Direct Observation of Z-Scheme Route in Cu31 S16 /Znx Cd1-x S Heteronanoplates for Highly Efficient Photocatalytic Hydrogen Evolution.

Although photocatalytic hydrogen production from water holds great potential as a renewable and sustainable energy alternative, the practical application of the technology demands cost-effective, simple photocatalytic systems with high efficiency in hydrogen evolution reaction (HER). Herein, the synthesis and characterization of Cu31 S16 /Znx Cd1-x S heterostructured nanoplates (Cu31 S16 /ZnCdS HNPs) as a high photocatalytic system are reported. The cost-effective, hierarchical structures are easily prepared using the Cu31 S16 NPs as the seed by the epitaxial growth of the ZnCdS nanocrystals (NCs). The Cu31 S16 /ZnCdS without the noble metal cocatalyst exhibits a high HER rate of 61.7 mmol g-1  h-1 , which is 8,014 and 17 times higher than that of Cu31 S16 and ZnCdS, respectively, under visible light irradiation. The apparent quantum yield (AQY) of Cu31 S16 /ZnCdS reaches 67.9% at 400 nm with the highest value so far in the reported ZnCdS-based photocatalysts. The excellent activity and stability of the Cu31 S16 /ZnCdS are attributed to the formation of a strong internal electric field (IEF) and the Z-scheme pathway. The comprehensive experiments and theoretical calculations provide the direct evidences of the Z-scheme route. This work may offer a way for the design and development of efficient photocatalysts to achieve solar-to-chemical energy conversion at a practically useful level.

Photo-self-Fenton Reaction Mediated by Atomically Dispersed Ag-Co Photocatalysts toward Efficient Degradation of Organic Pollutants.

Achieving the complete mineralization of persistent pollutants in wastewater is still a big challenge. Here, we propose an efficient photo-self-Fenton reaction for the degradation of different pollutants using the high-density (Ag: 22 wt %) of atomically dispersed AgCo dual sites embedded in graphic carbon nitride (AgCo-CN). Comprehensive experimental measurements and density functional theory (DFT) calculations demonstrate that the Ag and Co dual sites in AgCo-CN play a critical role in accelerating the photoinduced charge separation and forming the self-Fenton redox centers, respectively. The bimetallic AgCo-CN exhibited excellent photocatalytic performance toward the phenol even under extreme conditions due to an efficient degradation pathway and in situ generation of the hydrogen peroxide producing the main active oxygen species (⋅OH and 1 O2 ) and showed long-term activity in a self-design photo-Filter reactor for the purification of the phenol. Our discoveries pave the way for the design of efficient single-atoms photocatalysts-based photo-self-Fenton reaction for recalcitrant pollutant treatment.

Infrared Light-Induced Anomalous Defect-Mediated Plasmonic Hot Electron Transfer for Enhanced Photocatalytic Hydrogen Evolution.

Efficient utilization of infrared (IR) light, which occupies almost half of the solar energy, is an important but challenging task in solar-to-fuel transformation. Herein, we report the discovery of CuS@ZnS core@shell nanocrystals (CSNCs) with strong localized surface plasmon resonance (LSPR) characteristics in the IR light region showing enhanced photocatalytic activity in hydrogen evolution reaction (HER). A unique "plasmon-induced defect-mediated carrier transfer" (PIDCT) at the heterointerfaces of the CSNCs divulged by time-resolved transient spectroscopy enables producing a high quantum yield of 29.2%. The CuS@ZnS CSNCs exhibit high activity and stability in H2 evolution under near-IR light irradiation. The HER rate of CuS@ZnS CSNCs at 26.9 µmol h-1 g-1 is significantly higher than those of CuS NCs (0.4 µmol h-1 g-1) and CuS/ZnS core/satellite heterostructured NCs (15.6 µmol h-1 g-1). The PIDCT may provide a viable strategy for the tuning of LSPR-generated carrier kinetics through controlling the defect engineering to improve photocatalytic performance.

Plasmonic p-n Junction for Infrared Light to Chemical Energy Conversion.

