Improved Plasmonic Hot‑Electron Capture in Au Nanoparticle/Polymeric Carbon Nitride by Pt Single Atoms for Broad‑Spectrum Photocatalytic H_(2)Evolution

ABSTRACT Rationally designing broad-spectrum photocatalysts to harvest whole visible-light region photons and enhance solar energy conversion is a“holy grail”for researchers,but is still a challenging issue.Herein,based on the common polymeric carbon nitride(PCN),a hybrid co-catalysts system comprising plasmonic Au nanoparticles(NPs)and atomically dispersed Pt single atoms(PtSAs)with different functions was constructed to address this challenge.For the dual co-catalysts decorated PCN(PtSAs–Au_(2.5)/PCN),the PCN is photoexcited to generate electrons under UV and short-wavelength visible light,and the synergetic Au NPs and PtSAs not only accelerate charge separation and transfer though Schottky junctions and metal-support bond but also act as the co-catalysts for H_(2) evolution.Furthermore,the Au NPs absorb long-wavelength visible light owing to its localized surface plasmon resonance,and the adjacent PtSAs trap the plasmonic hot-electrons for H_(2) evolution via direct electron transfer effect.Consequently,the PtSAs–Au_(2.5)/PCN exhibits excellent broad-spectrum photocatalytic H_(2) evolution activity with the H_(2) evolution rate of 8.8 mmol g^(−1) h^(−1) at 420 nm and 264μmol g^(−1) h^(−1) at 550 nm,much higher than that of Au_(2.5)/PCN and PtSAs–PCN,respectively.This work provides a new strategy to design broad-spectrum photocatalysts for energy conversion reaction.

Construction of LSPR-enhanced 0D/2D CdS/MoO3‒x S-scheme heterojunctions for visible-light-driven photocatalytic H2 evolution

Plasmonic nonmetal semiconductors with localized surface plasmon resonance(LSPR)effects possess extended light-response ranges and can act as highly efficient H2 generation photocatalysts.Herein,an LSPR-enhanced 0D/2D CdS/MoO3‒x heterojunction has been synthesized by the growth of 0D CdS nanoparticles on 2D plasmonic MoO3‒x elliptical nanosheets via a simple coprecipitation method.Taking advantage of the LSPR effect of the MoO3‒x elliptical nanosheets,the light absorption of the CdS/MoO3‒x heterojunction was extended from 600 nm to the near-infrared region(1400 nm).Furthermore,the introduction of 2D plasmonic MoO3‒x elliptical nanosheets not only provided a platform for the growth of CdS nanoparticles,but also contributed to the construction of an LSPR-enhanced S-scheme structure due to the interface between the MoO3‒x and CdS,accelerating the separation of light-induced electrons and holes.Therefore,the CdS/MoO3‒x heterojunction exhibited higher photocatalytic H2 generation activity than pristine CdS under visible light irradiation,including under 420,450,550,and 650 nm monochromic light,as well as improved photo-corrosion performance.

Highly efficient visible-light photocatalytic H2 evolution over 2D–2D Cd S/Cu7S4 layered heterojunctions

Converting solar energy into clean and sustainable chemical fuels is a promising strategy for exploiting renewable energy.The application of photocatalytic water splitting technology in hydrogen production is important for sustainable energy development and environmental protection.In this study,for the first time,2D Cu7S4 co-catalysts were coupled on the surface of a CdS nanosheet photocatalyst by a one-step ultrasonic-assisted electrostatic self-assembly method at room temperature.The as-fabricated 2D^-2D CdS/Cu7S4 layered heterojunctions were demonstrated to be advanced composite photocatalysts that enhance the water splitting efficiency toward hydrogen production.The highest hydrogen evolution rate of the 2D^-2D CdS/2%Cu7S4 binary heterojunction photocatalyst was up to 27.8 mmol g^-1 h^-1 under visible light irradiation,with an apparent quantum efficiency of 14.7%at 420 nm,which was almost 10.69 times and 2.65 times higher than those of pure CdS nanosheets(2.6 mmol g^-1 h^-1)and CdS-2%CuS(10.5 mmol g^-1 h^-1),respectively.The establishment of the CdS/Cu7S4 binary-layered heterojunction could not only enhance the separation of photogenerated electron-hole(e--h+)pairs,improve the transfer of photo-excited electrons,and prolong the life-span of photo-generated electrons,but also enhance the light absorption and hydrogen-evolution kinetics.All these factors are important for the enhancement of the photocatalytic activity.Expectedly,the 2D^-2D interface coupling strategy based on CdS NSs can be extensively exploited to improve the hydrogen-evolution activity over various kinds of conventional semiconductor NSs.

