Iron‐Based Metal–Organic Frameworks as Catalysts for Visible Light‐Driven Water Oxidation

The development of earth‐abundant, active, and stable catalysts is important for solar energy conversion. Metal‐organic frameworks (MOFs) have been viewed as a promising class of porous materials, which may have innovative application in photocatalysis. In this paper, three types of Fe‐based MOFs and their aminofunctionalized derivatives have been fabricated and systematically studied as water oxidation catalysts (WOCs) for oxygen evolution under visible light irradiation. MIL‐101(Fe) possesses a higher current density and earlier onset potential and exhibits excellent visible light‐driven oxygen evolution activity than the other Fe‐based catalysts. It speeds up the oxygen evolution reaction rate with the higher initial turnover frequencies value of 0.10 s^?1. Our study demonstrates that Fe‐based MOFs as efficient WOCs are promising candidates for photocatalytic water oxidation process.     

Metal–Organic Frameworks and Their Derived Materials: Emerging Catalysts for a Sulfate Radicals‐Based Advanced Oxidation Process in Water Purification

With the ever‐growing environmental issues, sulfate radical (SO₄^??)‐based advanced oxidation processes (SR‐AOPs) have been attracting widespread attention due to their high selectivity and oxidative potential in water purification. Among various methods generating SO₄^??, employing heterogeneous catalysts for activation of peroxymonosulfate or persulfate has been demonstrated as an effective strategy. Therefore, the future advances of SR‐AOPs depend on the development of adequate catalysts with high activity and stability. Metal–organic frameworks (MOFs) with large surface area, ultrahigh porosity, and diversity of material design have been extensively used in heterogeneous catalysts, and more recently, enormous effort has been made to utilize MOFs‐based materials for SR‐AOPs applications. In this work, the state‐of‐the‐art research on pristine MOFs, MOFs composites, and their derivatives, such as oxides, metal/carbon hybrids, and carbon materials for SR‐AOPs, is summarized. The mechanisms, including radical and nonradical pathways, are also detailed in the discussion. This work will hopefully promote the future development of MOFs‐based materials toward SR‐AOPs applications.     

CO催化氧化催化剂活性成分研究进展

CO催化氧化消除在环保、氢燃料电池等许多领域具有重要应用,其催化剂活性成分可以使用单组分及多组分的贵金属、非贵金属、金属氧化物、复合氧化物等。非贵金属活性成分的使用对降低催化剂的成本具有重要意义。从催化剂活性成分的角度来审视不同催化剂的催化性能和构效关系,综述了CO催化氧化催化剂的研究现状。     

Enzyme–Metal Hybrid Catalysts for Chemoenzymatic Reactions

Enzyme–metal hybrid catalysts (EMHCs), which combine enzymatic and metal catalysis, provide tremendous possibilities for new chemoenzymatic cascade reactions. Here, an overview of the representative achievements in the design of EMHCs and their applications in chemoenzymatic cascade reactions are presented. The preparation of hybrid catalysts is classified into two categories: coimmobilized enzyme–metal heterogeneous catalysts and carrier‐free enzyme–metal bioconjugates. Examples of one‐pot chemoenzymatic cascade processes catalyzed by the hybrid catalysts are then provided as potential applications. Finally, the limitations and future perspectives of EMHCs are discussed.     

Designing Advanced Catalysts for Energy Conversion Based on Urea Oxidation Reaction

Urea oxidation reaction (UOR) is the underlying reaction that determines the performance of modern urea‐based energy conversion technologies. These technologies include electrocatalytic and photoelectrochemical urea splitting for hydrogen production and direct urea fuel cells as power engines. They have demonstrated great potentials as alternatives to current water splitting and hydrogen fuel cell systems with more favorable operating conditions and cost effectiveness. At the moment, UOR performance is mainly limited by the 6‐electron transfer process. In this case, various material design and synthesis strategies have recently been reported to produce highly efficient UOR catalysts. The performance of these advanced catalysts is optimized by the modification of their structural and chemical properties, including porosity development, heterostructure construction, defect engineering, surface functionalization, and electronic structure modulation. Considering the rich progress in this field, the recent advances in the design and synthesis of UOR catalysts for urea electrolysis, photoelectrochemical urea splitting, and direct urea fuel cells are reviewed here. Particular attention is paid to those design concepts, which specifically target the characteristics of urea molecules. Moreover, challenges and prospects for the future development of urea‐based energy conversion technologies and corresponding catalysts are also discussed.     

