Construction of a 2D Graphene‐Like MoS2/C3N4 Heterojunction with Enhanced Visible‐Light Photocatalytic Activity and Photoelectrochemical Activity

A novel graphene‐like MoS₂/C₃N₄ (GL‐MoS₂/C₃N₄) composite photocatalyst has been synthesized by a facile ethylene glycol (EG)‐assisted solvothermal method. The structure and morphology of this GL‐MoS₂/C₃N₄ photocatalyst have been investigated by a wide range of characterization methods. The results showed that GL‐MoS₂ was uniformly distributed on the surface of GL‐C₃N₄ forming a heterostructure. The obtained composite exhibited strong absorbing ability in the ultraviolet (UV) and visible regions. When irradiated with visible light, the composite photocatalyst showed high activity superior to those of the respective individual components GL‐MoS₂ and GL‐C₃N₄ in the degradation of methyl orange. The enhanced photocatalytic activity of the composite may be attributed to the efficient separation of electron–hole pairs as a result of the matching band potentials between GL‐MoS₂ and GL‐C₃N₄. Furthermore, a photocatalytic mechanism for the composite material has been proposed, and the photocatalytic reaction kinetics has been measured. Moreover, GL‐MoS₂/C₃N₄ could serve as a novel sensor for trace amounts of Cu²⁺ since it exhibited good selectivity for Cu²⁺ detection in water.     

Simultaneous Tuning Band Gaps of Cu2O and TiO2 to Form S-Scheme Hetero-Photocatalyst

Photocatalytic Z or S scheme merits higher redox potentials and faster charge separation. However, heterostructure photocatalysts with band gaps of bulk materials often have a type I band structure leading to poor photocatalytic activity. In view of this, we report simultaneous tuning of band gaps of Cu₂O and TiO₂, where quantum dot Cu₂O nanoparticles were formed on doped TiO₂ with Ti³⁺. The reduced size of Cu₂O made its conduction band more negative, whereas the introduction of Ti³⁺ made the absorption edge red shift to the visible light region. The as-formed heterostructure enabled an S-Scheme mechanism with remarkable activity and stability for visible light photodegradation of 4-chlorophenol (4-CP). The as-obtained photocatalysts’ activity demonstrated ca. 510-fold increase as compared to individual ones and a mechanical blend. The as-obtained photocatalysts maintained over 80 % for 5 cycles and 2 months exposure to O₂ did not decrease the degradation rate. ESR characterization and scavenger experiments proved the S-Scheme mechanism.     

Rational Design of MOF/COF Hybrid Materials for Photocatalytic H2 Evolution in the Presence of Sacrificial Electron Donors

Crystalline and porous covalent organic frameworks (COFs) and metal‐organic frameworks (MOFs) materials have attracted enormous attention in the field of photocatalytic H₂ evolution due to their long‐range order structures, large surface areas, outstanding visible light absorbance, and tunable band gaps. In this work, we successfully integrated two‐dimensional (2D) COF with stable MOF. By covalently anchoring NH₂‐UiO‐66 onto the surface of TpPa‐1‐COF, a new type of MOF/COF hybrid materials with high surface area, porous framework, and high crystallinity was synthesized. The resulting hierarchical porous hybrid materials show efficient photocatalytic H₂ evolution under visible light irradiation. Especially, NH₂‐UiO‐66/TpPa‐1‐COF (4:6) exhibits the maximum photocatalytic H₂ evolution rate of 23.41 mmol g^?1 h^?1 (with the TOF of 402.36 h^?1), which is approximately 20 times higher than that of the parent TpPa‐1‐COF and the best performance photocatalyst for H₂ evolution among various MOF‐ and COF‐based photocatalysts.     