Infrared (IR) light represents an untapped energy source accounting for almost half of all solar energy. Thus, there is a need to develop systems to convert IR light to fuel and make full use of this plentiful resource. Herein, we report photocatalytic H2 evolution driven by near- to shortwave-IR light (up to 2500 nm) irradiation, based on novel CdS/Cu7S4 heterostructured nanocrystals. The apparent quantum yield reached 3.8% at 1100 nm, which exceeds the highest efficiencies achieved by IR light energy conversion systems reported to date. Spectroscopic results revealed that plasmon-induced hot-electron injection at p-n heterojunctions realizes exceptionally long-lived charge separation (>273 µs), which results in efficient IR light to hydrogen conversion. These results pave the way for the exploration of undeveloped low-energy light for solar fuel generation.

Photoelectrocatalytic reduction of CO2 to methanol over a photosystem II-enhanced Cu foam/Si-nanowire system.

A solar-light double illumination photoelectrocatalytic cell (SLDIPEC) was fabricated for autonomous CO2 reduction and O2 evolution with the aid of photosystem II (PS-II, an efficient light-driven water-oxidized enzyme from nature) and utilized in a photoanode solution. The proposed SLPEC system was composed of Cu foam as the photoanode and p-Si nanowires (Si-NW) as the photocathode. Under solar irradiation, it exhibited a super-photoelectrocatalytic performance for CO2 conversion to methanol, with a high evolution rate (41.94mmol/hr), owing to fast electron transfer from PS-II to Cu foam. Electrons were subsequently trapped by Si-NW through an external circuit via bias voltage (0.5V), and a suitable conduction band potential of Si (-0.6eV) allowed CO2 to be easily reduced to CH3OH at the photocathode. The constructed Z-scheme between Cu foam and Si-NW can allow the SLDIPEC system to reduce CO2 (8.03mmol/hr) in the absence of bias voltage. This approach makes full use of the energy band mismatch of the photoanode and photocathode to design a highly efficient device for solving environmental issues and producing clean energy.

Type-I CdSe@CdS@ZnS Heterostructured Nanocrystals with Long Fluorescence Lifetime.

Conventional single-component quantum dots (QDs) suffer from low recombination rates of photogenerated electrons and holes, which hinders their ability to meet the requirements for LED and laser applications. Therefore, it is urgent to design multicomponent heterojunction nanocrystals with these properties. Herein, we used CdSe quantum dot nanocrystals as a typical model, which were synthesized by means of a colloidal chemistry method at high temperatures. Then, CdS with a wide band gap was used to encapsulate the CdSe QDs, forming a CdSe@CdS core@shell heterojunction. Finally, the CdSe@CdS core@shell was modified through the growth of the ZnS shell to obtain CdSe@CdS@ZnS heterojunction nanocrystal hybrids. The morphologies, phases, structures and performance characteristics of CdSe@CdS@ZnS were evaluated using various analytical techniques, including transmission electron microscopy, X-ray diffraction, UV-vis absorption spectroscopy, fluorescence spectroscopy and time-resolved transient photoluminescence spectroscopy. The results show that the energy band structure is transformed from type II to type I after the ZnS growth. The photoluminescence lifetime increases from 41.4 ns to 88.8 ns and the photoluminescence quantum efficiency reaches 17.05% compared with that of pristine CdSe QDs. This paper provides a fundamental study and a new route for studying light-emitting devices and biological imaging based on multicomponent QDs.

Hot hole transfer at the plasmonic semiconductor/semiconductor interface.

Localized surface plasmon resonance (LSPR)-induced hot-carrier transfer provides an attractive alternative for light-harvesting using the full solar spectrum. This defect-mediated hot-carrier transfer is identical at the plasmonic semiconductor/semiconductor interface and can overcome the low efficiency of plasmonic energy conversion, thus boosting the efficiency of IR-light towards energy conversion. Here, using femtosecond transient absorption (TA) measurements, we directly observe the ultrafast non-radiative carrier dynamics of LSPR-driven hot holes created in CuS nanocrystals (NCs) and CuS/CdS hetero nanocrystals (HNCs). We demonstrate that in the CuS NCs, the relaxation dynamics follows multiple relaxation pathways. Two trap states are populated by the LSPR-induced hot holes in times (100-500 fs) that efficiently compete with the conventional LSPR mechanism (250 fs). The trapped hot holes intrinsically relax in 20-40 ps and then decay in 80 ns and 700 ns. In the CuS/CdS HNCs, once the CuS trap states have been populated by the LSPR-generated hot holes, the holes get transferred through plasmon induced transit hole transfer (PITCT) mechanism in 200-300 ps to the CdS acceptor phase and relax in 1-8 and 40-50 µs. The LSPR-recovery shows a weak excitation wavelength and fluence dependence, while the dynamics of the trap states remains largely unaffected. The direct observation of formation and decay processes of trap states and hole transfer from trap states provides important insight into controlling the LSPR-induced relaxation of degenerate semiconductors.