过渡金属氧化物非均相催化过硫酸氢盐(PMS)活化及氧化降解水中污染物的研究进展

近年来,水体中富集的难降解污染物导致了诸多环境问题,传统水处理工艺并不能对其进行有效处理。高级氧化技术是目前处理难降解污染物的最有效方法。过渡金属氧化物非均相催化过硫酸氢盐(PMS)活化生成硫酸根自由基(SO_4~-·)处理水体中难降解污染物是近些年新兴的高级氧化技术,与以生成羟基自由基(·OH)为基础的传统高级氧化技术相比,该技术具有对pH适应范围更宽、中性条件下氧化性更强、自由基半衰期更长的优势,同时也克服了均相催化体系中金属离子的二次污染、难以重复利用的问题,受到环境领域学者的广泛关注,为去除水体中抗生素、激素等难降解污染物提供了新的思路和方法。然而,由于活性点位的减少,相较于均相催化,非均相催化的催化效率更低,同时也存在催化稳定性差、难以回收等不足。针对上述问题,近几年除了探寻对PMS的活化具有催化活性的新型过渡金属氧化物外,研究者主要从催化材料的负载、改性以及复合三方面进行尝试,并取得了丰富的研究成果,在发挥非均相催化经济、环保优势的同时,大幅提高了催化剂的催化效率及可回收性,为其步入实际应用做出了巨大的贡献。在众多过渡金属元素中,钴、铁、锰的氧化物已被证明对PMS的活化具有催化活性并得到了广泛的研究。其中,由于钴离子对PMS表现出最强的活化能力,因此对钴系氧化物研究得最早。随后,铁及锰的氧化物因环境友好、廉价易得的优势逐渐成为钴氧化物的替代品。近五年的研究工作将纳米碳、介孔材料以及金属-有机框架等引入催化剂的制备合成中,对过渡金属氧化物进行负载和改性,加强了催化材料的电子传递速度和化学稳定性,为解决催化剂的催化效率低与催化稳定性差等问题提供了有效方法。此外,以两种过渡金属元素为催化核心的二元复合材料,在降低催化剂制作成本的同时,还可以实现催化剂效能和稳定性的双重提高。文章介绍了钴系氧化物、锰系氧化物、铁系氧化物等三种能够催化PMS活化的一元非均相催化剂的研究进展,并阐述了二元复合催化剂的研究现状,总结了现阶段研究的不足并对未来的发展方向做出了展望,以期为制备经济高效的过渡金属氧化物催化剂提供参考。     

Catalysis of a Single Transition Metal Site for Water Oxidation: From Mononuclear Molecules to Single Atoms

Low-cost, nonprecious transition metal (TM) catalysts toward efficient water oxidation are of critical importance to future sustainable energy technologies. The advances in structure engineering of water oxidation catalysts (WOCs) with single TM centers as active sites, for example, single metallic molecular complexes (SMMCs), supported SMMCs, and single-atom catalysts (SACs) in recent reports are examined. The efforts made on these configurations in terms of design principle, advanced characterization, performances and theoretical studies, are critically reviewed. A clear roadmap with the correlations between the single-TM-site-based structures (coordination and geometric structure, TM species, support), and the catalytic performances in water oxidation is provided. The insights bridging SMMCs with SACs are also given. Finally, the challenges and opportunities in the single-TM-site catalysis are proposed.     

Phthalocyanine–Virus Nanofibers as Heterogeneous Catalysts for Continuous‐Flow Photo‐Oxidation Processes

The generation of highly reactive oxygen species (ROS) at room temperature for application in organic synthesis and wastewater treatment represents a great challenge of the current chemical industry. In fact, the development of biodegradable scaffolds to support ROS‐generating active sites is an important prerequisite for the production of environmentally benign catalysts. Herein, the electrostatic cocrystallization of a cationic phthalocyanine (Pc) and negatively charged tobacco mosaic virus (TMV) is described, together with the capacity of the resulting crystals to photogenerate ROS. To this end, a novel peripherally crowded zinc Pc (1) is synthesized. With 16 positive charges, this photosensitizer shows no aqueous aggregation, and is able to act as a molecular glue in the unidimensional assembly of TMV. A step‐wise decrease of ionic strength in mixtures of both components results in exceptionally long fibers, constituted by hexagonally bundled viruses thoroughly characterized by electron and confocal microscopy. The fibers are able to produce ROS in a proof‐of‐concept microfluidic device, where they are immobilized and irradiated in several cycles, showing a resilient performance. The bottom‐up approach also enables the light‐triggered disassembly of fibers after use. This work represents an important example of a biohybrid material with projected application in light‐mediated heterogeneous catalysis.     

