In-situ synthesis of CdS/g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> hybrid nanocomposites with enhanced visible photocatalytic activity

A novel and simple in situ synthetic strategy was used to fabricate CdS/g-C₃N₄ hybrid nanocomposite catalysts with visible-light-driven photocatalytic activity from cadmium-containing carbon nitride compounds. X-ray diffraction measurements, high-resolution transmission electron microscopy images, and Fourier transform infrared spectra showed heterojunctions with a close interface between the g-C₃N₄ and the CdS nanoparticles and nanorods in the composite. Ultraviolet visible diffuse reflectance spectra exhibited a red shift that further presented the CdS in the polymer g-C₃N₄ skeleton, which allowed the efficient utilization of the solar spectrum for creating photogenerated electrons and holes. The photoluminescence spectra of the nanocomposites suggested charge transfer from g-C₃N₄ to CdS. The photocurrent intensity of hybrid nanocomposites was 2.3 times than that of pure g-C₃N₄ sample, and photocatalytic activity for the photodegradation of methyl orange was 2.5 times, and hydrogen evolution reaction was 2.8 times. Enhanced photocatalytic activity and photocurrent for the CdS/g-C₃N₄ hybrid nanocomposites were achieved.     

Delayed Photoelectron Transfer in Pt‐Decorated CdS Nanorods under Hydrogen Generation Conditions

Noble‐metal‐decorated colloidal semiconductor nanocrystals are currently receiving significant attention for photocatalytic hydrogen generation. A detailed knowledge of the charge‐carrier dynamics in these hybrid systems under hydrogen generation conditions is crucial for improving their performance. Here, a transient absorption spectroscopy study is conducted on colloidal, Pt‐decorated CdS nanorods addressing this issue. Surprisingly, under hydrogen generation conditions (i.e., in the presence of the hole‐scavenger sodium sulfite), photoelectron transfer to the catalytically active Pt is slower than without the hole scavenger, where no significant hydrogen generation occurs. This unexpected behavior can be explained by different degrees of localization of the electron wavefunction in the presence and absence of holes on the nanorods, which modify the electron transfer rates to the Pt. The results show that solely optimizing charge transfer rates in photocatalytic nanosystems is no guarantee of improved performance. Instead, the collective Coulomb interaction‐mediated electron–hole dynamics need to be considered.     

Low‐Energy Facets on CdS Allomorph Junctions with Optimal Phase Ratio to Boost Charge Directional Transfer for Photocatalytic H2 Fuel Evolution

Low‐energy facets on CdS allomorph junctions with optimal phase ratio are designed to boost charge directional transfer for photocatalytic H₂ fuel evolution. Fermi energy level difference between low‐energy facets as driving force promotes electrons directional transfer to hexagonal CdS(102) facet and holes to cubic CdS(111) facet. The optimal allomorphs CdS presents superior photocatalytic H₂ evolution rate of 32.95 mmol g^?1 h^?1 with release in a large amount of visible H₂ bubbles, which is much higher than single‐phase CdS with high‐energy facets and even supports noble metal photocatalysts. This scientific perspective on low‐energy facets of allomorph junctions with optimal phase ratio breaks the long‐held view of pursuing high‐energy crystal surfaces, which will break the understanding on surface structure crystal facet engineering of photocatalytic materials.     

Unraveling Photoexcited Charge Transfer Pathway and Process of CdS/Graphene Nanoribbon Composites toward Visible‐Light Photocatalytic Hydrogen Evolution

Converting solar energy into chemical fuels is increasingly receiving a great deal of attention. In this work, CdS nanoparticles (NPs) are solvothermally anchored onto graphene nanoribbons (GNRs) that are longitudinally unzipped from multiwalled carbon nanotubes. The as‐synthesized CdS/GNR nanocomposites with recyclability present GNR content‐dependent activity in visible‐light‐driven hydrogen evolution from water splitting. In a range of 1–10 wt% GNRs, the CdS/GNR composites with 2 wt% GNRs achieves the greatest hydrogen evolution rate of 1.89 mmol h^?1 g^?1. The corresponding apparent quantum efficiency is 19.3%, which is ≈3.7 times higher than that of pristine CdS NPs. To elucidate the underlying photocatalytic mechanism, a systematic characterization, including in situ irradiated X‐ray photoelectron spectroscopy and Kelvin probe measurements, is performed. In particular, the interfacial charge transfer pathway and process from CdS NPs to GNRs is revealed. This work may open avenues to fabricate GNR‐based nanocomposites for solar‐to‐chemical energy conversion and beyond.     