Enhancement of AFB1 Removal Efficiency via Adsorption/Photocatalysis Synergy Using Surface-Modified Electrospun PCL-g-C3N4/CQDs Membranes.

Aflatoxin B1 (AFB1) is a highly toxic mycotoxin produced by aspergillus species under specific conditions as secondary metabolites. In this study, types of PCL (Polycaprolactone) membranes anchored (or not) to g-C3N4/CQDs composites were prepared using electrospinning technology with (or without) the following surface modification treatment to remove AFB1. These membranes and g-C3N4/CQDs composites were characterized by SEM, TEM, UV-vis, XRD, XPS and FTIR to analyze their physical and chemical properties. Among them, the modified PCL-g-C3N4/CQDs electrospun membranes exhibited an excellent ability to degrade AFB1 via synergistic effects of adsorption and photocatalysis, and the degradation rate of 0.5 µg/mL AFB1 solution was observed to be up to 96.88% in 30 min under visible light irradiation. Moreover, the modified PCL-g-C3N4/CQDs electrospun membranes could be removed directly after the reaction process without centrifugal or magnetic separation, and the regeneration was a green approach synchronized with the reaction under visible light avoiding physical or chemical treatment. The mechanism of adsorption by electrostatic attraction and hydrogen bonding interaction was revealed and the mechanism of photodegradation of AFB1 was also proposed based on active species trapping experiments. This study illuminated the highly synergic adsorption and photocatalytic AFB1 removal efficiency without side effects from the modified PCL-g-C3N4/CQDs electrospun membranes, thereby offering a continual and green solution to AFB1 removal in practical application.

Electrospun Membranes Anchored with g-C3N4/MoS2 for Highly Efficient Photocatalytic Degradation of Aflatoxin B1 under Visible Light.

The degradation of aflatoxin (AF) is a topic that always exists along with the food and feed industry. Photocatalytic degradation as an advanced oxidation technology has many benefits, including complete inorganic degradation, no secondary contamination, ease of activity under moderate conditions, and low cost compared with traditional physical, chemical, and biological strategies. However, photocatalysts are usually dispersed during photocatalytic reactions, resulting in energy and time consumption in the separation process. There is even a potential secondary pollution problem from the perspective of food safety. In this regard, three electrospun membranes anchored with g-C3N4/MoS2 composites were prepared for highly efficient photocatalytic degradation of aflatoxin B1 (AFB1) under visible light. These photocatalytic membranes were characterized by XRD, SEM, TEM, FTIR, and XPS. The factors influencing the degradation efficiency of AFB1, including pH values and initial concentrations, were also probed. The three kinds of photocatalytic membranes all exhibited excellent ability to degrade AFB1. Among them, the photocatalytic degradation efficiency of the photocatalytic membranes prepared by the coaxial methods reached 96.8%. The experiment is with an initial concentration of 0.5 µg/mL (500 PPb) after 60 min under visible light irradiation. The mechanism of degradation of AFB1 was also proposed based on active species trapping experiments. Moreover, the prepared photocatalytic membranes exhibited excellent photocatalytic activity even after five-fold use in the degradation of AFB1. These studies showed that electrospun membranes anchored with g-C3N4/MoS2 composites have a high photocatalytic ability which is easily removed from the reacted medium for reuse. Thereby, our study offers a highly effective, economical, and green solution for AFB1 degradation in the foodstuff for practical application.

Photogenerated hole traps in metal-organic-framework photocatalysts for visible-light-driven hydrogen evolution.

