Synergistic utilization of TiO2-photo-generated holes and electrons is a potential protocol for catalytic C–C bond formation reactions.

Covalent organic frameworks (COFs) are defined as highly porous and crystalline polymers, constructed and connected via covalent bonds, extending in two- or three-dimension. Compared with other porous materials such as zeolite and active carbon, the versatile and alternative constituent elements, chemical bonding types and characteristics of ordered skeleton and pore, enable the rising large family of COFs more available to diverse applications including gas separation and storage, optoelectronics, proton conduction, energy storage and in particular, catalysis. As the representative candidate of next-generation catalysis materials, because of their large surface area, accessible and size-tunable open nano-pores, COFs materials are suitable for incorporating external useful active ingredients such as ligands, complexes, even metal nanoparticles deposition and substrate diffusion. These advantages make it capable to catalyze a variety of useful organic reactions such as important C-C bond formations. By appropriate pore-engineering in COFs materials, even enantioselective asymmetric C-C bond formations could be realized with excellent yield and ee value in much shorter reaction time compared with their monomer and oligomer analogues. This review will mainly introduce and discuss the paragon examples of COFs materials for application in C-C bond formation reactions for the organic synthetic purpose.

The T 1–T 2 dual-mode contrast agents for magnetic resonance imaging (MRI) can generate self-complementary confirmed T 2 and T 1 images, hence greatly improving the reliability. Facilely synthesizing nanoparticles with the ultrasensitive contrast property remains extremely challenging in nanoscience. Moreover, uncovering the mechanism correlating the signal enhancements and chemical constituents is vital for designing novel efficient synergistically enhanced T 1–T 2 dual-mode MRI nanoprobes. Herein, we report a one-pot facile method to synthesize the superparamagnetic manganese oxide-doped iron oxide (Fe3O4/MnO) nanoparticles for T 1–T 2 dual-mode MR imaging. Under external magnetic field, the local magnetic field intensities of MnO and Fe3O4 could be simultaneously enhanced through embedding MnO into Fe3O4 nanoparticles and hence can cause synergistic T 1 and T 2 contrast enhancements. Moreover, a novel and facile cost-effective method for large-scale synthesis of hydroxyl–polyethylene glycol–phosphonic acid-stabilizing ligands is designed. The facile synthetic method and surface coating strategy of superparamagnetic Fe3O4/MnO nanoparticles offer an idea for the chemical design and preparation of superparamagnetic nanoparticles with ultrasensitive MRI contrast abilities for disease evaluation and treatment.

Fulfilling the direct inert C–H bond functionalization of raw materials that are earth-abundant and commercially available for the synthesis of diverse targeted organic compounds is very desirable and its implementation would mean a great reduction of the synthetic steps required for substrate prefunctionalization such as halogenation, borylation, and metalation. Successful C–H bond functionalization mainly resorts to homogeneous transition-metal catalysis, albeit sometimes suffering from poor catalyst reusability, nontrivial separation, and severe biotoxicity. TiO2 photocatalysis displays multifaceted advantages, such as strong oxidizing ability, high chemical stability and photostability, excellent reusability, and low biotoxicity. The chemical reactions started and delivered by TiO2 photocatalysts are well known to be widely used in photocatalytic water-splitting, organic pollutant degradation, and dye-sensitized solar cells. Recently, TiO2 photocatalysis has been demonstrated to possess the unanticipated ability to trigger the transformation of inert C–H bonds for C–C, C–N, C–O, and C–X bond formation under ultraviolet light, sunlight, and even visible-light irradiation at room temperature. A few important organic products, traditionally synthesized in harsh reaction conditions and with specially functionalized group substrates, are continuously reported to be realized by TiO2 photocatalysis with simple starting materials under very mild conditions. This prominent advantage—the capability of utilizing cheap and readily available compounds for highly selective synthesis without prefunctionalized reactants such as organic halides, boronates, silanes, etc.—is attributed to the overwhelmingly powerful photo-induced hole reactivity of TiO2 photocatalysis, which does not require an elevated reaction temperature as in conventional transition-metal catalysis. Such a reaction mechanism, under typically mild conditions, is apparently different from traditional transition-metal catalysis and beyond our insights into the driving forces that transform the C–H bond for C–C bond coupling reactions. This review gives a summary of the recent progress of TiO2 photocatalytic C–H bond activation for C–C coupling reactions and discusses some model examples, especially under visible-light irradiation.

