Visible Light-induced Oxygen Generation and Cyclic Water Cleavage Sensitized by Porphyrins

Zinctetramethylpyridylporphyrin (ZnTMPyP⁴⁺) in acidic aqueous solution sensitizes efficiently oxygen generation by visible light in the presence of acceptors such as Fe³⁺ - and Ag⁺-ions and colloidal RuO₂/TiO₂ redox catalyst. Hydrogen and oxygen are cogenerated under visible light illumination of ZnTMPyP⁴⁺ solutions when a bifunctional catalyst (Pt and RuO₂ codeposited onto TiO₂) is employed.     

Photocatalytic Water Splitting Under Visible Light with Particulate Semiconductor Catalysts

Photocatalytic water splitting (PWS) is the most promising technology to produce H₂ energy directly from renewable water and solar light. PWS has made a remarkable progress last decades under ultra-violet (UV) light, but there are many technical challenges remaining for PWS under visible light. Several approaches are taken in search of photocatalysts efficient for PWS under visible light: (i) to find new single phase materials, (ii) to decorate UV-active photocatalysts with a photosensitizer absorbing visible light, (iii) to tune the band gap energy by modifying cations or anions of UV-active photocatalysts with substitutional doping, and (iv) to fabricate multi-component photocatalysts by forming composites or solid solutions. This article discusses the above approaches based on our experimental results as well as data available in the literature. At the moment, the greatest challenge to the progress of visible light PWS is the low efficiency of light utilization. Finding new photocatalytic materials with unique structure and phase is still the key to the success. In addition, the synthesis of these materials with high crystallinity and high surface area is also important, because these properties exert great impact on the activity of the material of the same structure and phase. Finally, smart combination and modification of known materials could also be fruitful.     

Visible Light Induced Water Cleavage in CdS Dispersions Loaded with Pt and RuO2, Hole Scavenging by RuO2

Illumination of aqueous CdS dispersions loaded with Pt and RuO₂ by visible light produces hydrogen and oxygen in stoichiometric proportion. No degradation of the photocatalyst is noted after 60 h of irradiation time. The RuO₂ deposit on the particle surface greatly accelerates the transfer of holes from the semiconductor valence band to the aqueous solution thus inhibiting photocorrosion.     

Integrated Systems for Water Cleavage by Visible Light; Sensitization of TiO2 Particles by Surface Derivatization with Ruthenium Complexes

Irradiation of acidic (pH 2) solutions of RuL₃²⁺ 2Cl^? (L = diisopropyl 2,2′-bipyridine-4,4′ -dicarboxylate) in the presence of TiO₂ at 100°C leads to the loss of one bipyridyl ligand and the chemical fixation of RuL₂ at the surface of teh TiO₂ particles through formation of Ru-O-Ti bonds. These surface complexes are very stable and shift the absorption onset of TiO₂ beyond 600 mm. Efficient sensitization H₂-generation is achieved with this system beginning in the wave length domain between 590 and 665 nm. Preliminary water cleavage experiments with bifunctional TiO₂/Pt/RuO₂ redox catalyst are reported.     

可见光照射下SiW12O4-40/Resin光催化剂活化H2O2降解染料的研究

将杂多酸(SiW12O4-40)负载到阴离子交换树脂上,得到SiW12O4-40/Resin(SWR)固相光催化剂,在可见光的照射下,可以有效地活化H2O2降解染料.以罗丹明B(Rhodamine B,RhB)为模型化合物,研究了不同条件下RhB的降解动力学,以及降解过程中其UV-vis光谱及体系的总有机碳(Total Organic Carbon,TOC)变化情况,结果表明RhB的共轭芳环结构被破坏,矿化率为24.2%.其它染料如孔雀绿(Malachite Green,MG)和吖啶橙(Acridine Orange,AO)等也可以被降解和矿化.催化剂的循环实验表明SWR固相光催化剂易于分离,并且具有良好的稳定性,可以重复利用.     

