One‐Dimensional Hybrid Nanostructures for Heterogeneous Photocatalysis and Photoelectrocatalysis

Semiconductor‐based photocatalysis and photoelectrocatalysis have received considerable attention as alternative approaches for solar energy harvesting and storage. The photocatalytic or photoelectrocatalytic performance of a semiconductor is closely related to the design of the semiconductor at the nanoscale. Among various nanostructures, one‐dimensional (1D) nanostructured photocatalysts and photoelectrodes have attracted increasing interest owing to their unique optical, structural, and electronic advantages. In this article, a comprehensive review of the current research efforts towards the development of 1D semiconductor nanomaterials for heterogeneous photocatalysis and photoelectrocatalysis is provided and, in particular, a discussion of how to overcome the challenges for achieving full potential of 1D nanostructures is presented. It is anticipated that this review will afford enriched information on the rational exploration of the structural and electronic properties of 1D semiconductor nanostructures for achieving more efficient 1D nanostructure‐based photocatalysts and photoelectrodes for high‐efficiency solar energy conversion.     

Two-dimensional photocatalyst design: A critical review of recent experimental and computational advances

In recent years, two-dimensional (2D) semiconductor photocatalysts have been widely applied in water splitting, CO₂ reduction, N₂ fixation, as well as many other important photoreactions. Photocatalysts in the form of 2D nanosheet possess many inherent advantages over traditional 3D nanopowder photocatalysts, including improved light absorption characteristics, shorter electron and hole migration paths to the photocatalysts’ surface (thus minimizing undesirable electron-hole pair recombination), and abundant surface defects which allow band gap modulation and facilitate charge transfer from the semiconductor to adsorbates. When synergistically exploited and optimized, these advantages can impart 2D photocatalysts with remarkable activities relative to their 3D counterparts. Accordingly, a wide range of experimental approaches is now being explored for the synthesis of 2D photocatalysts, with computational methods increasingly being used for identification of promising new 2D photocatalytic materials. Herein, we critically review recent literatures related to 2D photocatalyst development and design. Particular emphasis is placed on 2D photocatalyst synthesis and the importance of computational studies for the fundamental understanding of 2D photocatalyst electronic structure, band gap structure, charge carrier mobility and reaction pathways. We also explore the practical challenges of using 2D photocatalysts, such as their difficulty to synthesize in large quantity and also their characterization. The overarching aim of this review is to provide a snapshot of recent work targeting high-performance 2D photocatalysts for efficient solar energy conversion, thus laying a firm base for future advancements in this rapidly expanding area of photocatalysis research.     

Recent Progress of Three-dimensionally Ordered Macroporous (3DOM) Materials in Photocatalytic Applications: A Review

In recent years, three-dimensionally ordered macroporous (3DOM) materials have attracted tremendous interest in the field of photocatalysis due to the periodic spatial structure and unique physicochemical properties of 3DOM catalysts. In this review, the fundamentals and principles of 3DOM photocatalysts are briefly introduced, including the overview of 3DOM materials, the photocatalytic principles based on 3DOM materials, and the advantages of 3DOM materials in photocatalysis. The preparation methods of 3DOM materials are also presented. The structure and properties of 3DOM materials and their effects on photocatalytic performance are briefly summarized. More importantly, 3DOM materials, as a supported catalyst, are extensively employed to combine with various common materials, including metal nanoparticles, metal oxides, metal sulfides, and carbon materials, to enhance photocatalytic performance. Finally, the prospects and challenges for the development of 3DOM materials in the field of photocatalysis are presented.     

