11-04 DOI: 10.1039/d4qi02228a

Zongsu Han, Joshua Rushlow, Yihao Yang, Jiatong Huo, Wei Shi, Hong-Cai Zhou

The extraction of lithium has become increasingly critical due to the soaring demand for lithium-ion batteries, which power a wide range of products from smartphones to electric vehicles. Lithium, the lightest metal, boasts exceptional energy density, making it ideal for portable electronics and renewable energy storage solutions, addressing environmental pollution issues simultaneously. However, extracting and recycling lithium ion is highly challenging due to its low natural abundance, significant mining difficulties, and environmental concerns. Metal-organic frameworks (MOFs), with their intricate and designable structures as well as abundant and regulated pore environments, have emerged as promising candidates for lithium extraction. The tailored porous structures of MOFs could enable efficient lithium ion sieving and capture. This review aims to discuss the design principles of targeted MOFs and their lithium extraction capabilities, as well as the common analysis methods during these processes. We seek to provide a comprehensive summary of the field and promote the development of advanced materials for practical lithium extraction applications.

由于从智能手机到电动汽车等各种产品对锂离子电池的需求急剧增长，锂的提取变得越来越重要。锂是最轻的金属，具有极高的能量密度，是便携式电子产品和可再生能源存储解决方案的理想选择，同时还能解决环境污染问题。然而，由于锂离子的天然丰度低、开采难度大以及环境问题，锂离子的提取和回收利用极具挑战性。金属有机框架（MOFs）具有复杂的可设计结构以及丰富而规范的孔隙环境，已成为锂提取的理想候选材料。MOFs 的定制多孔结构可实现高效的锂离子筛分和捕获。本综述旨在讨论目标 MOFs 的设计原理及其锂萃取能力，以及这些过程中的常用分析方法。我们希望对该领域进行全面总结，并促进先进材料在实际锂萃取应用中的发展。

引用次数: 0

Strontium doping RuO2 electrocatalyst with abundant oxygen vacancies for boosting OER performance 具有丰富氧空位的锶掺杂 RuO2 电催化剂可提高 OER 性能

IF 7 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers

Pub Date : 2024-11-02 DOI: 10.1039/d4qi02070g

Bei An, Xiaoqian Li, Yuan Lin, Fanfan Shang, Huijie He, Hairui Cai, Xiaoxiao Zeng, Weitong Wang, Shengchun Yang, Bin Wang

Oxygen evolution reaction (OER) plays a crucial role as the anode reaction of electrolytic water in various applications. To date, it is still a great challenge to develop highly active and durable electrocatalysts for acidic electrolytic water. Herein, we highlight an effective strategy to regulate the oxidation state of Ru species and oxygen vacancies in RuO2 by introducing Sr heteroatom into its lattice based on the principle of charge equilibrium. The as-prepared Sr0.1RuOx exhibits excellent OER activity with an overpotential of 201 mV at the current density of 10 mA cm-2, which should be ascribed to the higher proportion of Ru4+ induced by Sr doping. Moreover, both experimental and theoretical calculations revealed that the introduced oxygen vacancies inhabited Ru to be overoxidized to Run>4+ during the OER process, thus enhancing the stability of Sr0.1RuOx. Therefore, the PEM electrolyzer by using Sr0.1RuOx as the anode catalyst can be operated for 240 hours at 10 mA cm-2 without obvious attenuation. This work presented an effective strategy to regulate the structure of the OER electrocatalysts with excellent performance.

氧进化反应（OER）作为电解水的阳极反应，在各种应用中发挥着至关重要的作用。迄今为止，为酸性电解水开发高活性、高持久性的电催化剂仍是一项巨大挑战。在此，我们着重介绍一种有效的策略，即根据电荷平衡原理，通过在 RuO2 晶格中引入 Sr 杂原子来调节 RuO2 中 Ru 物种和氧空位的氧化态。制备出的 Sr0.1RuOx 具有优异的 OER 活性，在电流密度为 10 mA cm-2 时过电位为 201 mV，这应该归因于 Sr 掺杂导致 Ru4+ 的比例升高。此外，实验和理论计算均表明，在 OER 过程中，引入的氧空位使 Ru 过度氧化为 Run>4+，从而提高了 Sr0.1RuOx 的稳定性。因此，使用 Sr0.1RuOx 作为阳极催化剂的 PEM 电解槽可在 10 mA cm-2 的条件下运行 240 小时而无明显衰减。这项研究提出了一种调节 OER 电催化剂结构的有效策略，并取得了优异的性能。