g-C3N4/SnS2 Heterostructure: a Promising Water Splitting Photocatalyst

Graphite-like carbon nitride (g-C₃N₄) based heterostrutures has attracted intensive attention due to their prominent photocatalytic performance. Here, we explore the g-C₃N₄/SnS₂ coupling effect on the electronic structures and optical absorption of the proposed g-C₃N₄/SnS₂ heterostructure through performing extensive hybrid functional calculations. The obtained geometric structure, band structures, band edge positions and optical absorptions clearly reveal that the g-C₃N₄ monolayer weakly couples to SnS₂ sheet, and forms a typical van der Waals heterojunction. The g-C₃N₄/SnS₂ heterostructure can effectively harvest visible light, and its valence band maximum and conduction band minimum locate in energetically favorable positions for both water oxidation and reduction reactions. Remarkably, the charge transfer from the g-C₃N₄ monolayer to SnS₂ sheet leads to the built-in interface polarized electric field, which is desirable for the photogenerated carrier separation. The built-in interface polarized electric field as well as the nice band edge alignment implys that the g-C₃N₄/SnS₂ heterostructure is a promising g-C₃N₄ based water splitting photocatalyst with good performance.     

The g-ZnO/Hf2CO2 vdW heterostructure: A novel two-dimensional material for sunlight-driven photocatalytic water splitting

In this work, by first-principles calculations, we investigate the structural, photoelectric, and catalytic properties of g-ZnO/Hf₂CO₂ vdW heterostructures to explore highly efficient photocatalysts of water splitting. Results show that the AA-stacking g-ZnO/Hf₂CO₂ vdW heterostructure (AA-HS) with an indirect bandgap of 1.738 eV has a typical type-II band alignment, which is benefit to effectively separate the photogenerated carriers into different layers and prevent their recombination. The conduction band minimum (CBM) and valence band maximum (VBM) of AA-HS straddling the water redox potentials makes it satisfies the requirements of photocatalytic water splitting at pH = 7. In addition, to evaluate the photocatalytic performance of AA-HS during oxidation evolution reaction (OER) process in water splitting, we calculated the change of Gibbs free energies of the intermediates on heterostructure under different conditions. Results show the Gibbs free energy decreases continuously at pH = 7 and U = 1.93 V. What's more, the AA-HS has good sunlight-absorption ability. External biaxial strain is not conducive to improving catalytic performance of AA-HS.     

Lattice-matched in-situ construction of 2D/2D T-SrTiO3/CsPbBr3 heterostructure for efficient photocatalysis of CO2 reduction

The elaborate regulation of heterostructure interface to accelerate the interfacial charge separation is one of practicable approaches to improve the photocatalytic CO₂ reduction performance of halide perovskite (HP) materials. Herein, we report an in-situ growth strategy for the construction of 2D CsPbBr₃ based heterostructure with perovskite oxide (SrTiO₃) nanosheet as substrate (CsPbBr₃/SrTiO₃). Lattice matching and matchable energy band structures between CsPbBr₃ and SrTiO₃ endow CsPbBr₃/SrTiO₃ heterostructure with an efficient interfacial charge separation. Moreover, the interfacial charge transfer rate can be further accelerated by etching SrTiO₃ with NH₄F to form flat surface capped with Ti?O bonds. The resultant 2D/2D T-SrTiO₃/CsPbBr₃ heterostructure exhibits an impressive photocatalytic activity for CO₂ conversion with a CO yield of 120.2 ± 4.9 μmol g^?1 h^?1 at the light intensity of 100 mW/cm² and water as electron source, which is about 10 and 7 times higher than those of the pristine SrTiO₃ and CsPbBr₃ nanosheets, surpassing the reported halide perovskite-based photocatalysts under the same conditions.     

One-pot hydrothermal synthesis of willow branch-shaped MoS2/CdS heterojunctions for photocatalytic H2 production under visible light irradiation