Remarkable Piezophoto Coupling Catalysis Behavior of BiOX/BaTiO3 (X = Cl,Br, Cl0.166Br0.834) Piezoelectric Composites

Polarization field engineering of piezoelectric materials is considered as an advisable strategy in fine‐tuning photocatalytic performance which has drawn much attention recently. However, the efficient charge separation that determines the photocatalytic reactivities of these materials is quite restricted. Herein, a judicious combination of piezoelectric and photocatalytic performances of BiOX/BaTiO₃ (X = Cl, Br, Cl_0.166Br_0.834) to enable a high piezophotocatalytic activity is demonstrated. Under the synergic advantages of chemical potential difference and piezoelectric potential difference in BiOX/BaTiO₃ composites, the photoinduced carriers recombination is largely halted, which directly contributes to the significantly promoted piezophotocatalytic activity of piezoelectric composites. Inspiringly, the BiOBr/BaTiO₃ composites under light irradiation with auxiliary ultrasonic activation result in an ultrahigh and stable photocatalytic performance, which is much higher than the total of those by isolated photocatalysis and piezocatalysis, and can rival current excellent photocatalytic system. In fact, the theoretical piezoelectric potential difference of BiOBr/BaTiO₃ composites reaches 100 mV, which far exceeds the pure BaTiO₃ of 31.21 mV and BiOBr of 30 mV, respectively. First, fabrication of BiOX/BaTiO₃ piezoelectric composites and its remarkable piezophoto coupling catalysis behavior lays new ground for developing high‐efficiency piezoelectric photocatalysts in purifying wastewater, killing bacteria, and other piezophototronic processes.     

Protonation‐Assisted Exfoliation of N‐Containing 2D Conjugated Polymers

Ultrathin 2D conjugated polymer nanosheets are an emerging class of photocatalysts for solar‐to‐chemical energy conversion. Until now, the majority of ultrathin 2D polymer photocatalysts are produced through exfoliation of layered polymers. Unfortunately, it still remains a great challenge to exfoliate layered polymers into ultrathin nanosheets with high yields. In this work, a liquid‐phase protonation‐assisted exfoliation is demonstrated to enable remarkably improved exfoliation yields of various 2D N‐containing conjugated polymers such as g‐C₃N₄, C₂N, and aza‐CMP. The exfoliation yields are only 2–15% in pure water whereas they can be substantially improved to 41–56% in 12 m HCl. The exfoliated ultrathin nanosheets possess average thicknesses less than 5 nm and can be easily dispersed in aqueous solutions. More importantly, the exfoliated nanosheets exhibit significantly enhanced photocatalytic activity toward photocatalytic water splitting compared to their bulk counterparts. Further characterizations and computational calculations reveal that protonation of the heterocyclic nitrogen sites in the conjugated polymer frameworks can lead to strong hydrogen bonding between the polymer surfaces and water molecules, resulting in facilitated exfoliation of polymers into the liquid phase. This study unveils an important protocol toward producing ultrathin 2D N‐containing conjugated polymer nanosheets for future solar energy conversion.     

Graphene in Photocatalysis: A Review

In recent years, heterogeneous photocatalysis has received much research interest because of its powerful potential applications in tackling many important energy and environmental challenges at a global level in an economically sustainable manner. Due to their unique optical, electrical, and physicochemical properties, various 2D graphene nanosheets‐supported semiconductor composite photocatalysts have been widely constructed and applied in different photocatalytic fields. In this review, fundamental mechanisms of heterogeneous photocatalysis, including thermodynamic and kinetics requirements, are first systematically summarized. Then, the photocatalysis‐related properties of graphene and its derivatives, and design rules and synthesis methods of graphene‐based composites are highlighted. Importantly, different design strategies, including doping and sensitization of semiconductors by graphene, improving electrical conductivity of graphene, increasing eloectrocatalytic active sites on graphene, strengthening interface coupling between semiconductors and graphene, fabricating micro/nano architectures, constructing multi‐junction nanocomposites, enhancing photostability of semiconductors, and utilizing the synergistic effect of various modification strategies, are thoroughly summarized. The important applications including photocatalytic pollutant degradation, H₂ production, and CO₂ reduction are also addressed. Through reviewing the significant advances on this topic, it may provide new opportunities for designing highly efficient 2D graphene‐based photocatalysts for various applications in photocatalysis and other fields, such as solar cells, thermal catalysis, separation, and purification.     