可见光照射下SiW12O40^4-／Resin光催化剂活化H2O2降解染料的研究

将杂多酸（SiW12O40^4-）负载到阴离子交换树脂上，得到SiW12O40^4-／Resin（SWR）固相光催化剂，在可见光的照射下，可以有效地活化H2O2降解染料．以罗丹明B（RhodamineB，RhB）为模型化合物，研究了不同条件下RhB的降解动力学，以及降解过程中其UV—vis光谱及体系的总有机碳（Total Organic Carbon，TOC）变化情况，结果表明RhB的共轭芳环结构被破坏，矿化率为24．2％．其它染料如孔雀绿（Malacllite Green，MG）和吖啶橙（Acridine Orange，AO）等也可以被降解和矿化．催化剂的循环实验表明SWR固相光催化剂易于分离，并且具有良好的稳定性，可以重复利用．     

C=C Bond Oxidative Cleavage of BODIPY Photocages by Visible Light

Photocages for protection and the controlled release of bioactive compounds have been widely investigated. However, the vast majority of these photocages employ the cleavage of single bonds and high-energy ultraviolet light. The construction of a photoactivation system that uses visible light to cleave unsaturated bonds still remains a challenge. Herein, we report a regioselective oxidative cleavage of C=C bonds from a boron-dipyrrolemethene (BODIPY)-based photocage by illumination at 630 nm, resulting in a free aldehyde and a thiol fluorescent probe. This strategy was demonstrated in live HeLa cells, and the generated α-formyl-BODIPY allowed real-time monitoring of aldehyde release in the cells. In particular, it is shown that a mannose-functionalized photocage can target HepG2 cells.     

Simultaneous Generation of H2O2 and Formate by Co-Electrolysis of Water and CO2 over Bifunctional Zn/SnO2 Nanodots

Hydrogen peroxide (H₂O₂) and formate are important chemicals used in various chemical manufacturing industries. One promising approach for the simultaneous production of these chemicals is coupling anodic two-electron water oxidation with cathodic CO₂ reduction in an electrolyzer using nonprecious bifunctional electrocatalysts. Herein, we report an innovative hybrid electrosynthesis strategy using Zn-doped SnO₂ (Zn/SnO₂) nanodots as bifunctional redox electrocatalysts to achieve Faradaic efficiencies of 80.6 % and 92.2 % for H₂O₂ and formate coproduction, respectively, along with excellent stability for at least 60 h at a current density of ≈150 mA cm⁻². Through a combination of physicochemical characterizations, including operando attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), isotope labeling mass spectrometry (MS)/¹H NMR and quasi-in situ electron paramagnetic resonance (EPR), with density functional theory (DFT) calculations, we discovered that the Zn dopant facilitates the coupling of *OH intermediates to promote H₂O₂ production and optimizes the adsorption of *OCHO intermediates to accelerate formate formation. Our findings offer new insights into designing more efficient bifunctional electrocatalyst-based pair-electrosynthesis system for the coproduction of H₂O₂ and formate feedstocks.     

Hydrogen Evolution from Water by Visible Light,a Homogeneous Three Component Test System for Redox Catalysis

Irradiation by visible light of a neutral aqueous solution containing Ru (bipy) as a sensitizer, methylviologen (MV⁺²) as an electron acceptor and triethanolamine or cysteine as an electron donor leads to the formation of stable methylviologen radical cation (MV⁺). The kinetics and mechanism of the photoinduced reactions occurring in such a system were explored by laser photolysis technique. In the presence of Adams catalyst MV⁺ is reoxidized by water under simultaneous evolution of hydrogen. Optimum conditions for the water reduction under continuous illumination are elaborated and implications for an energy conversion system discussed.     