Investigation of the Photocatalytic Hydrogen Production of Semiconductor Nanocrystal-Based Hydrogels

Destabilization of a ligand-stabilized semiconductor nanocrystal solution with an oxidizing agent can lead to a macroscopic highly porous self-supporting nanocrystal network entitled hydrogel, with good accessibility to the surface. The previously reported charge carrier delocalization beyond a single nanocrystal building block in such gels can extend the charge carrier mobility and make a photocatalytic reaction more probable. The synthesis of ligand-stabilized nanocrystals with specific physicochemical properties is possible, thanks to the advances in colloid chemistry made in the last decades. Combining the properties of these nanocrystals with the advantages of nanocrystal-based hydrogels will lead to novel materials with optimized photocatalytic properties. This work demonstrates that CdSe quantum dots, CdS nanorods, and CdSe/CdS dot-in-rod-shaped nanorods as nanocrystal-based hydrogels can exhibit a much higher hydrogen production rate compared to their ligand-stabilized nanocrystal solutions. The gel synthesis through controlled destabilization by ligand oxidation preserves the high surface-to-volume ratio, ensures the accessible surface area even in hole-trapping solutions and facilitates photocatalytic hydrogen production without a co-catalyst. Especially with such self-supporting networks of nanocrystals, the problem of colloidal (in)stability in photocatalysis is circumvented. X-ray photoelectron spectroscopy and photoelectrochemical measurements reveal the advantageous properties of the 3D networks for application in photocatalytic hydrogen production.     

Au NPs@MoS2 Sub‐Micrometer Sphere‐ZnO Nanorod Hybrid Structures for Efficient Photocatalytic Hydrogen Evolution with Excellent Stability

MoS₂ shows promising applications in photocatalytic water splitting, owing to its uniquely optical and electric properties. However, the insufficient light absorption and lack of performance stability are two crucial issues for efficient application of MoS₂ nanomaterials. Here, Au nanoparticles (NPs)@MoS₂ sub‐micrometer sphere‐ZnO nanorod (Au NPs@MoS₂‐ZnO) hybrid photocatalysts have been successfully synthesized by a facile process combining the hydrothermal method and seed‐growth method. Such photocatalysts exhibit high efficiency and excellent stability for hydrogen production via multiple optical‐electrical effects. The introduction of Au NPs to MoS₂ sub‐micrometer spheres forming a core–shell structure demonstrates strong plasmonic absorption enhancement and facilitates exciton separation. The incorporation of ZnO nanorods to the Au NPs@MoS₂ hybrids further extends the light absorption to a broader wavelength region and enhances the exciton dissociation. In addition, mutual contacts between Au NPs (or ZnO nanorods) and the MoS₂ spheres effectively protect the MoS₂ nanosheets from peeling off from the spheres. More importantly, efficiently multiple exciton separations help to restrain the MoS₂ nanomaterials from photocorrosion. As a result, the Au@MoS₂‐ZnO hybrid structures exhibit an excellent hydrogen gas evolution (3737.4 μmol g^?1) with improved stability (91.9% of activity remaining) after a long‐time test (32 h), which is one of the highest photocatalytic activities to date among the MoS₂ based photocatalysts.     

Nonepitaxial Gold‐Tipped ZnSe Hybrid Nanorods for Efficient Photocatalytic Hydrogen Production

For the first time, colloidal gold (Au)–ZnSe hybrid nanorods (NRs) with controlled size and location of Au domains are synthesized and used for hydrogen production by photocatalytic water splitting. Au tips are found to grow on the apices of ZnSe NRs nonepitaxially to form an interface with no preference of orientation between Au(111) and ZnSe(001). Density functional theory calculations reveal that the Au tips on ZnSe hybrid NRs gain enhanced adsorption of H compared to pristine Au, which favors the hydrogen evolution reaction. Photocatalytic tests reveal that the Au tips on ZnSe NRs effectively enhance the photocatalytic performance in hydrogen generation, in which the single Au‐tipped ZnSe hybrid NRs show the highest photocatalytic hydrogen production rate of 437.8 µmol h^?1 g^?1 in comparison with a rate of 51.5 µmol h^?1 g^?1 for pristine ZnSe NRs. An apparent quantum efficiency of 1.3% for hydrogen evolution reaction for single Au‐tipped ZnSe hybrid NRs is obtained, showing the potential application of this type of cadmium (Cd)‐free metal–semiconductor hybrid nanoparticles (NPs) in solar hydrogen production. This work opens an avenue toward Cd‐free hybrid NP‐based photocatalysis for clean fuel production.     