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引用次数: 0

Zero-dimensional cuprous halide scintillator with ultra-high anti-water stability for X-ray imaging† 用于 X 射线成像的具有超高抗水稳定性的零维卤化亚铜闪烁体

IF 6.1 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers

Pub Date : 2024-11-01 DOI: 10.1039/D4QI02149E

Jing-Ning Lv, Na Lin, Jia-Yi Zhang, Yu-Meng Liu, Li-Chuang Niu, Jie Shi, Xiao-Wu Lei and Zhi-Wei Chen

Zero-dimensional (0D) cuprous organic–inorganic hybrid halides have emerged as a new kind of scintillator due to their high light yield and adjustable emission properties in the whole visible spectral range. However, their practical application in the radiation industry is seriously hindered by the instability of Cu^I ions under humid atmospheres and oxidizing environments. Herein, we designed a new Cu(I)-based halide of [CEOMTPP]₂Cu₄Br₆ (CEOMTPP = ethoxycarbonylmethyl(triphenyl) phosphonium cation) containing a discrete [Cu₄Br₆]²⁻ nanocluster, which displays strong broadband yellow light emission with near-unity photoluminescence quantum yield (PLQY) and large Stokes shift of 206 nm. Remarkably, [CEOMTPP]₂Cu₄Br₆ shows ultra-high anti-water and anti-oxidation stability with steady emitting performance in water for over one year and in an acid–base aqueous solution for one day. Benefiting from the near-unity PLQY, large Stokes shift and negligible self-absorption, [CEOMTPP]₂Cu₄Br₆ exhibits excellent scintillation properties with a high light yield of 69 500 phonon per meV and low detection limit of 113.0 nGy s⁻¹. Furthermore, a high spatial resolution of 14.5 lp mm⁻¹ is achieved in X-ray imaging based on a [CEOMTPP]₂Cu₄Br₆@EVA composite-assembled scintillation screen, demonstrating its potential application in medical photography. This research provides a fundamental structural engineering strategy to design highly efficient and stable low-dimensional Cu(I) halides for X-ray radiation application.

零维（0D）亚铜有机-无机杂化卤化物因其在整个可见光谱范围内的高产光率和可调发射特性而成为一种新型闪烁体。然而，由于 CuI 离子在潮湿大气和氧化环境下的不稳定性，严重阻碍了它们在辐射行业的实际应用。在此，我们设计了一种新的铜(I)基卤化物[CEOMTPP]2Cu4Br6（CEOMTPP = 乙氧基羰基甲基（三苯基）鏻阳离子），其中含有一个离散的[Cu4Br6]2-纳米团簇，它能以接近均一的光致发光量子产率（PLQY）和 206 nm 的大斯托克斯偏移显示出强烈的宽带黄光发射。值得注意的是，[CEOMTPP]2Cu4Br6 具有超高的抗水和抗氧化稳定性，在水中可稳定发光一年以上，在酸碱水溶液中可稳定发光一天。由于[CEOMTPP]2Cu4Br6 具有近乎统一的 PLQY、较大的斯托克斯偏移和可忽略的自吸收，因此具有优异的闪烁特性，光产率高达 69 500 phonon per meV，探测限低至 113.0 nGy s-1。此外，基于[CEOMTPP]2Cu4Br6@EVA 复合组装的闪烁屏在 X 射线成像中实现了 14.5 lp mm-1 的高空间分辨率，证明了其在医学摄影中的潜在应用。这项研究为设计用于 X 射线辐射的高效、稳定的低维 Cu（I）卤化物提供了基本的结构工程策略。

