Synergistic Metal-Nonmetal Active Sites in a Metal-Organic Cage for Efficient Photocatalytic Synthesis of Hydrogen Peroxide in Pure Water

Photocatalytic synthesis of hydrogen peroxide (H₂O₂) is a potential clean method, but the long distance between the oxidation and reduction sites in photocatalysts hinders the rapid transfer of photogenerated charges, limiting the improvement of its performance. Here, a metal-organic cage photocatalyst, Co₁₄(L−CH₃)₂₄ , is constructed by directly coordinating metal sites (Co sites) used for the O₂ reduction reaction (ORR) with non-metallic sites (imidazole sites of ligands) used for the H₂O oxidation reaction (WOR), which shortens the transport path of photogenerated electrons and holes, and improves the transport efficiency of charges and activity of the photocatalyst. Therefore, it can be used as an efficient photocatalyst with a rate of as high as 146.6 μmol g⁻¹ h⁻¹ for H₂O₂ production under O₂-saturated pure water without sacrificial agents. Significantly, the combination of photocatalytic experiments and theoretical calculations proves that the functionalized modification of ligands is more conducive to adsorbing key intermediates (*OH for WOR and *HOOH for ORR), resulting in better performance. This work proposed a new catalytic strategy for the first time; i.e., to build a synergistic metal-nonmetal active site in the crystalline catalyst and use the host–guest chemistry inherent in the metal-organic cage (MOC)to increase the contact between the substrate and the catalytically active site, and finally achieve efficient photocatalytic H₂O₂ synthesis.     

Hydrothermal Preparation and Characterization of TiO2/BiVO4 Composite Catalyst and its Photolysis of Water to Produce Hydrogen

In the present work, bismuth vanadate composited photocatalysts were synthesized and characterized. X‐ray diffractometry and Raman results showed that the particles were well crystallized, and formed by the complex of monoclinic BiVO₄ and TiO₂. On electron microscopy, the photocatalyst exhibited high crystallization, agglutination and irregular shape, and was surrounded by numerous TiO₂ particles. The study of surface areas showed that the specific surface area of 30‐BiVO₄/TiO₂ composited was 112 m²·g^?1, which was nearly 10 times that of pure BiVO₄. The ultraviolet–visible diffuse reflectance spectra indicated the composited photocatalyst were activated in visible light. The activity of photocatalytic water splitting was studied. The results showed that monomer BiVO₄ photocatalyst was not able to produce hydrogen under any light source. BiVO₄/TiO₂ composited photocatalysts, however, were capable of generating hydrogen. Under UV light irradiation for 120 min, 1 g catalyst dispersed in 50 mL deionized water produced almost 1 mL hydrogen, such that the productivity of hydrogen was higher than that of P25‐TiO₂. Photocatalytic decomposition of water under visible light also confirmed that the BiVO₄/TiO₂ composited photocatalyst had the ability of water splitting.     

Grafting Molecular Cobalt‐oxo Cubane Catalyst on Polymeric Carbon Nitride for Efficient Photocatalytic Water Oxidation

In this work, we have successfully constructed a cobalt–oxo (Co^III₄O₄) cubane complex on polymeric carbon nitride (PCN) through pyridine linkage. The covalently grafted Co^III₄O₄ cubane units were uniformly distributed on the PCN surface. The product exhibited greatly enhanced photocatalytic activities for water oxidation under visible‐light irradiation. Further characterizations and spectroscopic analyses revealed that the grafted Co^III₄O₄ cubane units could effectively capture the photogenerated holes from excited PCN, lower the overpotential of oxygen evolution reaction (OER), and serve as efficient catalysts to promote the multi‐electron water oxidation process. This work provides new insight into the future development of efficient photocatalysts by grafting molecular catalysts for artificial photosynthesis.     