Carbon–Graphitic Carbon Nitride Hybrids for Heterogeneous Photocatalysis

Polymeric graphitic carbon nitride (g-C₃N₄) and various carbon materials have experienced a renaissance as viable alternates in photocatalysis due to their captivating metal-free features, favorable photoelectric properties, and economic adaptabilities. Although numerous efforts have focused on the integration of both materials with optimized photocatalytic performance in recent years, the direct parameters for this emerging enhancement are not fully summarized yet. Fully understanding the synergistic effects between g-C₃N₄ and carbon materials on photocatalytic action is vital to further development of metal-free semiconductors in future studies. Here, recent advances of carbon/g-C₃N₄ hybrids on various photocatalytic applications are reviewed. The dominant governing factors by inducing carbon into g-C₃N₄ photocatalysts with involving photocatalytic mechanism are highlighted. Five typical carbon-induced enhancement effects are mainly discussed here, i.e., local electric modification, band structure tailoring, multiple charge carrier activation, chemical group functionalization, and abundant surface-modified engineering. Photocatalytic performance of carbon-induced g-C₃N₄ photocatalysts for addressing directly both the renewable energy storage and environmental remediation is also summarized. Finally, perspectives and ongoing challenges encountered in the development of metal-free carbon-induced g-C₃N₄ photocatalysts are presented.     

Black Phosphorus,a Rising Star 2D Nanomaterial in the Post‐Graphene Era: Synthesis,Properties, Modifications,and Photocatalysis Applications

Semiconductor photocatalysis, a sustainable and renewable technology, is deemed to be a new path to resolve environmental pollution and energy shortage. The development of effective photocatalysts, especially the metal‐free photocatalysts, is a critical determinant of this technique. The recently emerged 2D material of black phosphorus with distinctive properties of tunable direct bandgap, ultrahigh charge mobility, fortified optical absorption, large specific surface area, and anisotropic structure has captured enormous attention since the first exfoliation of bulk black phosphorus into mono‐ or few layered phosphorene in 2014. In this article, the state‐of‐the‐art preparation methods are first summarized for bulk black phosphorus, phosphorene, and black phosphorus quantum dot and then the fundamental structure and electronic and optical properties are analyzed to evaluate its feasibility as a metal‐free photocatalyst. Various modifications on black phosphorus are also summarized to enhance its photocatalytic performance. Furthermore, the multifarious applications such as solar to energy conversion, organic removal, disinfection, nitrogen fixation, and photodynamic therapy are discussed and some of the future challenges and opportunities for black phosphorus research are proposed. This review reveals that the rising star of black phosphorus will be a multifunctional material in the postgraphene era.     

Recent Progress of Single-Atom Photocatalysts Applied in Energy Conversion and Environmental Protection

Photocatalysis driven by solar energy is a feasible strategy to alleviate energy crises and environmental problems. In recent years, significant progress has been made in developing advanced photocatalysts for efficient solar-to-chemical energy conversion. Single-atom catalysts have the advantages of highly dispersed active sites, maximum atomic utilization, unique coordination environment, and electronic structure, which have become a research hotspot in heterogeneous photocatalysis. This paper introduces the potential supports, preparation, and characterization methods of single-atom photocatalysts in detail. Subsequently, the fascinating effects of single-atom photocatalysts on three critical steps of photocatalysis (the absorption of incident light to produce electron-hole pairs, carrier separation and migration, and interface reactions) are analyzed. At the same time, the applications of single-atom photocatalysts in energy conversion and environmental protection (CO₂ reduction, water splitting, N₂ fixation, organic macromolecule reforming, air pollutant removal, and water pollutant degradation) are systematically summarized. Finally, the opportunities and challenges of single-atom catalysts in heterogeneous photocatalysis are discussed. It is hoped that this work can provide insights into the design, synthesis, and application of single-atom photocatalysts and promote the development of high-performance photocatalytic systems.     