Photocatalytic, recyclable CdS nanoparticle-carbon nanotube hybrid sponges

Semiconducting nanoparticles with lower bandgap (e.g., CdS) are alternative photocatalysts to TiO2, since they have a potentially wider range light of absorption and improved catalytic efficiency. However, they must be securely anchored on a porous substrate for practical applications. Here, we report a hybrid porous photocatalyst fabricated by grafting 4?C6 nm diameter CdS nanoparticles uniformly throughout the entire macroporous structure of a three-dimensional carbon nanotube (CNT) sponge. The unique feature of our structure is that only the CdS nanoparticles grafted on the outside surface are active in photocatalysis, while other nanoparticles are stored inside the sponge in the fresh state for use when the catalyst is recycled. Our CdS-CNT hybrid sponges show high efficiency in removing organic contaminants from water. Spectroscopic measurements show that the hybrid sponges are multifunctional, simultaneously performing organic molecular adsorption (using the inter-CNT spacing), and photocatalytic decomposition (by the CdS nanoparticles grafted on the surface), both of which contribute to water purification. Furthermore, the surface part of the sponges can be stripped off to expose inner nanoparticles for use when the catalyst is recycled, without performance degradation.      

One‐Dimensional Densely Aligned Perovskite‐Decorated Semiconductor Heterojunctions with Enhanced Photocatalytic Activity

By using one‐dimensional rutile TiO₂ nanorod arrays as the structure‐directing scaffold as well as the TiO₂ source to two consecutive hydrothermal reactions, densely aligned SrTiO₃‐modified rutile TiO₂ heterojunction photocatalysts are crafted for the first time. The first hydrothermal processing yielded nanostructured rutile TiO₂ with the hollow openings on the top of nanorods (i.e., partially etched rutile TiO₂ nanorod arrays; denoted PE‐TNRAs). The subsequent second hydrothermal treatment in the presence of Sr²⁺ transforms the surface of partially etched rutile TiO₂ nanorods into SrTiO₃ nanoparticles via the concurrent dissolution of TiO₂ and precipitation of SrTiO₃ while retaining the cylindrical shape (i.e., forming SrTiO₃‐decorated rutile TiO₂ composite nanorods; denoted STO‐TNRAs). The structural and composition characterizations substantiate the success in achieving STO‐TNRA nanostructures. In comparison to PE‐TNRAs, STO‐TNRA photocatalysts exhibit higher photocurrents and larger photocatalytic degradation rates of methylene blue (3.21 times over PE‐TNRAs) under UV light illumination as a direct consequence of improved charge carrier mobility and enhanced electron/hole separation. Such 1D perovskite‐decorated semiconductor nanoarrays are very attractive for optoelectronic applications in photovoltaics, photocatalytic hydrogen production, among other areas.     

Ultrasmall MoOx Clusters as a Novel Cocatalyst for Photocatalytic Hydrogen Evolution

To enhance the performance of semiconductor photocatalysts, cocatalysts are used to accelerate surface reactions. Herein, ultrasmall molybdenum–oxygen (MoO_x) clusters are developed as a novel non‐noble cocatalyst, which significantly promotes the photocatalytic hydrogen generation rate of CdS nanowires (NWs). As indicated by extended X‐ray absorption fine structure analysis, direct bonds are formed between CdS NWs and MoO_x clusters, which guarantee the migration of photo‐generated charge carriers. Moreover, the MoO_x clusters induce deep electron trap states owing to the unique atomic arrangement and configuration with the generation of long‐lived electrons to enhance the activity. These findings may guide the design of efficient cocatalytic materials for solar water splitting and open a new avenue toward practical applications of ultrasmall clusters.     

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.     

Enhanced visible-light-responsive photocatalytic property of CdS and PbS sensitized ZnO nanocomposite photocatalysts

CdS and PbS nanoparticles sensitized ZnO nanorods were synthesized by successive ionic layer adsorption and reaction method. The photocatalytic activity of different structures was evaluated by photocatalytic degeneration yield of methyl orange. Co-sensitization of CdS and PbS nanoparticles on ZnO nanorods showed enhanced photocatalytic activity due to its response at visible light area and the stepwise band gap constructed in ZnO/CdS/PbS nanostructures.     