Synthesis of BiVO4-GO-PVDF nanocomposite: An excellent,newly designed material for high photocatalytic activity towards organic dye degradation by tuning band gap energies

BiVO_4-GO-PVDF (PVDF = Polyvinylidene Difluoride) photocatalyst is successfully synthesized by ultrasonication method and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and transmission electron microscopy techniques. Morphology of BiVO₄-GO-PVDF looks like a human embryo embedded inside an amniotic sac. Photocatalytic performance of BiVO₄-GO-PVDF for decolorization of methylene blue is investigated. BiVO₄-GO-PVDF system reveals enhanced photocatalytic activity degradation of methylene blue (MB), Rhodamine B (RhB) & Safranin-O (SO) in water under visible light irradiation as compared to the pure BiVO₄ catalyst, BiVO₄ & PTFE decorated on the graphene sheet. The experimental result reveals that the covering of graphene sheets in this composite catalyst enhances photocatalytic performance under visible light. This enhanced activity is mainly attributed to effective quenching of the photogenerated electron-hole pairs confirmed by photoluminescence spectra. Trapping experiments of radicals and holes were conducted to detect reactive species generated in the photocatalytic system, experimental results revealed that direct hole oxidation reaction is obviously dominant during photocatalytic reactions on the BiVO₄-GO-PVDF system.     

一步醇-水热法合成高效的F掺杂BiVO4光催化剂

以NH₄F为掺杂前体,采用简单的一步醇-水热法制备了F掺杂BiVO₄光催化剂。利用X射线衍射（XRD）、扫描电子显微镜（SEM）、X射线光电子能谱（XPS）、紫外-可见漫反射光谱（UV-Vis）和光致发光光谱（PL）表征了这些光催化剂的物理化学性质。在少量H₂O₂存在条件下,以可见光照射下光催化降解苯酚的反应测定了这些光催化剂的催化活性。研究表明,相较于未掺杂的BiVO₄样品而言,F掺杂BiVO₄样品不仅仍保留了单斜结构,而且有更高的结晶度、表面氧空位密度和光生电荷载流子分离效率,更强的光吸收和更低的带隙能。在这些F掺杂BiVO₄样品中,以n_F/n_Bi的理论值为1.0且带隙能为2.43 eV的F掺杂BiVO₄样品的光催化活性最好（90 min内苯酚的降解率可达95%）。这一优良的光催化性能与其具有最高的结晶度、表面氧空位密度和光生电荷载流子分离效率,最强的光吸收和最低的带隙能有关。     

Morphology Engineering of BiVO4 with CoOx Derived from Cobalt-containing Polyoxometalate as Co-catalyst for Oxygen Evolution

Bismuth vanadate (BiVO₄) as a metal oxidation semiconductor has stimulated extensive attention in the photocatalytic water splitting field. However, the poor transport ability and easy recombination of charge carriers limit photocatalytic water oxidation activity of pure BiVO₄. Herein, the photocatalytic activity of BiVO₄ is enhanced via adjusting its morphology and combination co-catalyst. First, the Cu-BiVO₄ was synthesized by copper doping to control the growth of {110} facet of BiVO₄, which is regarded for the separation of photo-generated charge carriers. Then the CoO_x in-situ generated from K₆[SiCo^II(H₂O)W₁₁O₃₉] ⋅ 16H₂O was photo-deposited on Cu-BiVO₄ surface as co-catalyst to speed up reaction kinetics. Cu-BiVO₄@CoO_x hybrid catalyst shows highest photocatalytic activity and best stability among all the prepared catalysts. Oxygen evolution is about 34.6 μmol in pH 4 acetic acid buffer under 420 nm LED irradiation, which is nearly 20 times higher than that of pure BiVO₄. Apparent quantum efficiency (AQE) in 1 h and O₂ yield are 1.83% and 23.1%, respectively. O₂ evolution amount nearly maintains the original value even after 5 cycles.     