Efficient electron-hole separation and carrier utilization are key factors in photocatalytic systems. Here, we use a metal-organic framework (NH2-UiO-66) modified with inner platinum nanoparticles and outer cadmium sulfide (CdS) nanoparticles to construct the ternary composite Pt@NH2-UiO-66/CdS, which has a spatially separated, hierarchical structure for enhanced visible-light-driven hydrogen evolution. Relative to pure NH2-UiO-66, Pt@NH2-UiO-66, and NH2-UiO-66/CdS samples, the Pt@NH2-UiO-66/CdS composite exhibits much higher hydrogen yields with an apparent quantum efficiency of 40.3% at 400 nm irradiation and stability over the most MOF-based photocatalysts. Transient absorption measurements reveal spatial charge-separation dynamics in the composites. The catalyst's high activity and durability are attributed to charge separation following an efficient photogenerated hole-transfer band-trap pathway. This work holds promise for enhanced MOF-based photocatalysis using efficient hole-transfer routes.

Efficient Self-Driving Photoelectrocatalytic Reactor for Synergistic Water Purification and H2 Evolution.

The photoelectrocatalytic (PEC) technique has attracted much attention to getting clear energy and environmental purification. Simultaneous reactions of solar energy generation could be used to apply for practical applications to maximize the functionality of reactor systems. Herein, we crafted a self-driving photoelectrocatalytic reactor system, comprising platinum (Pt) modified p-Si nanowires (Pt/Si-NWs) as a photocathode and TiO2 nanotube arrays (TiO2-NTAs) as a photoanode for synergistic H2 evolution and water purification, respectively. Hydrogen evolution in the cathode chamber and environmental remediation in the anode chamber were achieved with the aid of appropriate bandgap illumination and self-built bias voltage. The mismatch of Fermi levels between TiO2-NTAs and Si-NWs reduced the recombination rates of photoinduced electrons and holes through the formation of Z scheme and inner electric filed. The synergistic PEC reactions exhibited much higher activities than those achieved using other systems so far. This basic principal could be applied for fabricating other PEC reactors in photoelectro conversion devices and be established as design guidelines for reactors to maximize the PEC performance.

Solid-Phase Microwave Reduction of WO3 by GO for Enhanced Synergistic Photo-Fenton Catalytic Degradation of Bisphenol A.

The synergistic photocatalytic Fenton reaction is a powerful advanced oxidation technique for the degradation of persistent organic pollutants. However, microwave-induced thermal effects on the formation of novel structures facilitating the photocatalytic degradation have been rarely reported. Herein, a two-step microwave thermal strategy was developed to synthesize a new hybrid catalyst comprising defective WO3-x nanowires coupled with reduced graphene oxides (rGOs). Conventionally, microwave methods could induce superhot spots on the GO surface, resulting in the site-specific crystallization and oriented growth of WO3. However, in the solid phase, localized microwave thermal effects could reduce the interfacial area between WO3 and rGO and enhance the bonding between them. As for the unique structure and surface properties, the synthesized catalyst enhanced the light absorption, promoted the interfacial charge separation, and increased the carrier density in the photocatalytic processes. In addition, surface formation of W4+ provided a new pathway for Fe3+/Fe2+ cycling which linked the photocatalytic reaction and the Fenton process. The optimized catalyst exhibited a remarkable performance in the degradation of bisphenol A with a ∼83% removal yield via a photo-Fenton route. These microwave-induced functionalities of materials for synergistic reactions could also give a new avenue to other photoelectrocatalytic fields and solar cells.

Anomalous Photoinduced Hole Transport in Type I Core/Mesoporous-Shell Nanocrystals for Efficient Photocatalytic H2 Evolution.

Controlling the carrier dynamics in a semiconductor nanoparticulate photocatalyst is the key to developing catalytic activity. Generally, type I band alignment is unsuitable for photocatalysts because the photoinduced carriers accumulate in the narrow bandgap semiconductor. To avoid the termination of reactions and/or photocorrosion of materials caused by carrier accumulation, it is common to employ type II band alignment for photoenergy conversion systems instead of type I. However, CdS/ZnS core/mesoporous-shell heterostructures show superior photocatalytic activity despite having type I band alignment that is generally unfavorable for photocatalytic reactions. Transient absorption spectroscopy and time-resolved microwave conductivity revealed efficient photoinduced hole transfer from the CdS phase to the ZnS phase. The defect-mediated hole transfer from the CdS to the ZnS phase resulted in long-lived charge separation (>2.4 ms) leading to high photocatalytic performance. This study provides insight into defect-mediated carrier transfer in nanoparticulate photocatalysts, which could be used as a guideline for the design of highly active and stable nanoparticulate photocatalysts.