Controlled synthesis in large-scale of CdS mesospheres and photocatalytic activity

In the present work, we reported the controlled synthesis of CdS mesospheres composed of radially arranged nanorods by hydrothermal method without any surfactant. The as-prepared CdS mesospheres were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD patterns indicated that these CdS mesospheres present a hexagonal structure and free of deleterious phases. SEM micrographs showed that CdS mesospheres are composed of several nanoparticles with growth mechanism via aggregation of particles. The photocatalytic activities were investigated by degradation of reactive brilliant dye X-3B (C.I. Reactive Red 2) under visible light irradiation. Results show that 93% X-3B was degraded after 100 min irradiation by the best one sample. The results indicate that the as-prepared CdS samples are promising candidate materials for visible light responsive photocatalysts.     

Embedding Au Quantum Dots in Rimous Cadmium Sulfide Nanospheres for Enhanced Photocatalytic Hydrogen Evolution

Rational design and development of new‐generation photocatalysts with high hydrogen evolution activity is recognized as an effective strategy to settle energy crisis. To this regard, hybrid photocatalysts of Au quantum dots embedded in rimous cadmium sulfide nanospheres are synthesized by using a simple hydrothermal process followed by photoreduction. The rimous cadmium sulfide nanospheres with rough surface and irregular fissures greatly strengthen their adhesion and interaction with Au quantum dots, which effectively facilitates the separation, restrains the recombination, and accelerates the consumption of photoinduced electron‐hole pairs. Impressively, the highest photocatalytic activity for hydrogen generation (601.2 μmol h^?1 g^?1) and organic pollutant degradation (100% degradation in 80 min) is obtained by adjusting the Au mass loading to achieve uniform distribution. This work paves new way to the exploitation of highly efficient metal/semiconductor hybrid photocatalysts for clean energy generation and environment restoration.     

Hierarchical NiO@N‐Doped Carbon Microspheres with Ultrathin Nanosheet Subunits as Excellent Photocatalysts for Hydrogen Evolution

Achieving highly efficient hierarchical photocatalysts for hydrogen evolution is always challenging. Herein, hierarchical mesoporous NiO@N‐doped carbon microspheres (HNINC) are successfully fabricated with ultrathin nanosheet subunits as high‐performance photocatalysts for hydrogen evolution. The unique architecture of N‐doped carbon layers and hierarchical mesoporous structures from HNINC could effectively facilitate the separation and transfer of photo‐induced electron–hole pairs and afford rich active sites for photocatalytic reactions, leading to a significantly higher H₂ production rate than NiO deposited with platinum. Density functional theory calculations reveal that the migration path of the photo‐generated electron transfer is from Ni 3d and O 2p hybrid states of NiO to the C 2p state of graphite, while the photo‐generated holes locate at Ni 4s and Ni 4p hybrid states of NiO, which is beneficial to improve the separation of photo‐generated electron–hole pairs. Gibbs free energy of the intermediate state for hydrogen evolution reaction is calculated to provide a fundamental understanding of the high H₂ production rate of HNINC. This research sheds light on developing novel photocatalysts for efficient hydrogen evolution.     

Photocatalytic hydrogen evolution over surface-modified titanate nanotubes by 5-aminosalicylic acid decorated with silver nanoparticles

The efficiency of titanate-nanotubes-based photocatalysts towards hydrogen production was studied in the presence of the sacrificial agent, 2-propanol. The highest hydrogen production rate (~120 μmol h⁻¹ g⁻¹) was observed over surface-modified titanate nanotubes by 5-amino salicylic acid decorated with nanometer-sized silver nanoparticles. The X-ray diffraction analysis, transmission electron microscopy, nitrogen adsorption–desorption isotherms, and diffuse reflection spectroscopy were applied to characterize the prepared photocatalytic materials. The better photocatalytic performance of inorganic–organic hybrid materials in comparison to the pristine titanate nanotubes is a consequence of their improved light-harvesting ability due to the formation of interfacial charge transfer (ICT) complex, as well as the presence of metallic silver nanoparticles that suppress the recombination of photo-generated charge carriers. The spin trapping EPR experiments under irradiation of prepared photocatalysts with either UV or visible light were used to monitor the appearance of hydroxyl radicals and superoxide radical anions. The generation of superoxide radical anions under visible light irradiation was detected for hybrid materials, but not for the pristine titanate nanotubes. These results are a consequence of enhanced promotion of electrons to the conduction band due to extended absorption in visible spectral range in hybrids and support the higher efficiency of hydrogen generation observed for surface-modified titanate nanotubes by 5-amino salicylic acid decorated with silver nanoparticles.     