Noninvasively Modifying Band Structures of Wide‐Bandgap Metal Oxides to Boost Photocatalytic Activity

Although doping with appropriate heteroatoms is a powerful way of increasing visible light absorption of wide‐bandgap metal oxide photocatalysts, the incorporation of heteroatoms into the photocatalysts usually leads to the increase of deleterious recombination centers of photogenerated charge carriers. Here, a conceptual strategy of increasing visible light absorption without causing additional recombination centers by constructing an ultrathin insulating heterolayer of amorphous boron oxynitride on wide‐bandgap photocatalysts is shown. The nature of this strategy is that the active composition nitrogen in the heterolayer can noninvasively modify the electronic structure of metal oxides for visible light absorption through the interface contact between the heterolayer and metal oxides. The photocatalysts developed show significant improvements in photocatalytic activity under both UV–vis and visible light irradiation compared to the doped counterparts by conventional doping process. These results may provide opportunities for flexibly tailoring the electronic structure of metal oxides.     

Ultrathin two-dimensional materials for photo- and electrocatalytic hydrogen evolution

Sustainable hydrogen production via photocatalytic, electrocatalytic, and synergetic photoelectrocatalytic processes has been regarded as an effective strategy to address both energy and environmental crises. Due to their unique structures and properties, emerging ultrathin two-dimensional (2D) materials can bring about promising opportunities to realize high-efficiency hydrogen evolution. This review presents a critical appraisal of advantages and advancements for ultrathin 2D materials in catalytic hydrogen evolution, with an emphasis on structure–activity relationship. Furthermore, strategies for tailoring the microstructure, electronic structure, and local atomic arrangement, so as to further boost the hydrogen evolution activity, are discussed. Finally, we also present the existing challenges and future research directions regarding this promising field.     

Nanoconfined Nickel@Carbon Core–Shell Cocatalyst Promoting Highly Efficient Visible‐Light Photocatalytic H2 Production

The realization of large‐scale solar hydrogen (H₂) production relies on the development of high‐performance and low‐cost photocatalysts driven by sunlight. Recently, cocatalysts have demonstrated immense potential in enhancing the activity and stability of photocatalysts. Hence, the rational design of highly active and inexpensive cocatalysts is of great significance. Here, a facile method is reported to synthesize Ni@C core–shell nanoparticles as a highly active cocatalyst. After merging Ni@C cocatalyst with CdS nanorod (NR), a tremendously enhanced visible‐light photocatalytic H₂‐production performance of 76.1 mmol g^?1 h^?1 is achieved, accompanied with an outstanding quantum efficiency of 31.2% at 420 nm. The state‐of‐art characterizations (e.g., synchrotron‐based X‐ray absorption near edge structure) and theoretical calculations strongly support the presence of pronounced nanoconfinement effect in Ni@C core–shell nanoparticles, which leads to controlled Ni core size, intimate interfacial contact and rapid charge transfer, optimized electronic structure, and protection against chemical corrosion. Hence, the combination of nanoconfined Ni@C with CdS nanorod leads to significantly improved photocatalytic activity and stability. This work not only for the first time demonstrates the great potential of using highly active and inexpensive Ni@C core–shell structure to replace expensive Pt in photocatalysis but also opens new avenues for synthesizing cocatalyst/photocatalyst hybridized systems with excellent performance by introducing nanoconfinement effect.     

Polyaniline/Carbon Nitride Nanosheets Composite Hydrogel: A Separation‐Free and High‐Efficient Photocatalyst with 3D Hierarchical Structure

A polyaniline (PANI)/carbon nitride nanosheets (CNNS) composite hydrogel with 3D hierarchical nanostructure is synthesized via in situ polymerization. The 3D hierarchical structure is robust and stable, making the composite hydrogel separation‐free and easy to recycling. It is highly excellent in removing organic pollutant for PANI/CNNS composite hydrogel on account of the cooperation of adsorptive preconcentration and the following photocatalytic oxidation. Pollutants are first adsorbed and concentrated into the 3D hierarchical nanostructure of the composite hydrogel. Then the pollutants are in situ oxidized via photocatalysis. The promoted photocatalytic performance can be mainly ascribed to the outstanding interfacial charge separation and photoelectrochemical performance. A new idea of the construction of 3D hierarchical photocatalysts is presented, which can be applied in the sustainability field.     

