As a fascinating conjugated polymer, graphitic carbon nitride (g-C3N4) has become a new research hotspot and drawn broad interdisciplinary attention as a metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability, and “earth-abundant” nature. This critical review summarizes a panorama of the latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites, including (1) nanoarchitecture design of bare g-C3N4, such as hard and soft templating approaches, supramolecular preorganization assembly, exfoliation, and template-free synthesis routes, (2) functionalization of g-C3N4 at an atomic level (elemental doping) and molecular level (copolymerization), and (3) modification of g-C3N4 with well-matched energy levels of another semiconductor or a metal as a cocatalyst to form heterojunction nanostructures. The constructi...

Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer To Achieving Sustainability?

In this review, we highlight the use of organic photoredox catalysts in a myriad of synthetic transformations with a range of applications. This overview is arranged by catalyst class where the photophysics and electrochemical characteristics of each is discussed to underscore the differences and advantages to each type of single electron redox agent. We highlight both net reductive and oxidative as well as redox neutral transformations that can be accomplished using purely organic photoredox-active catalysts. An overview of the basic photophysics and electron transfer theory is presented in order to provide a comprehensive guide for employing this class of catalysts in photoredox manifolds.

Organic Photoredox Catalysis

A review on g-C3N4-based photocatalysts

Photocatalytic water splitting represents a promising strategy for clean, low-cost, and environmental-friendly production of H2 by utilizing solar energy. There are three crucial steps for the photocatalytic water splitting reaction: solar light harvesting, charge separation and transportation, and the catalytic H2 and O2 evolution reactions. While significant achievement has been made in optimizing the first two steps in the photocatalytic process, much less efforts have been put into improving the efficiency of the third step, which demands the utilization of cocatalysts. To date, cocatalysts based on rare and expensive noble metals are still required for achieving reasonable activity in most semiconductor-based photocatalytic systems, which seriously restricts their large-scale application. Therefore, seeking cheap, earth-abundant and high-performance cocatalysts is indispensable to achieve cost-effective and highly efficient photocatalytic water splitting. This review for the first time summarizes all the developed earth-abundant cocatalysts for photocatalytic H2- and O2-production half reactions as well as overall water splitting. The roles and functional mechanism of the cocatalysts are discussed in detail. Finally, this review is concluded with a summary, and remarks on some challenges and perspectives in this emerging area of research.

Earth-abundant cocatalysts for semiconductor-based photocatalytic water splitting

In recent years, photoredox catalysis has come to the forefront in organic chemistry as a powerful strategy for the activation of small molecules. In a general sense, these approaches rely on the ability of metal complexes and organic dyes to convert visible light into chemical energy by engaging in single-electron transfer with organic substrates, thereby generating reactive intermediates. In this Perspective, we highlight the unique ability of photoredox catalysis to expedite the development of completely new reaction mechanisms, with particular emphasis placed on multicatalytic strategies that enable the construction of challenging carbon–carbon and carbon–heteroatom bonds.

http://pubs.acs.org/doi/pdf/10.1021/acs.joc.6b01449

Photoredox Catalysis in Organic Chemistry

Photocatalysts based on g-C3N4 by loading cocatalysts or constructing heterojunctions have shown great potential in solar-driven water oxidation. However, the intrinsic drawbacks of g-C3N4, such as poor mass diffusion and charge separation efficiency, remain as the bottleneck to achieve highly efficient water oxidation. Here we report a simple protonation method to improve the activity of g-C3N4. Studies using valence band X-ray photoelectron spectra and steady-state and time-resolved spectroscopy reveal that the promotion of catalytic ability originates from the higher thermodynamical driving force and longer-lived charge separation state, which may provide guidance in designing efficient polymeric semiconductor photocatalysts with desirable kinetics for water oxidation.

Enhanced Driving Force and Charge Separation Efficiency of Protonated g-C3N4 for Photocatalytic O2 Evolution

Graphdiyne (GDY), a novel large π-conjugated carbon material, for the first time, is introduced as the hole transfer layer into a photoelectrochemical water splitting cell (PEC). Raman and ultraviolet photoelectron spectroscopic studies indicate the existence of relatively strong π–π interactions between GDY and 4-mercaptopyridine surface-functionalized CdSe quantum dots, beneficial to the hole transportation and enhancement of the photocurrent performance. Upon exposure to a Xe lamp, the integrated photocathode produces a current density of nearly −70 μA cm–2 at a potential of 0 V vs NHE in neutral aqueous solution. Simultaneously, the photocathode evolves H2 with 90 ± 5% faradic efficiency over three times and exhibits good stability within 12 h. All of the results indicate that GDY is a promising hole transfer material to fabricate a PEC device for water splitting by solar energy.