{"title":"Zero-dimensional cuprous halide scintillator with ultra-high anti-water stability for X-ray imaging†","authors":"Jing-Ning Lv, Na Lin, Jia-Yi Zhang, Yu-Meng Liu, Li-Chuang Niu, Jie Shi, Xiao-Wu Lei and Zhi-Wei Chen","doi":"10.1039/D4QI02149E","DOIUrl":"10.1039/D4QI02149E","url":null,"abstract":"Zero-dimensional (0D) cuprous organic–inorganic hybrid halides have emerged as a new kind of scintillator due to their high light yield and adjustable emission properties in the whole visible spectral range. However, their practical application in the radiation industry is seriously hindered by the instability of CuI ions under humid atmospheres and oxidizing environments. Herein, we designed a new Cu(I)-based halide of [CEOMTPP]2Cu4Br6 (CEOMTPP = ethoxycarbonylmethyl(triphenyl) phosphonium cation) containing a discrete [Cu4Br6]2− nanocluster, which displays strong broadband yellow light emission with near-unity photoluminescence quantum yield (PLQY) and large Stokes shift of 206 nm. Remarkably, [CEOMTPP]2Cu4Br6 shows ultra-high anti-water and anti-oxidation stability with steady emitting performance in water for over one year and in an acid–base aqueous solution for one day. Benefiting from the near-unity PLQY, large Stokes shift and negligible self-absorption, [CEOMTPP]2Cu4Br6 exhibits excellent scintillation properties with a high light yield of 69 500 phonon per meV and low detection limit of 113.0 nGy s−1. Furthermore, a high spatial resolution of 14.5 lp mm−1 is achieved in X-ray imaging based on a [CEOMTPP]2Cu4Br6@EVA composite-assembled scintillation screen, demonstrating its potential application in medical photography. This research provides a fundamental structural engineering strategy to design highly efficient and stable low-dimensional Cu(I) halides for X-ray radiation application.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 23","pages":" 8555-8563"},"PeriodicalIF":6.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561973","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}

引用次数: 0

Moss-like CoB/CeO2 heterojunction as an efficient electrocatalyst for oxygen evolution reaction under alkaline conditions 苔藓状 CoB/CeO2 异质结作为碱性条件下氧进化反应的高效电催化剂

IF 7 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers

Pub Date : 2024-11-01 DOI: 10.1039/d4qi02325k

Weijie Fang, Chaofan Liu, Jiang Wu, Weikai Fan, Le Chen, Zaiguo Fu, Lin Peng, Ping He, Jia Lin, Zhongwei Chen

Heterostructure construction has become increasingly recognized as an effective strategy to enhance oxygen evolution reaction (OER) performance due to the exposed active surfaces and improved mass/charge transfer. Inspired by natural plant structures, this study develops a unique moss-like amorphous/crystalline (CoB/CeO2) heterojunction. This distinctive moss-like morphology facilitates the formation of staggered sheet structures in the catalyst, providing more active sites and open channels for reaction intermediates and gas release. Benefiting from the hydrophilic properties offered by the moss-like morphology, CoB/CeO2 exhibits excellent OER catalytic performance in 1M KOH, requiring only 247 mV at 100 mA cm−2. Physicochemical characterization and mechanistic studies reveal that the close nanoscale features between CoB and CeO2 create abundant binary interfaces, optimize the electronic configuration, induce changes in electronic states, and provide abundant defect sites, thereby enhancing charge transfer capabilities. This work presents a new paradigm for the design of efficient and durable OER electrocatalysts.

由于活性表面外露和质量/电荷转移得到改善，异质结构作为一种提高氧进化反应（OER）性能的有效策略已被越来越多的人所认可。受天然植物结构的启发，本研究开发了一种独特的苔藓状非晶/晶体（CoB/CeO2）异质结。这种独特的苔藓状形态有利于在催化剂中形成交错的片状结构，为反应中间体和气体释放提供更多的活性位点和开放通道。得益于苔藓状形态带来的亲水性能，CoB/CeO2 在 1M KOH 中表现出卓越的 OER 催化性能，在 100 mA cm-2 的条件下仅需 247 mV。理化表征和机理研究表明，CoB 和 CeO2 之间紧密的纳米级特征创造了丰富的二元界面，优化了电子构型，引起了电子状态的变化，并提供了丰富的缺陷位点，从而增强了电荷转移能力。这项工作为设计高效、耐用的 OER 电催化剂提供了一种新的范例。