TiO2/Bi2O3纳米复合体的制备及可见光催化产氢性能

首先采用相分离的水解-溶剂热法制备了Bi₂O₃纳米粒子,然后利用简单的湿化学法在Bi₂O₃表面负载不同比例的TiO₂纳米颗粒,进而得到TiO₂/Bi₂O₃纳米复合体。通过气氛调控的表面光电压谱(SPS)等测试表明,表面负载适量的TiO₂后能够提高Bi₂O₃光生电荷分离。可见光催化产氢和降解污染物测试结果进一步证明,表面负载适量的TiO₂后可显著提高其可见光催化活性,其中Ti/Bi摩尔比为7%时具有最高的光催化活性。这主要归因于TiO₂具有较为合适的导带能级位置,可以接收Bi₂O₃在可见光激发下所产生的高能级电子,从而抑制光生电子-空穴对复合,并且维持了高能级电子较高的还原能力。     

Ester Reduction with H2 on Bifunctional Metal-Acid Catalysts: Implications of Metal Identity on Rates and Selectivities

Esters reduce to form ethers and alcohols on contact with metal nanoparticles supported on Brønsted acidic faujasite (M-FAU) that cleave C−O bonds by hydrogenation and hydrogenolysis pathways. Rates and selectivities for each pathway depend on the metal identity (M=Co, Ni, Cu, Ru, Rh, Pd, and Pt). Pt-FAU gives propyl acetate consumption rates up to 100 times greater than other M-FAU catalysts and provides an ethyl propyl ether selectivity of 34 %. Measured formation rates, kinetic isotope effects, and site titrations suggest that ester reduction involves a bifunctional mechanism that implicates the stepwise addition of H* atoms to the carbonyl to form hemiacetals on the metal sites, followed by hemiacetal diffusion to a nearby Brønsted acid site to dehydrate to ethers or decompose to alcohol and aldehyde. The rates of reduction of propyl acetate appear to be determined by the H* addition to the carbonyl and by the C−O cleavage of hemiacetal.     

ZnCo2O4纳米粒子的可见光催化性能

研究了共沉淀分解法制备的ZnCo₂O₄纳米粒子的光学和可见光催化性能,并对其晶体结构和微观结构用X射线衍射、热重/差热分析、透射电镜和高分辨透射电镜等手段进行了表征.结果表明,制备的纳米粒子为纯相的ZnCO₂O₄,平均粒径约为10-20 nm.紫外-可见吸收光谱估计出ZnCo₂O₄纳米粒子的能带隙为3.39和2.09 eV.可见光（λ>420 nm）照射下,纳米粒子表现出降解亚甲基蓝溶液的光催化活性.ZnCo₂O₄纳米粒子的光催化活性可以归结为紫外和可见光下纳米粒子吸收光子（能量大于能带隙）的能力,以及它们的纳米尺寸,基于实验结果,本文提出了ZnCO₂O₄可能的能带结构.     

Visible Light Mediated Aryl Migration by Homolytic C−N Cleavage of Aryl Amines

The photocatalytic preparation of aminoalkylated heteroarenes from haloalkylamides via a 1,4‐aryl migration from nitrogen to carbon, conceptually analogous to a radical Smiles rearrangement, is reported. This method enables the substitution of amino groups in heteroaromatic compounds with aminoalkyl motifs under mild, iridium(III)‐mediated photoredox conditions. It provides rapid access to thienoazepinone, a pharmacophore present in multiple drug candidates for potential treatment of different conditions, including inflammation and psychotic disorders.     

可见光下高催化活性不同结构Sr/TiO2催化剂的制备和表征

采用分步沉积法制备不同Sr/Ti 摩尔比例的Sr/TiO₂催化剂, 以X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、傅里叶变换红外(FT-IR) 光谱、紫外-可见漫反射光谱(UV-Vis RDS)等手段对样品进行了表征, 以可见光催化降解亚甲基蓝为模型反应考察样品光催化活性. 结果表明, 催化剂的活性和结构随Sr/Ti 摩尔比(n(Sr)/n(Ti))的变化而变化, 当n(Sr)/n(Ti)≤3/2 时, 催化剂呈由TiO₂和SrTiO₃组成的球状结构; 而当n(Sr)/n(Ti)在3/2 与4/1 之间时, 催化剂呈片状结构, 且随着n(Sr)/n(Ti)增大, 催化剂组成由SrTiO₃ 和Sr₂₄ 变为Sr₂₄和Sr(OH)₂·H₂O; 当n(Sr)/n(Ti)=9/1 时, 催化剂呈以Sr(OH)₂·H₂O为主的针状结构. 其中, n(Sr)/n(Ti)=4/1的样品表现出最高的光催化活性, 一级反应速率为SrTiO₃钙钛矿催化剂的5.0倍, 商用P25的86.7倍.     