Visible-light-driven Oxygen Vacancy and Carbon Doping of C@TiO2-x Photocatalyst for Enhanced Pollutants Degradation Performance

Oxygen Vacancy (OVs) and carbon doping of the photocatalyst body will significantly enhance the photocatalytic efficiency. However, synchronous regulation of these two aspects is challenging. In this paper, a novel C@TiO_2-x photocatalyst was designed by coupling the surface defect and doping engineering of titania, which can effectively remove rhodamine B (RhB) and has a relatively high performance with wide pH range, high photocatalytic activity and good stability. Within 90 minutes, the photocatalytic degradation rate of RhB by C@TiO_2-x (94.1 % at 20 mg/L) is 28 times higher than that of pure TiO₂. Free radical trapping experiments and electron spin resonance techniques reveal that superoxide radicals (⋅O²⁻) and photogenerated holes (h⁺) play key roles in the photocatalytic degradation of RhB. This study demonstrates the possibility of regulating photocatalysts to degrade pollutants in wastewater based on an integrated strategy.     

A Hydrogen Farm Strategy for Scalable Solar Hydrogen Production with Particulate Photocatalysts

Scalable solar hydrogen production by water splitting using particulate photocatalysts is promising for renewable energy utilization. However, photocatalytic overall water splitting is challenging owing to slow water oxidation kinetics, severe reverse reaction, and H₂/O₂ gas separation. Herein, mimicking nature photosynthesis, a practically feasible approach named Hydrogen Farm Project (HFP) is presented, which is composed of solar energy capturing and hydrogen production subsystems integrated by a shuttle ion loop, Fe³⁺/Fe²⁺. Well‐defined BiVO₄ crystals with precisely tuned {110}/{010} facets are ideal photocatalysts to realize the HFP, giving up to 71 % quantum efficiency for photocatalytic water oxidation and full forward reaction with nearly no reverse reaction. An overall solar‐to‐chemical efficiency over 1.9 % and a solar‐to‐hydrogen efficiency exceeding 1.8 % could be achieved. Furthermore, a scalable HFP panel for solar energy storage was demonstrated under sunlight outdoors.     

Enhancement of Solar Fuel Production Schemes by Using a Ru,Rh,Ru Supramolecular Photocatalyst Containing Hydroxide Labile Ligands

Polyazine‐bridged Ru^IIRh^IIIRu^II complexes with two halide ligands, Cl^? or Br^?, bound to the catalytically active Rh center are efficient single‐component photocatalysts for H₂O reduction to H₂ fuel, with the coordination environment on Rh impacting photocatalysis. Herein reported is a new, halide‐free Ru^IIRh^IIIRu^II photocatalyst with OH^? ligands bound to Rh, further enhancing the photocatalytic reactivity of the structural motif. H₂ production experiments using the photocatalyst bearing OH^? ligands at Rh relative to the analogues bearing halides at Rh in solvents of varying polarity (DMF, CH₃CN, and H₂O) suggest that ion pairing with halides deactivates photocatalyst function, representing an exciting phenomenon to exploit in the development of catalysts for solar H₂ production schemes.     

Hydrothermal Synthesis and Characterization of Visible-Light-Driven Dumbbell-Like BiVO4 and Ag/BiVO4 Photocatalysts

Visible-light-driven dumbbell-like BiVO₄ and Ag/BiVO₄ photocatalysts has been successfully synthesized by a simple hydrothermal method at 180 °C for 24 h. The as-synthesized photocatalysts were characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and UV–Vis absorption spectroscopy. The results obtained showed that ethylenediamine, citric acid, pH and hydrothermal reaction temperature have pronounced effects on the morphology of BiVO₄. Transmission electron microscopy observation shows that the Ag nanoparticles are homogenously dispersed on the surface of the BiVO₄ nanorods. Photocatalytic activities of the dumbbell-like BiVO₄ and Ag-loaded BiVO₄ photocatalysts were also evaluated by using methylene blue as a representative dye indicator under visible light irradiation. It is found that the photocatalytic performance of the as-synthesized BiVO₄ is obviously improved with the incorporation of the Ag nanoparticles. Mechanism for the enhancement of the photocatalytic activity of the Ag/BiVO₄ photocatalyst is also discussed.     