Willow branch-shaped MoS₂/CdS heterojunctions are successfully synthesized for the first time by a facile one-pot hydrothermal method. The as-prepared samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption measurements, diffuse reflectance spectroscopy, and photoelectrochemical and photoluminescence spectroscopy tests. The photocatalytic hydrogen evolution activities of the samples were evaluated under visible light irradiation. The resulting MoS₂/CdS heterojunctions exhibit a much improved photocatalytic hydrogen evolution activity than that obtained with CdS and MoS₂. In particular, the optimized MC-5 (5 at.% MoS₂/CdS) photocatalyst achieved the highest hydrogen production rate of 250.8 μmol h^-1, which is 28 times higher than that of pristine CdS. The apparent quantum efficiency (AQE) at 420 nm was 3.66%. Further detailed characterizations revealed that the enhanced photocatalytic activity of the MoS₂/CdS heterojunctions could be attributed to the efficient transfer and separation of photogenerated charge carriers resulting from the core-shell structure and the close contact between MoS₂ nanosheets and CdS single-crystal nanorods, as well as to increased visible light absorption. A tentative mechanism for photocatalytic H₂ evolution by MoS₂/CdS heterojunctions was proposed. This work will open up new opportunities for developing more efficient photocatalysts for water splitting.     

Amino‐Assisted Anchoring of CsPbBr3 Perovskite Quantum Dots on Porous g‐C3N4 for Enhanced Photocatalytic CO2 Reduction

Halide perovskite quantum dots (QDs) have great potential in photocatalytic applications if their low charge transportation efficiency and chemical instability can be overcome. To circumvent these obstacles, we anchored CsPbBr₃ QDs (CPB) on NH_x‐rich porous g‐C₃N₄ nanosheets (PCN) to construct the composite photocatalysts via N?Br chemical bonding. The 20 CPB‐PCN (20 wt % of QDs) photocatalyst exhibits good stability and an outstanding yield of 149 μmol h^?1 g^?1 in acetonitrile/water for photocatalytic reduction of CO₂ to CO under visible light irradiation, which is around 15 times higher than that of CsPbBr₃ QDs. This study opens up new possibilities of using halide perovskite QDs for photocatalytic application.     

Adjusting the Reduction Potential of Electrons by Quantum Confinement for Selective Photoreduction of CO2 to Methanol

The production of CH₃OH from the photocatalytic CO₂ reduction reaction (PCRR) presents a promising route for the clean utilization of renewable resources, but charge recombination, an unsatisfying stability and a poor selectivity limit its practical application. In this paper, we present the design and fabrication of 0D/2D materials with polymeric C₃N₄ nanosheets and CdSe quantum dots (QDs) to enhance the separation and reduce the diffusion length of charge carriers. The rapid outflow of carriers also restrains self‐corrosion and consequently enhances the stability. Furthermore, based on quantum confinement effects of the QDs, the energy of the electrons could be adjusted to a level that inhibits the hydrogen evolution reaction (HER, the main competitive reaction to PCRR) and improves the selectivity and activity for CH₃OH production from the PCRR. The band structures of photocatalysts with various CdSe particle sizes were also investigated quantitatively to establish the relationship between the band energy and the photocatalytic performance.     

Rational Design and Application of Covalent Organic Frameworks for Solar Fuel Production

Harnessing solar energy and converting it into renewable fuels by chemical processes, such as water splitting and carbon dioxide (CO₂) reduction, is a highly promising yet challenging strategy to mitigate the effects arising from the global energy crisis and serious environmental concerns. In recent years, covalent organic framework (COF)-based materials have gained substantial research interest because of their diversified architecture, tunable composition, large surface area, and high thermal and chemical stability. Their tunable band structure and significant light absorption with higher charge separation efficiency of photoinduced carriers make them suitable candidates for photocatalytic applications in hydrogen (H₂) generation, CO₂ conversion, and various organic transformation reactions. In this article, we describe the recent progress in the topology design and synthesis method of COF-based nanomaterials by elucidating the structure-property correlations for photocatalytic hydrogen generation and CO₂ reduction applications. The effect of using various kinds of 2D and 3D COFs and strategies to control the morphology and enhance the photocatalytic activity is also summarized. Finally, the key challenges and perspectives in the field are highlighted for the future development of highly efficient COF-based photocatalysts.     