磷化镍@镍-氮-碳双功能催化剂电还原CO2-H2O制合成气

电催化还原CO₂由于具有温和的反应条件、反应产物组成可调、环境友好等优点,是CO₂转化技术中最有前景的方法之一,然而目前发展的电催化CO₂还原技术仍未达到工业化盈利所需的技术经济指标。因此,通过简单的两电子转移,将CO₂-H₂O电还原为合成气通常被认为是电化学还原CO₂过程中较有前景的实现盈利的途径之一,因此研究能够精确调控合成气比例的非贵金属电催化剂至关重要。在本文中,我们提出了通过三元纳米复合材料的分子工程学设计的进行了高活性、可实现特定比例合成气制备的双功能电催化剂的合成策略。将三聚氰胺、三苯基膦(TPP)和乙酸镍研磨并溶解在乙醇中,通过旋蒸得到三元纳米复合材料,在850 ℃下热解2 h得到催化剂。该方法简单、易操作并且易于放大。该系列双功能电催化剂的比表面积和孔体积均随着三苯基膦量的增加而增加,且分级孔结构有利于提供活性位以及促进物质传输。此外,拉曼图谱表明材料的缺陷度由于前驱体中三苯基膦的增加而增加。另外,X射线光电子能谱验证了析氢反应活性位点Ni-P和CO₂电催化活性为位点Ni-N的存在。因此,该系列电催化剂的性能具有较大的调控空间,可从CO产物主导调控至H₂产物主导。电化学性能通过在CO₂饱和0.5 mol·L^-1 KHCO₃溶液中进行线性扫描伏安法以及恒电位电解进行评价。结果表明催化剂的活性受材料表面P/Ni-N_x比例的影响。最高的CO法拉第效率为91%,由不含磷化镍的纯Ni-N-C材料在-0.8 V (相对于可逆氢电极(RHE))电位下实现。在-0.7至-1.1 V (vs RHE)电位区间内,合成气流中CO/H₂的摩尔比可从2 : 5调整至10 : 1,并能与磷化镍和镍-氮-炭组分的摩尔比关联。此外,我们还对优化的催化剂在-0.7 V电位下的稳定性进行了测试,合成气摩尔比例在8 h内保持在1.2-1.3,说明材料具有良好的稳定性。本工作将温室气体CO₂和H₂O转化成比例可调的合成气,为双功能电催化剂的工程设计提供了新的方向。     

Porous and Water Stable 2D Hybrid Metal Halide with Broad Light Emission and Selective H2O Vapor Sorption

In this work we report a strategy for generating porosity in hybrid metal halide materials using molecular cages that serve as both structure-directing agents and counter-cations. Reaction of the [2.2.2] cryptand (DHS) linker with Pb^II in acidic media gave rise to the first porous and water-stable 2D metal halide semiconductor (DHS)₂Pb₅Br₁₄. The corresponding material is stable in water for a year, while gas and vapor-sorption studies revealed that it can selectively and reversibly adsorb H₂O and D₂O at room temperature (RT). Solid-state NMR measurements and DFT calculations verified the incorporation of H₂O and D₂O in the organic linker cavities and shed light on their molecular configuration. In addition to porosity, the material exhibits broad light emission centered at 617 nm with a full width at half-maximum (FWHM) of 284 nm (0.96 eV). The recorded water stability is unparalleled for hybrid metal halide and perovskite materials, while the generation of porosity opens new pathways towards unexplored applications (e.g. solid-state batteries) for this class of hybrid semiconductors.