Effect of TiO2 nanoparticle shape on hydrogen evolution via water splitting

Pt/TiO2 nanospheres and nanorods were used to generate hydrogen via water splitting and the effect of the shapes of TiO2 nanoparticles were evaluated for hydrogen evolution. TiO2 nanorods exhibited an increase in charge transfer rate between the nanoparticle surface and the electrolyte. This led to improvement in the rate of photo-catalytic hydrogen evolution during the decomposition of water.     

Ultrathin Co(Ni)-doped MoS<Subscript>2</Subscript> nanosheets as catalytic promoters enabling efficient solar hydrogen production

The design of efficient artificial photosynthetic systems that harvest solar energy to drive the hydrogen evolution reaction via water reduction is of great importance from both the theoretical and practical viewpoints.Integrating appropriate co-catalyst promoters with strong light absorbing materials represents an ideal strategy to enhance the conversion efficiency of solar energy in hydrogen production.Herein,we report,for the first time,the synthesis of a class of unique hybrid structures consisting of ultrathin Co(Ni)-doped MoS2 nanosheets (co-catalyst promoter) intimately grown on semiconductor CdS nanorods (light absorber).The as-synthesized one-dimensional CdS@doped-MoS2 heterostructures exhibited very high photocatalytic activity (with a quantum yield of 17.3％) and stability towards H2 evolution from the photoreduction of water.Theoretical calculations revealed that Ni doping can increase the number of uncoordinated atoms at the edge sites of MoS2 nanosheets to promote electron transfer across the CdS/MoS2 interfaces as well as hydrogen reduction,leading to an efficient H2 evolution reaction.     

In Situ Irradiated X‐Ray Photoelectron Spectroscopy Investigation on a Direct Z‐Scheme TiO2/CdS Composite Film Photocatalyst

Inspired by nature, artificial photosynthesis through the construction of direct Z‐scheme photocatalysts is extensively studied for sustainable solar fuel production due to the effectiveness in enhancing photoconversion efficiency. However, there is still a lack of thorough understanding and direct evidence for the direct Z‐scheme charge transfer in these photocatalysts. Herein, a recyclable direct Z‐scheme composite film composed of titanium dioxide and cadmium sulfide (TiO₂/CdS) is prepared for high‐efficiency photocatalytic carbon dioxide (CO₂) reduction. In situ irradiated X‐ray photoelectron spectroscopy (ISI‐XPS) confirms the direct Z‐scheme charge‐carrier migration pathway in the photocatalytic system. Furthermore, density functional theory simulation identifies the intrinsic cause for the formation of the direct Z‐scheme heterojunction between the TiO₂ and the CdS. Thanks to the significantly enhanced redox abilities of the charge carriers in the direct Z‐scheme system, the photocatalytic CO₂ reduction performance of the optimized TiO₂/CdS is 3.5, 5.4, and 6.3 times higher than that of CdS, TiO₂, and commercial TiO₂ (P25), respectively, in terms of methane production. This work is a valuable guideline in preparation of highly efficient recyclable nanocomposite for photoconversion applications.     

High Density Unaggregated Au Nanoparticles on ZnO Nanorod Arrays Function as Efficient and Recyclable Photocatalysts for Environmental Purification

Photodegradation of organic pollutants in aqueous solution is a promising method for environmental purification. Photocatalysts capable of promoting this reaction are often composed of noble metal nanoparticles deposited on a semiconductor. Unfortunately, the separation of these semiconductor‐metal nanopowders from the treated water is very difficult and energy consumptive, so their usefulness in practical applications is limited. Here, a precisely controlled synthesis of a large‐scale and highly efficient photocatalyst composed of monolayered Au nanoparticles (AuNPs) chemically bound to vertically aligned ZnO nanorod arrays (ZNA) through a bifunctional surface molecular linker is demonstrated. Thioctic acid with sufficient steric stabilization is used as a molecular linker. High density unaggregated AuNPs bonding on entire surfaces of ZNA are successfully prepared on a conductive film/substrate, allowing easy recovery and reuse of the photocatalysts. Surprisingly, the ZNA‐AuNPs heterostructures exhibit a photodegradation rate 8.1 times higher than that recorded for the bare ZNA under UV irradiation. High density AuNPs, dispersed perfectly on the ZNA surfaces, significantly improve the separation of the photogenerated electron‐hole pairs, enlarge the reaction space, and consequently enhance the photocatalytic property for degradation of chemical pollutants. Photoelectron, photoluminescence and photoconductive measurements confirm the discussion on the charge carrier separation and photocatalytic experimental data. The demonstrated higher photodegradation rates demonstrated indicate that the ZNA‐AuNPs heterostructures are candidates for the next‐generation photocatalysts, replacing the conventional slurry photocatalysts.