纳米金催化剂Au/ZnAl-LDHs的制备及在CO常温氧化反应中的活性及稳定性

以人工合成的双羟基金属氢氧化物ZnAl-LDHs为载体,将预先制备的金溶胶通过静电吸附的方式负载到载体上,获得了纳米金催化剂Au/ZnAl-LDHs,用X射线粉末衍射(XRD)表征了催化剂的物相,用透射电镜(TEM)观察了纳米金颗粒的粒径分布,以CO的常温催化氧化为模型反应,分别考察了金溶胶制备过程中金前体HAuCl4·6H2O的浓度和还原剂THPC的用量、负载过程的pH值以及金的负载量等因素对金催化剂的活性和稳定性的影响。结果表明:在制备金溶胶的过程中,降低HAuCl4·6H2O的浓度并提高还原剂THPC的用量,可以制备出粒径分布处于1~7nm之间、平均粒径仅3.87nm的负载型纳米金颗粒,其对CO的常温转化率为100%,且其催化活性的稳定性明显提高;而在金溶胶的吸附负载过程中,使体系的pH值处于6~7的范围,有利于金溶胶在ZnAl-LDHs载体上的吸附负载,从而得到实际负载量更接近理论负载量的金催化剂样品,当金的实际负载量接近1%(质量分数)时,能够确保对CO的常温氧化转化率达到100%。     

Ultra-Highly Active Ni-Doped MOF-5 Heterogeneous Catalysts for Ethylene Dimerization

Here, an ultra-highly active Ni-MOF-5 catalyst with high Ni loading for ethylene dimerization is reported. The Ni-MOF-5 catalysts are synthesized by a facile one-pot co-precipitation method at room temperature, where Ni²⁺ replaces Zn²⁺ in MOF-5. Unlike Zn²⁺ with tetrahedral coordination in MOF-5, Ni²⁺ is coordinated with extra solvent molecules except for four-oxygen from the framework. After removing coordinated solvent molecules, Ni-MOF-5 achieves an ethylene turnover frequency of 352 000 h⁻¹, corresponding to 9040 g of product per gram of catalyst per hour, at 35 °C and 50 bar, far exceeding the activities of all reported heterogeneous catalysts. The high Ni loading and full exposure structure account for the excellent catalytic performance. Isotope labeling experiments reveal that the catalytic process follows the Cossee–Arlman mechanism, rationalizing the high activity and selectivity of the catalyst. These results demonstrate that Ni-MOF-5 catalysts are very promising for industrial catalytic ethylene dimerization.     

Strongly Coupled CoO Nanoclusters/CoFe LDHs Hybrid as a Synergistic Catalyst for Electrochemical Water Oxidation

Exploiting high‐performance, robust, and cost‐effective electrocatalysts for the oxygen evolution reaction (OER) is crucial for electrochemical energy storage and conversion technologies. Engineering the interfacial structure of hybrid catalysts often induces synergistically enhanced electrocatalytic performance. Herein, a new strongly coupled heterogeneous catalyst with proper interfacial structures, i.e., CoO nanoclusters decorated on CoFe layered double hydroxides (LDHs) nanosheets, is prepared via a simple one‐step pulsed laser ablation in liquid method. Thorough spectroscopic characterizations reveal that strong chemical couplings at the hybrid interface trigger charge transfer from Co^II in the oxide to Fe^III in the LDHs through the interfacial Fe? O? Co bond, leading to considerable amounts of high oxidation state Co^III sites present in the hybrid. Interestingly, the CoO/CoFe LDHs exhibit pronounced synergistic effects in electrocatalytic water oxidation, with substantially enhanced intrinsic catalytic activity and stability relative to both components. The hybrid catalyst achieves remarkably low OER overpotential and Tafel slope in alkaline medium, outperforming that of Ru/C and manifesting itself among the most active Co‐based OER catalysts.     