BiVO4/ZnFe2O4同型异质结光阳极的构筑及其光电催化分解水性能

光生电子-空穴对的复合被认为是限制BiVO₄材料光电催化转换效率的重要原因之一。基于此,通过简单的水热-煅烧方法构筑了 BiVO₄/ZnFe₂O₄同型异质结光阳极,BiVO₄/ZnFe₂O₄复合光阳极在 1.23 V(vs RHE)下的光电流密度为 3.33 mA·cm^-2,较纯BiVO₄提升了2倍 (1.20 mA·cm^-2)。相关的结构及性能测试表明,BiVO₄和ZnFe₂O₄形成了带隙错开的n-n异质结,使得光生载流子得到有效分离,更有效地参与水氧化过程,进而提高了BiVO₄的光电催化水分解性能。     

Photocatalytic Degradation of Palm Oil Mill Effluent (POME) Waste Using BiVO4 Based Catalysts

Disposal of palm oil mill effluent (POME), which is highly polluting from the palm oil industry, needs to be handled properly to minimize the harmful impact on the surrounding environment. Photocatalytic technology is one of the advanced technologies that can be developed due to its low operating costs, as well as being sustainable, renewable, and environmentally friendly. This paper reports on the photocatalytic degradation of palm oil mill effluent (POME) using a BiVO₄ photocatalyst under UV-visible light irradiation. BiVO₄ photocatalysts were synthesized via sol-gel method and their physical and chemical properties were characterized using several characterization tools including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), surface area analysis using the BET method, Raman spectroscopy, electron paramagnetic resonance (EPR), and UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS). The effect of calcination temperature on the properties and photocatalytic performance for POME degradation using BiVO₄ photocatalyst was also studied. XRD characterization data show a phase transformation of BiVO₄ from tetragonal to monoclinic phase at a temperature of 450 °C (BV-450). The defect site comprising of vanadium vacancy (V_v) was generated through calcination under air and maxima at the BV-450 sample and proposed as the origin of the highest reaction rate constant (k) of photocatalytic POME removal among various calcination temperature treatments with a k value of 1.04 × 10⁻³ min⁻¹. These findings provide design guidelines to develop efficient BiVO₄-based photocatalyst through defect engineering for potential scalable photocatalytic organic pollutant degradation.     

盐酸溶液处理钒酸铋增强可见光催化活性及其机理

采用盐酸水溶液处理BiVO₄ 的方法获得增强的光催化活性. 在0.1 mol·L^-1 酸溶液中浸渍反应6 h,BiVO₄ 的可见光催化降解苯酚的活性提高了3.5 倍. 采用X 射线衍射(XRD), 扫描电镜(TEM)和漫反射光谱(DRS)等表征手段研究处理后样品的晶相组成和表面形貌, 结合不同酸和氯化物处理的对照实验, 结果表明,在H⁺和Cl^-的协同作用下, BiVO₄表面部分溶出并以BiOCl 沉积, 形成了表面具有凹陷沟壑的BiVO₄颗粒与片状结构BiOCl 的复合物. 采用悬浮液光电压法测定BiOCl 平带电位, 通过BiVO₄和BiOCl 的能带分析及其混合颗粒的光催化活性测试, 确证二者间不存在颗粒间电子转移效应. 增强的光催化活性主要归因于BiVO₄表面形成了有助于光生电荷迁移的凹凸不平结构. 这种表面处理方法有望成为一种增强半导体化合物光催化活性的有效途径.     

Bistability of an iron-cobalt binuclear complex

Bistability of the four cis/trans isomers of the proposed iron-cobalt binuclear complex [(CO)₂(benzoate-)Fe^II/III(-terephthalate-)Co^III/II(-benzoate)(CO)₂]¹⁺, arising from the Fe^II/III ↔ Co^III/II intramolecular charge transfer (IMCT) is investigated computationally at (TD)DFT-B3LYP/LanL2DZ level of theory. Energies, geometries, atomic charges, and the UV-Vis spectra are considered in this investigation. Results approve IMCT bistability of all cis/trans isomers by locating two stable states with distinctly different structures and charge distributions (Fe^II-Co^III and Fe^III-Co^II oxidation states). Also, well-defined first-order saddle points between these two IMCT states are found and characterized using QST2/QST3 method. Based on the analysis of the calculated charge distributions and the 0.35-1.66 eV activation (barrier) energies of the Fe^II-Co^III ↔ Fe^III-Co^II IMCT reactions, it can be predicted that electric field or NIR radiation may be used to switch between the two IMCT states of this bistable binuclear complex. It is also found that the cis/trans isomerization has significant effects on the energetics of this IMCT reaction, and that the trans-Fe^II/III-trans-Co^III/II isomer is the best candidate for prospective switching application due to having the least energy dissipation and the largest charge transfer.     