In situ preparation of Bi2O3/(BiO)2CO3 composite photocatalyst with enhanced visible-light photocatalytic activity

A Bi₂O₃/(BiO)₂CO₃ (BO/BOC) composite photocatalyst was in situ prepared via calcinating (BiO)₂CO₃. The as-prepared Bi₂O₃/(BiO)₂CO₃ composites displayed enhanced photocatalytic activity for the degradation of RhB under visible light. The structure–activity relationship between catalyst structure and properties was investigated by SEM, XRD, XPS, FTIR, BET, DRS and photoelectrochemical tests. Apart from the increased absorption of visible light, the accelerated charge separation and transfer was achieved via the intimate contact and matched band structure between Bi₂O₃ and (BiO)₂CO₃. The formation of heterogeneous structures could promote the production of reactive oxygen species (·O₂^?) and eventually improve the photocatalytic performance for the removal of organic contaminants. This heating treatment strategy might be extended for improving light absorbance and charge carriers separation for other UV-based photocatalysts.

     

MoS_2/g-C_3N_4复合材料的制备及可见光催化性能

首先在N-甲基吡咯烷酮溶液中超声剥离得到少层的MoS_2,将其与石墨相氮化碳(g-C_3N_4)复合,制得MoS_2/g-C_3N_4复合材料。采用X射线衍射(XRD),扫描电镜(SEM),X射线光电子能谱(XPS),傅里叶变换红外光谱(FTIR),Raman光谱,紫外-可见漫反射吸收光谱(DRS)和光致荧光(PL)技术对复合材料进行表征。可见光下考察MoS_2/g-C_3N_4复合材料光催化降解罗丹明B(Rh B)的活性,结果表明:将少量MoS_2与g-C_3N_4复合可明显提高光催化活性,且1%(w/w)MoS_2/g-C_3N_4复合物的光催化活性最高,可能的原因是MoS_2和g-C_3N_4匹配的能带结构,增大了界面间电荷的传输,降低了光生电子-空穴的复合,进而提高了光催化活性。     

Synthesis and Characterization of an α-Fe2O3-Decorated g-C3N4 Heterostructure for the Photocatalytic Removal of MO

This study describes the preparation of graphitic carbon nitride (g-C₃N₄), hematite (α-Fe₂O₃), and their g-C₃N₄/α-Fe₂O₃ heterostructure for the photocatalytic removal of methyl orange (MO) under visible light illumination. The facile hydrothermal approach was utilized for the preparation of the nanomaterials. Powder X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive X-ray (EDX), and Brunauer–Emmett–Teller (BET) were carried out to study the physiochemical and optoelectronic properties of all the synthesized photocatalysts. Based on the X-ray photoelectron spectroscopy (XPS) and UV-visible diffuse reflectance (DRS) results, an energy level diagram vs. SHE was established. The acquired results indicated that the nanocomposite exhibited a type-II heterojunction and degraded the MO dye by 97%. The degradation ability of the nanocomposite was higher than that of pristine g-C₃N₄ (41%) and α-Fe₂O₃ (30%) photocatalysts under 300 min of light irradiation. The formation of a type-II heterostructure with desirable band alignment and band edge positions for efficient interfacial charge carrier separation along with a larger specific surface area was collectively responsible for the higher photocatalytic efficiency of the g-C₃N₄/α-Fe₂O₃ nanocomposite. The mechanism of the nanocomposite was also studied through results obtained from UV-vis and XPS analyses. A reactive species trapping experiment confirmed the involvement of the superoxide radical anion (O₂^•−) as the key reactive oxygen species for MO removal. The degradation kinetics were also monitored, and the reaction was observed to be pseudo-first order. Moreover, the sustainability of the photocatalyst was also investigated.     

Au nanorods decorated TiO2 nanobelts with enhanced full solar spectrum photocatalytic antibacterial activity and the sterilization file cabinet application

TiO₂ photocatalysts have been widely studied and applied for removing bacteria, but its antibacterial efficiency is limited to the ultraviolet (UV) range of the solar spectrum. In this work, we use the gold (Au) nanorods to enhance the visible and near-infrared (NIR) light absorption of TiO₂ NBs, a typical UV light photocatalyst, thus the enhancement of its full solar spectrum (UV, visible and NIR) photocatalytic antibacterial properties is achieved. Preliminary surface plasmon resonance (SPR) enhancement photocatalytic antibacterial mechanism is suggested. On one hand, transverse and longitudinal SPR of Au NRs is beneficial for visible and NIR light utilization. On the other hand, Au NRs combined with TiO₂ NBs to form the heterostructure, which can improve the photogenerated carrier separation and direct electron transfer increases the hot electron concentration while Au NRs as the electron channel can well restrain charge recombination, finally produces the high yield of radical oxygen species and exhibits a superior antibacterial efficiency. Furthermore, we design a sterilization file cabinet with Au NR/TiO₂ NB heterostructures as the photocatalytic coating plates. Our study reveals that Au NR/TiO₂ NB heterostructure is a potential candidate for sterilization of bacteria and archives protection.     