Constructing low-cost Ni3C/twin-crystal Zn0.5Cd0.5S heterojunction/homojunction nanohybrids for efficient photocatalytic H2 evolution

The development of low-cost semiconductor photocatalysts for highly efficient and durable photocatalytic H2 evolution under visible light is very challenging.In this study,we combine low-cost metallic Ni3C cocatalysts with twin nanocrystal Zn0.5Cd0.5S(ZCS)solid solution homojunctions for an efficient visible-light-driven H2 production by a simple approach.As-synthesized Zn0.5Cd0.5S-1%Ni3C(ZCS-1)heterojunction/homojunction nanohybrid exhibited the highest photocatalytic H2-evolution rate of 783μmol h‒1 under visible light,which is 2.88 times higher than that of pristine twin nanocrystal ZCS solid solution.The apparent quantum efficiencies of ZCS and ZCS-1 are measured to be 6.13%and 19.25%at 420 nm,respectively.Specifically,the homojunctions between the zinc blende and wurtzite segments in twin nanocrystal ZCS solid solution can significantly improve the light absorption and separation of photogenerated electron-hole pairs.Furthermore,the heterojunction between ZCS and metallic Ni3C NP cocatalysts can efficiently trap excited electrons from ZCS solid solution and enhance the H2-evolution kinetics at the surface for improving catalytic activity.This study demonstrates a unique one-step strategy for constructing heterojunction/homojunction hybrid nanostructures for a more efficient photocatalytic H2 evolution compared to other noble metal photocatalytic systems.

Dual transfer channels of photo-carriers in 2D/2D/2D sandwich-like ZnIn2S4/g-C_(3)N_(4)/Ti_(3)C_(2) MXene S-scheme/Schottky heterojunction for boosting photocatalytic H2 evolution

Construction of multi-channels of photo-carrier migration in photocatalysts is favor to boost conversion efficiency of solar energy by promoting the charge separation and transfer.Herein,a ternary ZnIn_(2)S_(4)/g-C_(3)N_(4)/Ti_(3)C_(2) MXene hybrid composed of S-scheme junction integrated Schottky-junction was fabricated using a simple hydrothermal approach.All the components(g-C_(3)N_(4),ZnIn_(2)S_(4) and Ti_(3)C_(2) MXene)demonstrated two-dimensional(2D)nanosheets structure,leading to the formation of a 2D/2D/2D sandwich-like structure with intimate large interface for carrier migration.Furthermore,the photogenerated carriers on the g-C_(3)N_(4) possessed dual transfer channels,including one route in S-scheme transfer mode between the g-C_(3)N_(4) and ZnIn_(2)S_(4) and the other route in Schottky-junction between g-C_(3)N_(4) and Ti_(3)C_(2) MXene.Consequently,a highly efficient carrier separation and transport was realized in the ZnIn_(2)S_(4)/g-C_(3)N_(4)/Ti_(3)C_(2) MXene heterojunction.This ternary sample exhibited wide light response from 200 to 1400 nm and excellent photocatalytic H_(2) evolution of 2452.1μmol∙g^(–1)∙h^(–1),which was 200,3,1.5 and 1.6 times of g-C_(3)N_(4),ZnIn_(2)S_(4),ZnIn_(2)S_(4)/Ti_(3)C_(2) MXene and g-C_(3)N_(4)/ZnIn_(2)S_(4) binary composites.This work offers a paradigm for the rational construction of multi-electron pathways to regulate the charge separation and migration via the introduction of dual-junctions in catalytic system.

Immobilization of metal-organic molecular cage on g-C3N4 semiconductor for enhancement of photocatalytic H2 generation

A new compound based on immobilizing of Pd6(RuL3)8(BF4)28 (L=2-(pyridin-3-yl)-1H-imidazo [4,5-f][1,10]-phenanthroline) cage (MOC-16) on g-C3N4 was synthesized. Infrared spectrum and powder X-ray diffraction were used to characterize structure of hybrid MOC-16/g-C3N4, as well as UV-vis absorption spectrum and X-ray photoelectron spectroscopy were carried out to unveil photocatalytic mechanism. With the introduction of MOC-16, the absorption edge of MOC-16/g-C3N4 in UV-vis spectrum extended apparently to long-wavelength region compared with pristine g-C3N4. H2 evolution yielded with MOC-16/g-C3N4 in aqueous solution containing TEOA was much higher than that with RuL3/g-C3N4, Pd/RuL3/g-C3N4 and mixture of MOC-16 and g-C3N4, showing that the octahedral cage structure with high-efficient electron transfer and the interface interaction between MOC-16 and g-C3N4 were significant for improvement of H2 evolution.