BiVO4/ZnFe2O4同型异质结光阳极的构筑及其光电催化分解水性能

光生电子-空穴对的复合被认为是限制BiVO₄材料光电催化转换效率的重要原因之一。基于此,通过简单的水热-煅烧方法构筑了BiVO₄/ZnFe₂O₄同型异质结光阳极,BiVO₄/ZnFe₂O₄复合光阳极在1.23 V(vs RHE)下的光电流密度为3.33 mA·cm^-2,较纯BiVO₄提升了2倍(1.20 mA·cm^-2)。相关的结构及性能测试表明,BiVO₄和ZnFe₂O₄形成了带隙错开的n-n异质结,使得光生载流子得到有效分离,更有效地参与水氧化过程,进而提高了BiVO₄的光电催化水分解性能。     

Ag3PO4/BiVO4复合光催化剂的制备及可见光催化降解染料

结合回流法和原位沉淀法成功制备磷酸银/矾酸铋(Ag₃PO₄/BiVO₄)复合光催化剂. 通过X 射线衍射(XRD)、场发射扫描电子显微镜(FESEM)、能量色散X射线光谱(EDS)、紫外-可见漫反射光谱(UV-Vis DRS)及光致发光(PL)光谱对制备样品进行表征. XRD和FESEM结果表明成功制备Ag₃PO₄/BiVO₄复合光催化剂. 采用节能发光二极管灯(LED)作为可见光光源, 在低消耗光催化系统中评价制备样品可见光催化降解染料的活性.当Ag₃PO₄和BiVO₄的组成摩尔比为1:3 时, 复合Ag₃PO₄/BiVO₄光催化剂呈现出高于纯相Ag₃PO₄的催化活性,可减少Ag₃PO₄的使用量. Ag₃PO₄/BiVO₄复合光催化剂在中性溶液中表现出高活性, 同时证实其对阳离子染料的光催化降解效果强于阴离子染料. 在Ag₃PO₄/BiVO₄系统中, 超氧自由基和空穴是主要的活性物种. 经过三次循环利用, Ag₃PO₄/BiVO₄复合催化剂的可见光催化活性表现出不同程度的降低, 归因于降解过程中产生金属银.     

Effect of the Metal on Disulfide/Thiolate Interconversion: Manganese versus Cobalt

It has recently been proposed that disulfide/thiolate interconversion supported by transition‐metal ions is involved in several relevant biological processes. In this context, the present contribution represents a unique investigation of the effect of the coordinated metal (M) on the Mⁿ⁺?disulfide/M⁽ⁿ⁺¹⁾⁺?thiolate switch properties. Like its isostructural Co^II‐based parent compound, Co^II ₂ SS (Angew. Chem. Int. Ed.­ 2014 , 53, 5318), the new dinuclear disulfide‐bridged Mn^II complex Mn^II ₂ SS can undergo an M^II?disulfide/M^III?thiolate interconversion, which leads to the first disulfide/thiolate switch based on Mn. The coordination of iodide to the metal ion stabilizes the oxidized form, as the disulfide is reduced to the thiolate. The reverse process, which involves the reduction of M^III to M^II with the concomitant oxidation of the thiolates, requires the release of iodide. The Mn^II ₂ SS complex slowly reacts with Bu₄NI in CH₂Cl₂ to afford the mononuclear Mn^III?thiolate complex Mn^IIII . The process is much slower (ca. 16 h) and much less efficient (ca. 30 % yield) with respect to the instantaneous and quantitative conversion of Co^II ₂ SS into Co^IIII under similar conditions. This distinctive behavior can be rationalized by considering the different electrochemical properties of the involved Co and Mn complexes and the DFT‐calculated driving force of the disulfide/thiolate conversion. For both Mn and Co systems, M^II?disulfide/M^III?thiolate interconversion is reversible. However, when the iodide is removed with Ag⁺, the M^II ₂ SS complexes are regenerated, albeit much slower for Mn than for Co systems.     