Van der Waals Heterostructures Comprised of Ultrathin Polymer Nanosheets for Efficient Z‐Scheme Overall Water Splitting

Inspired by natural photosynthesis, Z‐scheme photocatalytic systems are very appealing for achieving efficient overall water splitting. Developing metal‐free Z‐scheme photocatalysts for overall water splitting, however, still remains challenging. The construction of polymer‐based van der Waals heterostructures as metal‐free Z‐scheme photocatalytic systems for overall water splitting is described using aza‐fused microporous polymers (CMP) and C₂N ultrathin nanosheets as O₂‐ and H₂‐evolving catalysts, respectively. Although neither polymer is able to split pure water using visible light, a 2:1 stoichiometric ratio of H₂ and O₂ was observed when aza‐CMP/C₂N heterostructures were used. A solar‐to‐hydrogen conversion efficiency of 0.23 % was determined, which could be further enhanced to 0.40 % by using graphene as the solid electron mediator to promote the interfacial charge‐transfer process. This study highlights the potential of polymer photocatalysts for overall water splitting.     

MoS2/g-C3N4复合材料的制备及可见光催化性能

首先在N-甲基吡咯烷酮溶液中超声剥离得到少层的MoS₂,将其与石墨相氮化碳（g-C₃N₄）复合,制得MoS₂/g-C₃N₄复合材料。采用X射线衍射（XRD）,扫描电镜（SEM）,X射线光电子能谱（XPS）,傅里叶变换红外光谱（FTIR）,Raman光谱,紫外-可见漫反射吸收光谱（DRS）和光致荧光（PL）技术对复合材料进行表征。可见光下考察MoS₂/g-C₃N₄复合材料光催化降解罗丹明B（RhB）的活性,结果表明：将少量MoS₂与g-C₃N₄复合可明显提高光催化活性,且1%（w/w）MoS₂/g-C₃N₄复合物的光催化活性最高,可能的原因是MoS₂和g-C₃N₄匹配的能带结构,增大了界面间电荷的传输,降低了光生电子-空穴的复合,进而提高了光催化活性。     

Copper-Sulfur-Nitrogen Cluster Providing a Local Proton for Efficient Carbon Dioxide Photoreduction

Atomically precise Cu clusters are highly desirable as catalysts for CO₂ reduction reaction (CO₂RR), and they provide an appropriate model platform for elaborating their structure–activity relationship. However, an efficient overall photocatalytic CO₂RR with H₂O using assembled Cu-cluster aggregates as single component photocatalyst has not been reported. Herein, we report a stable crystalline Cu−S−N cluster photocatalyst with local protonated N−H groups (denoted as Cu₆−NH ). The catalyst exhibits suitable photocatalytic redox potentials, high structural stability, active catalytic species, and a narrow band gap, which account for its outstanding photocatalytic CO₂RR performance under visible light, with ≈100 % selectivity for CO evolution. Remarkably, systematic isostructural Cu-cluster control experiments, in situ infrared spectroscopy, and density functional theory calculations revealed that the protonated pyrimidine N atoms in the Cu₆−NH cluster act as a proton relay station, providing a local proton during the photocatalytic CO₂RR. This efficiently lowers the energy barrier for the formation of the *COOH intermediate, which is the rate-limiting step, efficiently enhancing the photocatalytic performance. This work lays the foundation for the development of atomically precise metal-cluster-based photocatalysts.     