Near infrared light induced plasmonic hot hole transfer at a nano-heterointerface.

Localized surface plasmon resonance (LSPR)-induced hot-carrier transfer is a key mechanism for achieving artificial photosynthesis using the whole solar spectrum, even including the infrared (IR) region. In contrast to the explosive development of photocatalysts based on the plasmon-induced hot electron transfer, the hole transfer system is still quite immature regardless of its importance, because the mechanism of plasmon-induced hole transfer has remained unclear. Herein, we elucidate LSPR-induced hot hole transfer in CdS/CuS heterostructured nanocrystals (HNCs) using time-resolved IR (TR-IR) spectroscopy. TR-IR spectroscopy enables the direct observation of carrier in a LSPR-excited CdS/CuS HNC. The spectroscopic results provide insight into the novel hole transfer mechanism, named plasmon-induced transit carrier transfer (PITCT), with high quantum yields (19%) and long-lived charge separations (9.2 µs). As an ultrafast charge recombination is a major drawback of all plasmonic energy conversion systems, we anticipate that PITCT will break the limit of conventional plasmon-induced energy conversion.

Durian-Shaped CdS@ZnSe Core@Mesoporous-Shell Nanoparticles for Enhanced and Sustainable Photocatalytic Hydrogen Evolution.

In artificial photosynthesis, the establishment of design guidelines for nanostructures to maximize the photocatalytic performance remains a great challenge. In contrast with the intense research into band-offset tuning for photocatalysts, the relationship between nanostructures and photoinduced carrier dynamics has still been insufficiently explored. We synthesized durian-shaped CdS@ZnSe core@mesporous-shell nanoparticles ( d-CdS/ZnSe NPs) and investigated the carrier dynamics in photocatalytic hydrogen evolution. The cocatalyst-free d-CdS/ZnSe NPs exhibited high photocatalytic activity for H2 evolution (14.8% apparent quantum yield at 420 nm) and excellent stability (maintaining 80% activity after 72 h) under visible-light irradiation (>422 nm). The transient absorption measurement and flash photolysis time-resolved microwave conductivity unveiled that the ultra-long-lived charge separation (>6.2 ms) and swift hole transfer to the surfaces of ZnSe shell (11 ns) contribute the high catalytic activity and stability. The present work provides a novel insight into designing nanoparticulate photocatalysts with optimized performance.

Pt-Enhanced Mesoporous Ti3+/TiO2 with Rapid Bulk to Surface Electron Transfer for Photocatalytic Hydrogen Evolution.

Pt-doped mesoporous Ti3+ self-doped TiO2 (Pt-Ti3+/TiO2) is in situ synthesized via an ionothermal route, by treating metallic Ti in an ionic liquid containing LiOAc, HOAc, and a H2PtCl6 aqueous solution under mild ionothermal conditions. Such Ti3+-enriched environment, as well as oxygen vacancies, is proven to be effective for allowing the in situ reduction of Pt4+ ions uniformly located in the framework of the TiO2 bulk. The photocatalytic H2 evolution of Pt-Ti3+/TiO2 is significantly higher than that of the photoreduced Pt loaded on the original TiO2 and commercial P25. Such greatly enhanced activity is due to the various valence states of Pt (Ptn+, n = 0, 2, or 3), forming Pt-O bonds embedded in the framework of TiO2 and ultrafine Pt metal nanoparticles on the surface of TiO2. Such Ptn+-O bonds could act as the bridges for facilitating the photogenerated electron transfer from the bulk to the surface of TiO2 with a higher electron carrier density (3.11 × 1020 cm-3), about 2.5 times that (1.25 × 1020 cm-3) of the photoreduced Pt-Ti3+/TiO2 sample. Thus, more photogenerated electrons could reach the Pt metal for reducing protons to H2.