Unique Cd1-xZnxS@WO3-x and Cd1-xZnxS@WO3-x/CoOx/NiOx Z-scheme photocatalysts for efficient visible-light-induced H2 evolution

Artificial Z-scheme photocatalytic systems have received considerable attention in recent years because they can achieve wide light-absorption, high charge-separation efficiency, and strong redox ability simultaneously. Nevertheless, it is still challenging to exploit low-cost and stable Zscheme photocatalysts with highly-efficient H2 evolution from solar water-splitting so far. Herein, we report a novel all-solidstate Z-scheme photocatalyst Cd1-xZnxS@WO3-x consisting of Cd1-xZnxS nanorods coated with oxygen-deficient WO3-x amorphous layers. The Cd1-xZnxS@WO3-x exhibits an outstanding H2 evolution reaction(HER) activity as compared with Pt-loaded Cd1-xZnxS and most WO3- and Cd S-based photocatalysts, due to the generation of stronger reducing electrons through the appropriate Zn-doping in Cd1-xZnxS and the enhanced charge transfer by introducing oxygen vacancies(W^5+/OVs) into the ultrathin WO3-x amorphous coatings. The optimal HER rate of Cd1-xZnxS@WO3- xis determined to be 21.68 mmol h^-1 g^-1, which is further raised up to 28.25 mmol h^-1 g^-1(about 12 times more than that of Pt/Cd1-xZnxS) when Cd1-xZnxS@WO3-x is hybridized by Co Ox and Ni Oxdual cocatalysts(Cd1-xZnxS@WO3-x/CoOx/NiOx)through in-situ photo-deposition. Moreover, the corresponding apparent quantum yield(AQY) at 420 nm is significantly increased from 34.6% for Cd1-xZnxS@WO3-x to 60.8% for Cd1-xZnxS@WO3-x/CoOx/NiOx. In addition, both Cd1-xZnxS@WO3-x and Cd1-xZnxS@WO3-x/CoOx/NiOx demonstrate good stability towards HER. The results displayed in this work will inspire the rational design and synthesis of high-performance nanostructures for photocatalytic applications.

Cobalt-containing covalent organic frameworks for visible light-driven hydrogen evolution

Covalent organic frameworks(COFs) have recently emerged as a new class of photocatalysts.However,integrated design is crucial to maximizing the performance of COF-incorporating photocatalytic systems.Herein,we compare two strategies of installing earth-abundant metal-based catalytic centers into the matrice of a 2 D COF named NUS-55.Compared to NUS-55(Co)prepared from the post-synthetic metalation of coordination sites within the COF,the molecular co-catalyst impregnated NUS-55/[Co(bpy)3]Cl2 achieves a seven-fold improvement in visible light-driven H2 evolution rate to 2,480 μmol g^-1h^-1,with an apparent quantum efficiency(AQE) of 1.55% at 450 nm.Our results show that the rational design of molecular anchoring sites in COFs for the introduction of catalytic metal sites can be a viable strategy for the development of highly efficient photocatalysts with enhanced stability and photocatalytic activities.

Accumulation of localized charge on the surface of polymeric carbon nitride boosts the photocatalytic activity

The random mobility of charge carriers is a main factor causing the low photocatalytic efficiency of gCN.Thus,the controllable migration of charge carriers is a rational strategy to suppress the charge recombination and facilitate charge separation.Herein,an ethylenediamine modified g-C_(3)N_(4)displays improved photocatalytic activity.The excellent charge separation efficiency is confirmed to be a key factor for the enhancement.The TEM observation after photo-depositing Pt nanoparticles and DFT calculations verify the accumulation of electrons on some areas of g-C_(3)N_(4)surface.The increased-NH_(2)groups significantly tune the electronic structure of g-C_(3)N_(4)after the modification.The generation of midgap states also affects the charge separation.Our reports provide a simple method to manage the migration of charge carriers and enable electrons directional transfer,which suppresses the recombination and improves the photocatalytic activity.