A Bi/BiOI/(BiO)2CO3 heterostructure for enhanced photocatalytic NO removal under visible light

Narrow-band BiOI photocatalysts usually suffer from low photocatalysis efficiency under visible light exposure because of rapid charge recombination. In this work, to overcome this deficiency of photosensitive BiOI, oxygen vacancies, Bi particles, and Bi₂O₂CO₃ were co-induced in BiOI via a facile in situ assembly method at room temperature using NaBH₄ as the reducing agent. In the synthesized ternary Bi/BiOI/(BiO)₂CO₃, the oxygen vacancies, dual heterojunctions (i.e., Bi/BiOI and BiOI/(BiO)₂CO₃), and surface plasmon resonance effect of the Bi particles contributed to efficient electron-hole separation and an increase in charge carrier concentration, thus boosting the overall visible light photocatalysis efficiency. The as-prepared catalysts were applied for the removal of NO in concentrations of parts per billion from air in continuous air flow under visible light illumination. Bi/BiOI/(BiO)₂CO₃ exhibited a highly enhanced NO removal ratio of 50.7%, much higher than that of the pristine BiOI (1.2%). Density functional theory calculations and experimental results revealed that the Bi/BiOI/(BiO)₂CO₃ composites promoted the production of reactive oxygen species for photocatalytic NO oxidation. Thus, this work provides a new strategy to modify narrow-band semiconductors and explore other bismuth-containing heterostructured visible-light-driven photocatalysts.     

Semiconductor/Covalent‐Organic‐Framework Z‐Scheme Heterojunctions for Artificial Photosynthesis

A strategy to covalently connect crystalline covalent organic frameworks (COFs) with semiconductors to create stable organic–inorganic Z‐scheme heterojunctions for artificial photosynthesis is presented. A series of COF–semiconductor Z‐scheme photocatalysts combining water‐oxidation semiconductors (TiO₂, Bi₂WO₆, and α‐Fe₂O₃) with CO₂ reduction COFs (COF‐316/318) was synthesized and exhibited high photocatalytic CO₂‐to‐CO conversion efficiencies (up to 69.67 μmol g^?1 h^?1), with H₂O as the electron donor in the gas–solid CO₂ reduction, without additional photosensitizers and sacrificial agents. This is the first report of covalently bonded COF/inorganic‐semiconductor systems utilizing the Z‐scheme applied for artificial photosynthesis. Experiments and calculations confirmed efficient semiconductor‐to‐COF electron transfer by covalent coupling, resulting in electron accumulation in the cyano/pyridine moieties of the COF for CO₂ reduction and holes in the semiconductor for H₂O oxidation, thus mimicking natural photosynthesis.     

BiVO4‐TiO2 Composite Photocatalysts for Dye Degradation Formed Using the SILAR Method

Composite photocatalyst films have been fabricated by depositing BiVO₄ upon TiO₂ via a sequential ionic layer adsorption reaction (SILAR) method. The photocatalytic materials were investigated by XRD, TEM, UV/Vis diffuse reflectance, inductively coupled plasma optical emission spectrometry (ICP‐OES), XPS, photoluminescence and Mott–Schottky analyses. SILAR processing was found to deposit monoclinic‐scheelite BiVO₄ nanoparticles onto the surface, giving successive improvements in the films′ visible light harvesting. Electrochemical and valence band XPS studies revealed that the prepared heterojunctions have a type II band structure, with the BiVO₄ conduction band and valence band lying cathodically shifted from those of TiO₂. The photocatalytic activity of the films was measured by the decolourisation of the dye rhodamine 6G using λ>400 nm visible light. It was found that five SILAR cycles was optimal, with a pseudo‐first‐order rate constant of 0.004 min^?1. As a reference material, the same SILAR modification has been made to an inactive wide‐band‐gap ZrO₂ film, where the mismatch of conduction and valence band energies disallows charge separation. The photocatalytic activity of the BiVO₄–ZrO₂ system was found to be significantly reduced, highlighting the importance of charge separation across the interface. The mechanism of action of the photocatalysts has also been investigated, in particular the effect of self‐sensitisation by the model organic dye and the ability of the dye to inject electrons into the photocatalyst′s conduction band.