Polymeric Photocatalysts Based on Graphitic Carbon Nitride

Semiconductor‐based photocatalysis is considered to be an attractive way for solving the worldwide energy shortage and environmental pollution issues. Since the pioneering work in 2009 on graphitic carbon nitride (g‐C₃N₄) for visible‐light photocatalytic water splitting, g‐C₃N₄‐based photocatalysis has become a very hot research topic. This review summarizes the recent progress regarding the design and preparation of g‐C₃N₄‐based photocatalysts, including the fabrication and nanostructure design of pristine g‐C₃N₄, bandgap engineering through atomic‐level doping and molecular‐level modification, and the preparation of g‐C₃N₄‐based semiconductor composites. Also, the photo­catalytic applications of g‐C₃N₄‐based photocatalysts in the fields of water splitting, CO₂ reduction, pollutant degradation, organic syntheses, and bacterial disinfection are reviewed, with emphasis on photocatalysis promoted by carbon materials, non‐noble‐metal cocatalysts, and Z‐scheme heterojunctions. Finally, the concluding remarks are presented and some perspectives regarding the future development of g‐C₃N₄‐based photocatalysts are highlighted.     

Smart Utilization of Carbon Dots in Semiconductor Photocatalysis

Efficient capture of solar energy will be critical to meeting the energy needs of the future. Semiconductor photocatalysis is expected to make an important contribution in this regard, delivering both energy carriers (especially H₂) and valuable chemical feedstocks under direct sunlight. Over the past few years, carbon dots (CDs) have emerged as a promising new class of metal‐free photocatalyst, displaying semiconductor‐like photoelectric properties and showing excellent performance in a wide variety of photoelectrochemical and photocatalytic applications owing to their ease of synthesis, unique structure, adjustable composition, ease of surface functionalization, outstanding electron‐transfer efficiency and tunable light‐harvesting range (from deep UV to the near‐infrared). Here, recent advances in the rational design of CDs‐based photocatalysts are highlighted and their applications in photocatalytic environmental remediation, water splitting into hydrogen, CO₂ reduction, and organic synthesis are discussed.     

Modulation of Bi2MoO6‐Based Materials for Photocatalytic Water Splitting and Environmental Application: a Critical Review

Highly active photocatalysts driving chemical reactions are of paramount importance toward renewable energy substitutes and environmental protection. As a fascinating Aurivillius phase material, Bi₂MoO₆ has been the hotspot in photocatalytic applications due to its visible light absorption, nontoxicity, low cost, and high chemical durability. However, pure Bi₂MoO₆ suffers from low efficiency in separating photogenerated carriers, small surface area, and poor quantum yield, resulting in low photocatalytic activity. Various strategies, such as morphology control, doping/defect‐introduction, metal deposition, semiconductor combination, and surface modification with conjugative π structures, have been systematically explored to improve the photocatalytic activity of Bi₂MoO₆. To accelerate further developments of Bi₂MoO₆ in the field of photocatalysis, this comprehensive Review endeavors to summarize recent research progress for the construction of highly efficient Bi₂MoO₆‐based photocatalysts. Furthermore, benefiting from the enhanced photocatalytic activity of Bi₂MoO₆‐based materials, various photocatalytic applications including water splitting, pollutant removal, and disinfection of bacteria, were introduced and critically reviewed. Finally, the current challenges and prospects of Bi₂MoO₆ are pointed out. This comprehensive Review is expected to consolidate the existing fundamental theories of photocatalysis and pave a novel avenue to rationally design highly efficient Bi₂MoO₆‐based photocatalysts for environmental pollution control and green energy development.     