Fabrication of ternary dual Z-Scheme AgI/ZnIn2S4/BiVO4 heterojunction photocatalyst with enhanced photocatalytic degradation of tetracycline under visible light

In this study, a novel ternary AgI/ZnIn₂S₄/BiVO₄(AZB) composite photocatalyst was successfully prepared by hydrothermal method and in-situ precipitation method. The as-synthesized samples were characterized by XRD, SEM, TEM, XPS and so on, and the photocatalytic activity was evaluated through photocatalytic degradation of tetracycline (TC) under visible light irradiation. When the molar ratio of Bi to Ag was 1:1, the degradation rate of TC can reach 91.44 % within 150 min. The AZB heterojunction demonstrated outstanding efficiency with the apparent reaction rate constants of 0.02118 min^?1 for TC removal, was 4.68, 3.27 and 3.27 times higher than that of pure BiVO₄, AgI and ZnIn₂S₄. Based on active species trapping experiments and ESR analysis, a dual Z-Scheme pathways among BiVO₄, AgI and ZnIn₂S₄ for effective separation of photogenerated charges was recommended. This work provided a promising insight for the design of ternary dual Z-scheme heterojunction with multilevel electron transfer to present greater photo-absorption, charge separation, and photodegradation for environmental decontamination.     

Non-emissive RuII Polypyridyl Complexes as Efficient and Selective Photosensitizers for the Photooxidation of Benzylamines

Five new Ru^II polypyridyl complexes bearing N-(arylsulfonyl)-8-amidoquinolate ligands and three of their biscyclometalated Ir^III congeners have been prepared and employed as photocatalysts ( PC s) in the photooxidation of benzylamines with O₂. In particular, the new Ru^II complexes do not exhibit photoluminescence, rather they harvest visible light efficiently and are very stable in solution under irradiation with blue light. Their non-emissive behavior has been related to the low electrochemical energy gaps and rationalized on the basis of theoretical calculations (DFT analysis) that predict low S₀←T₁ energy values. Moreover, the Ru^II complexes, despite being non-emissive, display excellent activities in the selective photocatalytic transformation of benzylamines into the corresponding imines. The presence of an electron-withdrawing group (-CF3) on the arene ring of the N-(arylsulfonyl)-8-amidoquinolate ligand improves the photocatalytic activity of the corresponding photocatalyst. Furthermore, all the experimental evidence, including transient absorption spectroscopy measurements suggest that singlet oxygen is the actual oxidant. The Ir^III analogues are considerably more photosensitive and consequently less efficient photosensitizers ( PS s).     

In-situ construction of amorphous/crystalline contact Bi2S3/Bi4O7 heterostructures for enhanced visible-light photocatalysis

Constructing a heterojunction photocatalyst is a significant method to enhance photocatalytic activity because it can promote the separation of photogenerated carriers. Herein, amorphous/crystalline contact Bi₂S₃/Bi₄O₇ heterostructure was successfully synthesized by in-situ sulfidation of Bi₄O₇. The amorphous Bi₂S₃ is diffused on the surface of Bi₄O₇ rod, enhancing the visible light response and improving the transport of photogenerated carriers. Various characterizations confirm that the rapid separation of photogenerated carriers leads to increased photocatalytic performance. The optimized Bi₂S₃/Bi₄O₇ heterostructure photocatalyst (BiS-0.15) exhibits the highest Cr(VI) reduction (0.01350 min⁻¹) and RhB oxidation (0.08011 min⁻¹) activity, which is much higher than that of pure Bi₄O₇ and Bi₂S₃/Bi₄O₇ mixture under visible light irradiation. This work provides new insights into the construction of efficient novel photocatalysts.