Catalytic transfer hydrogenation reactions, based on hydrogen sources other than gaseous H2, are important processes that are preferential in both laboratories and factories. However, harsh conditions, such as high temperature, are usually required for most transition-metal catalytic and organocatalytic systems. Moreover, non-volatile hydrogen donors such as dihydropyridinedicarboxylate and formic acid are often required in these processes which increase the difficulty in separating products and lowered the whole atom economy. Recently, TiO2 photocatalysis provides mild and facile access for transfer hydrogenation of C=C, C=O, N=O and C-X bonds by using volatile alcohols and amines as hydrogen sources. Upon light excitation, TiO2 photo-induced holes have the ability to oxidatively take two hydrogen atoms off alcohols and amines under room temperature. Simultaneously, photo-induced conduction band electrons would combine with these two hydrogen atoms and smoothly hydrogenate multiple bonds and/or C-X bonds. It is heartening that practices and principles in the transfer hydrogenations of substrates containing C=C, C=O, N=O and C-X bond based on TiO2 photocatalysis have overcome a lot of the traditional thermocatalysis’ limitations and flaws which usually originate from high temperature operations. In this review, we will introduce the recent paragon examples of TiO2 photocatalytic transfer hydrogenations used in (1) C=C and C≡C (2) C=O and C=N (3) N=O substrates and in-depth discuss basic principle, status, challenges and future directions of transfer hydrogenation mediated by TiO2 photocatalysis.

Covalent organic frameworks (COFs) are a kind of porous crystalline polymeric material. They are constructed by organic module units connected with strong covalent bonds extending in two or three dimensions. COFs possess the advantages of low-density, large specific surface area, high thermal stability, developed pore-structure, long-range order, good crystallinity, and the excellent tunability of the monomer units and the linking reticular chemistry. These features endowed COFs with the ability to be applied in a plethora of applications, ranging from adsorption and separation, sensing, catalysis, optoelectronics, energy storage, mass transport, etc. In this paper, we will review the recent progress of COFs materials applied in photocatalytic CO2 reduction. The state-of-the-art paragon examples and the current challenges will be discussed in detail. The future direction in this research field will be finally outlooked.

TiO2 photocatalysis can be performed for the addition of pyridines to vinylarenes in an anti-Markovnikov manner. Seven examples with considerable yields (56-91%) and selectivity were demonstrated. A comparative survey of the involved process through ESR revealed a novel concerted two electron transfer pathway for these photocatalytic bimolecular addition reactions.

The importance of advanced energy-conversion devices such as water electrolysis has manifested dramatically over the past few decades because it is the current mainstay for the generation of green energy. Anodic oxygen evolution reaction (OER) in water splitting is one of the biggest obstacles because of its extremely high kinetic barrier. Conventional OER catalysts are mainly noble-metal oxides represented by IrO2 and RuO2, but these compounds tend to have poor sustainability. The attention on Prussian blue (PB) and its analogs (PBA) in the field of energy conversion systems was concentrated on their open-framework structure, as well as its varied composition comprised of Earth-abundant elements. The unique electronic structure of PBA enables its promising catalytic potential, and it can also be converted into many other talented compounds or structures as a precursor. This undoubtedly provides a new approach for the design of green OER catalysts. This article reviews the recent progress of the application of PBA and its derivatives in OER based on in-depth studies of characterization techniques. The structural design, synthetic strategy, and enhanced electrochemical properties are summarized to provide an outlook for its application in the field of OER. Moreover, due to the similarity of the reaction process of photo-driven electrolysis of water and the former one, the application of PBA in photoelectrolysis is also discussed.