The Nature of Photocatalytic “Water Splitting” on Silicon Nanowires

Silicon should be an ideal semiconductor material if it can be proven usable for photocatalytic water splitting, given its high natural abundance. Thus it is imperative to explore the possibility of water splitting by running photocatalysis on a silicon surface and to decode the mechanism behind it. It is reported that hydrogen gas can indeed be produced from Si nanowires when illuminated in water, but the reactions are not a real water‐splitting process. Instead, the production of hydrogen gas on the Si nanowires occurs through the cleavage of Si? H bonds and the formation of Si? OH bonds, resulting in the low probability of generating oxygen. On the other hand, these two types of surface dangling bonds both extract photoexcited electrons, whose competition greatly impacts on carrier lifetime and reaction efficiency. Thus surface chemistry holds the key to achieving high efficiency in such a photocatalytic system.     

Photocatalytic Synthesis of Dihydrobenzofurans by Oxidative [3+2] Cycloaddition of Phenols

We report a protocol for oxidative [3+2] cycloadditions of phenols and alkenes applicable to the modular synthesis of a large family of dihydrobenzofuran natural products. Visible‐light‐activated transition metal photocatalysis enables the use of ammonium persulfate as an easily handled, benign terminal oxidant. The broad range of organic substrates that are readily oxidized by photoredox catalysis suggests that this strategy may be applicable to a variety of useful oxidative transformations.     

Uniform Mesoporous Anatase Hollow Spheres: An Unexpectedly Efficient Fabrication Process and Enhanced Performance in Photocatalytic Hydrogen Evolution

Uniform mesoporous anatase hollow spheres with high crystallinity have been fabricated by an efficient method, in which biocompatible ethanedioic acid acts as the chelating agent during the Ostwald ripening process. The combination of high crystallinity, large surface area, and mesoporosity leads to an excellent photocatalytic activity. In solar water splitting, the hollow spheres exhibit remarkably enhanced photocatalytic performance that is 1.4 times of P25.     

Synthesis and Photocatalytic Properties of Titanium-Porphyrinic Aerogels

We present novel titanium-porphyrinic gels (TPGs) and titanium-porphyrinic aerogels (TPAs), in which porphyrinic ligand tetrakis(4-carboxyphenyl)porphyrin is coordinated to Ti-oxo clusters. These hierarchically porous TPAs, with micro-, meso-, and macropores and reactant-concentration-dependent Brunauer-Emmett-Teller surface areas of 407–738 m² g⁻¹, are prepared by CO₂ critical point drying of TPGs. Although the Ti⁴⁺ → Ti³⁺ photoreduction of TPAs is less efficient than that of crystalline microporous Ti-porphyrinic framework DGIST-1, prompt diffusion of O₂ and spin-trapping agents into the TPA pores causes the rapid generation of reactive oxygen species (ROS), as observed by EPR spectroscopy. When used as an ROS scavenger, large 1,3-diphenylisobenzofuran is degraded by the best-performing TPA 10 times faster than by DGIST-1, suggesting that the accessibility of molecules (reactants) to pores (reactive centers) strongly influences photocatalytic activity.     

Functionalized Membranes for Photocatalytic Hydrogen Production

Functionalized vesicles for photocatalytic hydrogen production in water have been prepared by co‐embedding of amphiphilic photosensitizers and a hydrogen‐evolving catalyst in phospholipid membranes. The self‐assembly allows a simple two‐dimensional arrangement of the multicomponent system with close spatial proximity, which gave turnover numbers up to 165 for the incorporated amphiphilic cobaloxime water reduction catalyst 3 b under optimized conditions in purely aqueous solution. Superior photocatalytic activity in fluid membranes indicates that mobility and dynamic reorganization of catalytic subunits in the membrane promote the visible‐light‐driven hydrogen production. The functionalized membranes represent nanostructured assemblies for hydrogen production in aqueous solution mimicking natural photosynthesis.     