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引用次数: 0

A novel extra-broadband visible-emitting garnet phosphor for efficient single-component pc-WLEDs† 用于高效单组分 pc-WLED 的新型超宽带可见光石榴石荧光粉

IF 6.1 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers

Pub Date : 2024-11-01 DOI: 10.1039/D4QI01824A

Qianyi Chen, Zhenjie Lun, Dongdan Chen, Yongsheng Sun, Puxian Xiong, Siyun Li, Shanhui Xu and Zhongmin Yang

The development of extra-broadband visible emission phosphors is crucial to achieve next-generation illumination with better color experience. Herein, a defect engineering strategy mediated by the structural cationic substitution is proposed and experimentally demonstrated for specific ultra-broadband emission in a garnet phosphor. The induced oxygen vacancies and interstitial cation through lattice distortion break the periodic potential field of the crystal and provide electronic levels in the band gap. As a result, excited by blue-light-emitting diodes, the novel Y₃Sc₂Al₃O₁₂:B³⁺ shows an ultra-broad emission with a full width at half maximum (FWHM) of ∼170 nm. Compared to general defect-emitting phosphors, the unique Y₃Sc₂Al₃O₁₂:B³⁺ exhibits excellent thermal quenching resistance and superior internal quantum efficiency of up to 95%. These findings not only show great promise of Y₃Sc₂Al₃O₁₂:B³⁺ as an extra-broadband emitter but also provide a new design strategy to achieve a full-visible-spectrum phosphor in a single-component material for white-light applications.

开发超宽带可见光发射荧光粉对于实现具有更好色彩体验的下一代照明至关重要。本文提出了一种以结构阳离子置换为介导的缺陷工程策略，并通过实验证明了石榴石荧光粉的特定超宽带发射。通过晶格畸变诱导的氧空位和间隙阳离子打破了晶体的周期势场，提供了带隙中的电子水平。因此，在蓝光发光二极管的激发下，新型 Y3Sc2Al3O12:B3+ 显示出超宽的发射，半最大值全宽（FWHM）达到 ∼ 170 nm。与一般的缺陷发光荧光粉相比，独特的 Y3Sc2Al3O12:B3+ 具有优异的抗热淬性能和高达 95% 的内部量子效率。这些发现不仅显示了 Y3Sc2Al3O12:B3+ 作为一种超宽带发光体的巨大前景，而且还提供了一种新的设计策略，即在单组分材料中实现白光应用中的全可见光谱荧光粉。

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引用次数: 0

Ni non-equivalent doped La-MOF toward enhanced photocatalytic CO2 reduction through oxygen vacancy regulation and electronic structure optimization 通过氧空位调节和电子结构优化掺杂非等价镍的 La-MOF 增强光催化二氧化碳还原能力

IF 7 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers

Pub Date : 2024-10-31 DOI: 10.1039/d4qi02143f

Tongzheng Zhang, Zhaohui Huang, Guanshun Xie, Le Liao, Changqiang Yu, Xiuqiang Xie, Nan Zhang

Photocatalytic CO2 reduction holds promise for mitigating global warming and achieving carbon neutrality. Metal-organic frameworks (MOFs) are particularly promising as photocatalysts due to their ability to tune metal-oxo cluster electronic structures and facilitate CO2 adsorption. In this study, chemically stable La-MOF modified with Ni-doped metal-oxo clusters has been synthesized through a one-pot solvent-thermal reaction. The experimental and in-situ test results show that the introduction of Ni atoms leads to the formation of oxygen vacancies(VOs)induced by the unsaturated coordination of La/Ni-MOF, which facilitates the adsorption and activation of CO2. The electronic structure of metal oxo (La-O- ) clusters is also effectively regulated, which enhances electron-accepting ability of La-O clusters and promotes the photo-induced electron transfer from the lowest unoccupied molecular orbital (LUMO) of electron donor to the conduction band (CB) of La-MOF. In addition, the additional built-in metal atom (Ni) acts as an active site for CO2 adsorption and activation, achieving effective charge transfer and activated CO2 adsorption integrated construction. The synergy of these effects leads to the optimal La/Ni-MOF withCO selectivity of 96.8% and theyield of 669.3 μmol/g, which is 2.5-fold and more than 5-fold as high as that of the pure La-MOF and Ni-MOF, respectively. This work provides a facile but efficient approach for the construction of coordination unsaturated metal sites and VOs as well as the regulation of the electronic structure of MOFs as efficient photocatalysts towards enhanced performances.