Graphdiyne: A Metal-Free Material as Hole Transfer Layer To Fabricate Quantum Dot-Sensitized Photocathodes for Hydrogen Production

Sunlight is our most abundant, clean and inexhaustible energy source However, its diffuse and intermittent nature makes it difficult to use directly, suggesting that we should instead store this energy One of the most attractive avenues for this involves using solar energy to split H2O and afford H2 through artificial photosynthesis, the practical realization of which requires low-cost, robust photocatalysts Colloidal quantum dots (QDs) of IIB–VIA semiconductors appear to be an ideal material from which to construct highly efficient photocatalysts for H2 photogeneration In this Review, we highlight recent developments in QD-based artificial photosynthetic systems for H2 evolution using sacrificial reagents These case studies allow us to introduce strategies — including size optimization, structural modification and surface design — to increase the H2 evolution activities of QD-based artificial photosystems Finally, we describe photocatalytic biomass reforming and unassisted photoelectrochemical H2O splitting — two new pathways that could make QD-based solar-to-fuel conversion practically viable and cost-effective in the near future Semiconducting quantum dots (QDs) can serve as light-absorbing components in efficient artificial photosynthetic systems for H2 evolution This Review describes how we can optimize QDs for H2 evolution using sacrificial reductants, before moving on to sustainable strategies for the photolysis of biomass or H2O

Semiconducting quantum dots for artificial photosynthesis

As one of the most critical approaches to resolve the energy crisis and environmental concerns, carbon dioxide (CO2 ) photoreduction into value-added chemicals and solar fuels (for example, CO, HCOOH, CH3 OH, CH4 ) has attracted more and more attention. In nature, photosynthetic organisms effectively convert CO2 and H2 O to carbohydrates and oxygen (O2 ) using sunlight, which has inspired the development of low-cost, stable, and effective artificial photocatalysts for CO2 photoreduction. Due to their low cost, facile synthesis, excellent light harvesting, multiple exciton generation, feasible charge-carrier regulation, and abundant surface sites, semiconductor quantum dots (QDs) have recently been identified as one of the most promising materials for establishing highly efficient artificial photosystems. Recent advances in CO2 photoreduction using semiconductor QDs are highlighted. First, the unique photophysical and structural properties of semiconductor QDs, which enable their versatile applications in solar energy conversion, are analyzed. Recent applications of QDs in photocatalytic CO2 reduction are then introduced in three categories: binary II-VI semiconductor QDs (e.g., CdSe, CdS, and ZnSe), ternary I-III-VI semiconductor QDs (e.g., CuInS2 and CuAlS2 ), and perovskite-type QDs (e.g., CsPbBr3 , CH3 NH3 PbBr3 , and Cs2 AgBiBr6 ). Finally, the challenges and prospects in solar CO2 reduction with QDs in the future are discussed.

Semiconductor Quantum Dots: An Emerging Candidate for CO2 Photoreduction.

Covalent organic frameworks have recently gained increasing attention in photocatalytic hydrogen generation from water. However, their structure-property-activity relationship, which should be beneficial for the structural design, is still far-away explored. Herein, we report the designed synthesis of four isostructural porphyrinic two-dimensional covalent organic frameworks (MPor-DETH-COF, M = H2, Co, Ni, Zn) and their photocatalytic activity in hydrogen generation. Our results clearly show that all four covalent organic frameworks adopt AA stacking structures, with high crystallinity and large surface area. Interestingly, the incorporation of different transition metals into the porphyrin rings can rationally tune the photocatalytic hydrogen evolution rate of corresponding covalent organic frameworks, with the order of CoPor-DETH-COF < H2Por-DETH-COF < NiPor-DETH-COF < ZnPor-DETH-COF. Based on the detailed experiments and calculations, this tunable performance can be mainly explained by their tailored charge-carrier dynamics via molecular engineering. This study not only represents a simple and effective way for efficient tuning of the photocatalytic hydrogen evolution activities of covalent organic frameworks at molecular level, but also provides valuable insight on the structure design of covalent organic frameworks for better photocatalysis. Covalent organic frameworks (COFs) present well-defined materials for constructing structure-property-activity relationships. Herein, authors explore isostructural porphyrinic two-dimensional COFs with tunable of photocatalytic H2 production rates arising from tailored charge-carrier dynamics.

/pdf/rational-design-of-isostructural-2d-porphyrin-based-covalent-1oic1241ai.pdf

Xu-Bing Li

Papers

Enhanced Driving Force and Charge Separation Efficiency of Protonated g-C3N4 for Photocatalytic O2 Evolution

Graphdiyne: A Metal-Free Material as Hole Transfer Layer To Fabricate Quantum Dot-Sensitized Photocathodes for Hydrogen Production

Semiconducting quantum dots for artificial photosynthesis

Semiconductor Quantum Dots: An Emerging Candidate for CO2 Photoreduction.

Rational design of isostructural 2D porphyrin-based covalent organic frameworks for tunable photocatalytic hydrogen evolution