Phenols as Novel Photocatalytic Platforms for Organic Synthesis

In recent years, organic chemists have devoted a great deal of effort towards the implementation of novel green photocatalytic synthetic protocols. To this end, the development of new effective, non-toxic, inexpensive photocatalysts, which are capable of driving value-added chemical transformations, is highly desirable. Interestingly, phenols fulfill all these requirements due to their outstanding physicochemical features, therefore emerging as promising metal-free photocatalytic platforms for organic synthesis. This Perspective aims at highlighting the most recent applications of phenols in organic photocatalysis. More specifically, phenolate anions, formed upon deprotonation of phenols, are photo-active organic intermediates that may absorb light within the visible region. Thus, when in the excited states, these anions may be used as reductants to generate reactive open shell species from suitable precursors under mild operative conditions. Alternatively, phenolate anions and suitable radical precursors can form electron donor-acceptor (EDA) complexes. Specifically, the photochemical activity of these molecular aggregates can be used to initiate organic radical reactions. Lastly, forward-looking opportunities within this research field have been discussed.     

Intercalation of Highly Dispersed Metal Nanoclusters into a Layered Metal Oxide for Photocatalytic Overall Water Splitting

Metal nanoclusters (involving metals such as platinum) with a diameter smaller than 1 nm were deposited on the interlayer nanospace of KCa₂Nb₃O₁₀ using the electrostatic attraction between a cationic metal complex (e.g., [Pt(NH₃)₄]Cl₂) and a negatively charged two‐dimensional Ca₂Nb₃O₁₀^? sheet, without the aid of any additional reagent. The material obtained possessed eight‐fold greater photocatalytic activity for water splitting into H₂ and O₂ under band‐gap irradiation than the previously reported analog using a RuO₂ promoter. This study highlighted the superior functionality of Pt nanoclusters with diameters smaller than 1 nm for photocatalytic overall water splitting. This material shows the greatest efficiency among nanosheet‐based photocatalysts reported to date.     

Increasing visible-light absorption for photocatalysis with black BiOCl

Black BiOCl with oxygen vacancies was prepared by UV light irradiation with Ar blowing. The as-prepared black BiOCl sample showed 20 times higher visible light photocatalytic activity than white BiOCl for RhB degradation. The trapping experiment showed that the superoxide radical (O(2)(?-)) and holes (h(+)) were the main active species in aqueous solution under visible light irradiation.     

Considerations for a More Accurate Evaluation Method for Photocatalytic Water Splitting

Over the past decades, various photocatalysts have been developed and great progress has been achieved in the field of solar-driven photocatalytic water splitting. However, the lack of an accurate and comprehensive evaluation method greatly hinders the meaningful comparison between different systems and becomes a serious impediment for the development of photocatalysts. Although many researchers are aware of this, there has been little work in this area. In this Viewpoint, we first analyze the insufficiencies of the existing evaluation methods and then make preliminary suggestions, aiming to stimulate discussion in the research community and hopefully lead to a widely accepted and authoritative evaluation system to assess photocatalyst performance.     

Harvesting Solar Light with Crystalline Carbon Nitrides for Efficient Photocatalytic Hydrogen Evolution

Described herein is the photocatalytic hydrogen evolution using crystalline carbon nitrides (CNs) obtained by supramolecular aggregation followed by ionic melt polycondensation (IMP) using melamine and 2,4,6‐triaminopyrimidine as a dopant. The solid state NMR spectrum of ¹⁵N‐enriched CN confirms the triazine as a building unit. Controlling the amount and arrangements of dopants in the CN structure can dramatically enhance the photocatalytic performance for H₂ evolution. The polytriazine imide (PTI) exhibits the apparent quantum efficiency (AQE) of 15 % at 400 nm. This method successfully enables a substantial amount of visible light to be harvested for H₂ evolution, and provides a promising route for the rational design of a variety of highly active crystalline CN photocatalysts.     

染料敏化TiO_2可见光光催化降解罗丹明B

苝二酰亚胺(PTCDI)是一种n型半导体材料,在可见光区有很强的吸收,广泛用于有机光伏器件领域的研究.以PTCDI为光敏剂制备TiO2可见光光催化剂用以降解环境污染物的研究还鲜有报道.本文采用水热法制备苝二酰亚胺(PTCDI)和四磺酸酞菁铜(CuPcTs)敏化的TiO2复合样品.利用XRD、TEM、UV-Vis和荧光光谱对复合样品进行表面形貌和结构表征,以可见光光催化降解罗丹明B为模型反应.研究结果表明,染料敏化能够有效地拓宽样品的吸收光谱范围,提高可见光光催化活性;电子收集型的共敏化复合样品体现出了优于单一染料敏化样品的光催化活性.应用能带结构理论,阐明了单一染料敏化和共敏化样品的光生电子转移机制.