Recent Progress in Methanol‐to‐Olefins (MTO) Catalysts

Methanol conversion to olefins, as an important reaction in C1 chemistry, provides an alternative platform for producing basic chemicals from nonpetroleum resources such as natural gas and coal. Methanol‐to‐olefin (MTO) catalysis is one of the critical constraints for the process development, determining the reactor design, and the profitability of the process. After the construction and commissioning of the world's first MTO plant by Dalian Institute of Chemical Physics, based on high‐efficiency catalyst and fluidization technology in 2010, more attention has been attracted for a deep understanding of the reaction mechanism and catalysis principle, which has led to the continuous development of catalysts and processes. Herein, the recent progress in MTO catalyst development is summarized, focusing on the advances in the optimization of SAPO‐34 catalysts, together with the development efforts on catalysts with preferential ethylene or propylene selectivity.     

Nanoparticles@nanoscale metal-organic framework composites as highly efficient heterogeneous catalysts for size-and shape-selective reactions

Composites incorporating nanoparticles (NPs) within metal-organic frameworks (MOFs) find applications in many different fields.In particular,using MOF layers as molecular sieves built on the NPs could enable selectivity in heterogeneous catalysis.However,such composites typically exhibit low catalytic efficiency,due to the slow diffusion of the reactants in the long and narrow channels of the MOF shell.In order to improve the catalytic efficiency of these systems,here we report the fabrication of NPs incorporated in nanosized MOFs (NPs@nano-MOFs),obtained by reducing the size of the MOF crystals grown around the NPs.The crystal size of the composites was controlled by modulating the nucleation rate of the MOFs during the encapsulation of pre-synthesized and catalytically active NPs;in this way,NPs@MOF crystals smaller than 50 nm were synthesized and subsequently used as highly efficient catalysts.Due to the shorter path from the MOF surface to the active sites,the obtained Pt@nano-MOFs composites showed a higher conversion rate than their larger-sized counterparts in the synthesis of imines via cascade reaction of nitrobenzene and in the hydrogenation of olefins,while retaining the excellent size and shape selectivity associated with the molecular sieving effect of the MOF layer.The present strategy can also be applied to prepare other encapsulated nanostructures combining various types of NPs and nano-MOFs,thus highlighting the broad potential of this approach for developing optimized catalysts with high reactivity and selectivity.     

超临界水氧化环境中材料腐蚀的研究现状

超临界水氧化（SCWO）技术是近年发展起来的处理有机难溶废物的安全高效的新技术,在阐述超临界水的物理,化学性质的基础上,介绍了XCWO反应的工作原理和流,分析总结了世界范围内开展的SCWO的环境中材料的的腐蚀及监测技术等方面的研究动态,提出了我国SCWO技术研究的未来发展方向。     

Bimetallic Nickel‐Substituted Cobalt‐Borate Nanowire Array: An Earth‐Abundant Water Oxidation Electrocatalyst with Superior Activity and Durability at Near Neutral pH

There is an urgent demand to develop earth‐abundant electrocatalysts for efficient and durable water oxidation under mild conditions. A nickel‐substituted cobalt‐borate nanowire array is developed on carbon cloth (Ni‐Co‐Bi/CC) via oxidative polarization of NiCo₂S₄ nanoarray in potassium borate (K‐Bi). As a bimetallic electrocatalyst for water oxidation, such Ni‐Co‐Bi/CC is superior in catalytic activity and durability in 0.1 m K‐Bi (pH: 9.2), with a turnover frequency of 0.33 mol O₂ s^?1 at the overpotential of 500 mV and nearly 100% Faradaic efficiency. To drive a geometrical catalytic current density of 10 mA cm^?2, it only needs overpotential of 388 mV, 34 mV less than that for Co‐Bi/CC, outperforming reported non‐noble‐metal catalysts operating under benign conditions. Notably, its activity is maintained over 80 000 s. Density functional theory calculations suggest that the O* to OOH* conversion is the rate‐determining step and Ni substitution decreases the free energy on Co‐Bi from 2.092 to 1.986 eV.