光催化二氧化碳还原有望缓解全球变暖并实现碳中和。金属有机框架（MOFs）具有调整金属氧簇电子结构和促进二氧化碳吸附的能力，因此特别有希望成为光催化剂。本研究通过一锅溶剂热反应合成了化学性质稳定的掺镍金属氧簇修饰的 La-MOF。实验和原位测试结果表明，镍原子的引入导致了 La/Ni-MOF 不饱和配位诱导的氧空位（VOs）的形成，从而促进了 CO2 的吸附和活化。金属氧化物（La-O-）团簇的电子结构也得到了有效调节，从而增强了 La-O 团簇的电子接受能力，促进了光诱导电子从电子供体的最低未占分子轨道（LUMO）转移到 La-MOF 的导带（CB）。此外，附加的内置金属原子（镍）作为二氧化碳吸附和活化的活性位点，实现了有效的电荷转移和活化二氧化碳吸附的一体化构建。在这些效应的协同作用下，得到了最佳的 La/Ni-MOF ，其 CO 选择性为 96.8%，产率为 669.3 μmol/g，分别是纯 La-MOF 和 Ni-MOF 的 2.5 倍和 5 倍以上。这项工作为构建配位不饱和金属位点和 VOs 以及调节 MOFs 的电子结构以提高其作为高效光催化剂的性能提供了一种简便而有效的方法。

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引用次数: 0

A novel cerium-based metal-organic framework supported Pd catalyst for semi-hydrogenation of phenylacetylene 用于苯乙炔半加氢的新型铈基金属有机框架支撑钯催化剂

IF 7 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers

Pub Date : 2024-10-31 DOI: 10.1039/d4qi02225d

Xiangdi Zeng, Zi Wang, Meng He, Wanpeng Lu, Wenyuan Huang, Bing An, Jiangnan Li, Li Mufan, Ben Spencer, Sarah Day, Floriana Tuna, Eric J L McInnes, Martin Schroder, Sihai Yang

Phenylacetylene is a detrimental impurity in the polymerisation of styrene, capable of poisoning catalysts even at ppm levels and significantly degrading the quality of polystyrene. The semi-hydrogenation of phenylacetylene to styrene instead of ethylbenzene is, therefore, an important industrial process. We report a novel cerium(IV)-based metal-organic framework (denoted as Ce-bptc), which is comprised of {Ce6} clusters bridged by biphenyl-3,3’,5,5’-tetracarboxylate linkers. Ce-bptc serves as an ideal support for palladium nanoparticles and the Pd@Ce-bptc catalyst demonstrates an excellent catalytic performance for semi-hydrogenation of phenylacetylene, achieving a selectivity of 93% to styrene on full conversion under ambient conditions with excellent reusability. In situ synchrotron X-ray powder diffraction and electron paramagnetic resonance spectroscopy revealed the binding domain of phenylacetylene within Ce-bptc and details of the reaction mechanism.

苯乙炔是苯乙烯聚合过程中的一种有害杂质，即使在百万分之几的水平上也能毒害催化剂，并显著降低聚苯乙烯的质量。因此，将苯乙炔半氢化成苯乙烯而不是乙苯是一种重要的工业工艺。我们报告了一种新型的基于铈（IV）的金属有机框架（称为 Ce-bptc），它由联苯-3,3',5,5'-四羧酸链节桥接的 {Ce6} 簇组成。Ce-bptc 是钯纳米粒子的理想载体，Pd@Ce-bptc 催化剂在苯乙炔的半加氢反应中表现出优异的催化性能，在环境条件下完全转化时对苯乙烯的选择性达到 93%，并具有极佳的重复利用率。原位同步辐射 X 射线粉末衍射和电子顺磁共振光谱揭示了苯乙炔在 Ce-bptc 中的结合域和反应机理的细节。

引用次数: 0