Metal‐Free 2D/2D Phosphorene/g‐C3N4 Van der Waals Heterojunction for Highly Enhanced Visible‐Light Photocatalytic H2 Production

The generation of green hydrogen (H₂) energy using sunlight is of great significance to solve the worldwide energy and environmental issues. Particularly, photocatalytic H₂ production is a highly promising strategy for solar‐to‐H₂ conversion. Recently, various heterostructured photocatalysts with high efficiency and good stability have been fabricated. Among them, 2D/2D van der Waals (VDW) heterojunctions have received tremendous attention, since this architecture can promote the interfacial charge separation and transfer and provide massive reactive centers. On the other hand, currently, most photocatalysts are composed of metal elements with high cost, limited reserves, and hazardous environmental impact. Hence, the development of metal‐free photocatalysts is desirable. Here, a novel 2D/2D VDW heterostructure of metal‐free phosphorene/graphitic carbon nitride (g‐C₃N₄) is fabricated. The phosphorene/g‐C₃N₄ nanocomposite shows an enhanced visible‐light photocatalytic H₂ production activity of 571 µmol h^?1 g^?1 in 18 v% lactic acid aqueous solution. This improved performance arises from the intimate electronic coupling at the 2D/2D interface, corroborated by the advanced characterizations techniques, e.g., synchrotron‐based X‐ray absorption near‐edge structure, and theoretical calculations. This work not only reports a new metal‐free phosphorene/g‐C₃N₄ photocatalyst but also sheds lights on the design and fabrication of 2D/2D VDW heterojunction for applications in catalysis, electronics, and optoelectronics.     

Design of Heterostructured Hollow Photocatalysts for Solar‐to‐Chemical Energy Conversion

Direct conversion of solar energy into chemical energy in a sustainable manner is one of the most promising solutions to the energy crisis and environmental issues. Fabrication of highly active photocatalysts is of great significance for the practical applications of efficient solar‐to‐chemical energy conversion systems. Among various photocatalytic materials, semiconductor‐based heterostructured photocatalysts with hollow features show distinct advantages. Recent research efforts on rational design of heterostructured hollow photocatalysts toward photocatalytic water splitting and CO₂ reduction are presented. First, both single‐shelled and multishelled heterostructured photocatalysts are surveyed. Then, heterostructured hollow photocatalysts with tube‐like and frame‐like morphologies are discussed. It is intended that further innovative works on the material design of high‐performance photocatalysts for solar energy utilization can be inspired.     

Confinement Catalysis with 2D Materials for Energy Conversion

The unique electronic and structural properties of 2D materials have triggered wide research interest in catalysis. The lattice of 2D materials and the interface between 2D covers and other substrates provide intriguing confinement environments for active sites, which has stimulated a rising area of “confinement catalysis with 2D materials.” Fundamental understanding of confinement catalysis with 2D materials will favor the rational design of high‐performance 2D nanocatalysts. Confinement catalysis with 2D materials has found extensive applications in energy‐related reaction processes, especially in the conversion of small energy‐related molecules such as O₂, CH₄, CO, CO₂, H₂O, and CH₃OH. Two representative strategies, i.e., 2D lattice‐confined single atoms and 2D cover‐confined metals, have been applied to construct 2D confinement catalytic systems with superior catalytic activity and stability. Herein, the recent advances in the design, applications, and structure–performance analysis of two 2D confinement catalytic systems are summarized. The different routes for tuning the electronic states of 2D confinement catalysts are highlighted and perspectives on confinement catalysis with 2D materials toward energy conversion and utilization in the future are provided.     

New 2D Carbon Nitride Organic Materials Synthesis with Huge‐Application Prospects in CN Photocatalyst

In recent years, 2D materials are attracting increased attention because of their excellent properties. In this paper, new 2D carbon nitride (CN) organic materials are successfully prepared on the basis of the organic synthesis theory, and the thickness is about 1.5 nm. This new 2D CN organic material further strengthens the 2D materials family. Meanwhile, their synthetic mechanism is theoretically speculated. Then CN photocatalysts of several structures are obtained by roasting 2D CN organic materials. Through the photocatalytic hydrogen production experiments, the results exhibit that these kinds of photocatalysts have good photocatalytic effects compared to common g‐C₃N₄.