Plasmonic silver quantum dots coupled with hierarchical TiO2 nanotube arrays photoelectrodes for efficient visible-light photoelectrocatalytic hydrogen evolution.

A plasmonic Ag/TiO2 photocatalytic composite was designed by selecting Ag quantum dots (Ag QDs) to act as a surface plasmon resonance (SPR) photosensitizer for driving the visible-light driven photoelectrocatalytic hydrogen evolution. Vertically oriented hierarchical TiO2 nanotube arrays (H-TiO2-NTAs) with macroporous structure were prepared through a two-step method based on electrochemical anodization. Subsequently, Ag QDs, with tunable size (1.3-21.0 nm), could be uniformly deposited on the H-TiO2 NTAs by current pulsing approach. The unique structure of the as-obtained photoelectrodes greatly improved the photoelectric conversion efficiency. The as-obtained Ag/H-TiO2-NTAs exhibited strong visible-light absorption capability, high photocurrent density, and enhanced photoelectrocatalytic (PEC) activity toward photoelectrocatalytic hydrogen evolution under visible-light irradiation (λ>420 nm). The enhancement in the photoelectric conversion efficiency and activity was ascribed to the synergistic effects of silver and the unique hierarchical structures of TiO2 nanotube arrays, strong SPR effect, and anti-shielding effect of ultrafine Ag QDs.

C60-decorated CdS/TiO2 mesoporous architectures with enhanced photostability and photocatalytic activity for H2 evolution.

Fullerene (C60) enhanced mesoporous CdS/TiO2 architectures were fabricated by an evaporation induced self-assembly route together with an ion-exchanged method. C60 clusters were incorporated into the pore wall of mesoporous CdS/TiO2 with the formation of C60 enhanced CdS/TiO2 hybrid architectures, for achieving the enhanced photostability and photocatalytic activity in H2 evolution under visible-light irradiation. Such greatly enhanced photocatalytic performance and photostability could be due to the strong combination and heterojunctions between C60 and CdS/TiO2. The as-formed C60 cluster protection layers in the CdS/TiO2 framework not only improve the light absorption capability, but also greatly accelerated the photogenerated electron transfer to C60 clusters for H2 evolution.

An efficient dye-sensitized BiOCl photocatalyst for air and water purification under visible light irradiation.

A photosensitized BiOCl catalyst was found to be effective for photocatalytic water purification and air remediation under visible light irradiation (λ > 420 nm). Prepared by a solvothermal method, the BiOCl crystals possessed a 3D hierarchical spherical structure with the highly active facets exposed. When sensitized by Rhodamine B (RhB), the photocatalyst system was more active than N-doped TiO2 for breaking down 4-chlorophenol (4-CP, 200 ppm) and nitric monoxide (NO, 500 ppb). The high activity could be attributed to the hierarchical structure (supplying feasible reaction tunnels for adsorption and transition of reactants or products) and the efficient exposure of the {001} facets. The former provides an enriched oxygen atom density that promotes adsorption of cationic dye RhB, and creates an oxygen vacancy state. The HO˙ and ˙O2(-) radicals produced from the injected electrons from the excited dye molecule (RhB*) into the conduction band of BiOCl were responsible for the excellent photocatalytic performance of the RhB-BiOCl system.

C60/Bi2TiO4F2 heterojunction photocatalysts with enhanced visible-light activity for environmental remediation.

Fullerene (C60)-enhanced Bi2TiO4F2 hierarchical microspheres were prepared by a facile solvothermal method. Compared to the pure Bi2TiO4F2 photocatalyst, the C60/Bi2TiO4F2 samples exhibit much stronger photocatalytic performance for degrading Rhodamine B (RhB) and Eosin Y (EY) under visible light irradiation. Such greatly enhanced photocatalytic activity may be ascribed to strong combination and heterojunctions between C60 and Bi2TiO4F2, favorable for charge separation and light adsorption. Loading C60 on Bi2TiO4F2 results in a new photocatalytic mechanism (based on photo-generated hvb(+) and ·O2(-) radicals) different from that of pure Bi2TiO4F2.