PtPd bimetallic alloy nanoparticle (NP)-modified graphitic carbon nitride (g-C3N4) nanosheet photocatalysts were synthesized via chemical deposition precipitation. Characterization of the photocatalytic H2 evolution o...PtPd bimetallic alloy nanoparticle (NP)-modified graphitic carbon nitride (g-C3N4) nanosheet photocatalysts were synthesized via chemical deposition precipitation. Characterization of the photocatalytic H2 evolution of the g-C3N4 nanosheets shows that it was significantly enhanced when PtPd alloy NPs were introduced as a co-catalyst. The 0.2 wt% PtPd/g-C3N4 composite photocatalyst gave a maximum H2 production rate of 1600.8 μmol g^–1 h^–1. Furthermore, when K2HPO4 was added to the reaction system, the H2 production rate increased to 2885.0 μmol g^–1 h^–1. The PtPd/g-C3N4 photocatalyst showed satisfactory photocatalytic stability and was able to maintain most of its photocatalytic activity after four experimental photocatalytic cycles. In addition, a possible mechanism for the enhanced photocatalytic activity was proposed and verified by various photoelectric techniques. These results demonstrate that the synergistic effect between PtPd and g-C3N4 helps to greatly improve the photocatalytic activity of the composite photocatalyst.展开更多
Zirconia-supported CuO （CuO/ZrO2） composite photocatalysts were successfully synthesized via citric acid-assisted sol-gel technique. For comparison, CuO/ZrO2 materials were also prepared by solid state reaction and ...Zirconia-supported CuO （CuO/ZrO2） composite photocatalysts were successfully synthesized via citric acid-assisted sol-gel technique. For comparison, CuO/ZrO2 materials were also prepared by solid state reaction and co-precipitation method. The as-prepared powders were characterized by X-ray diffractometry （XRD）, transmission electron microscopy （TEM）, and thermogravimetric-differential thermal analysis （TG-DTA）. The photocatalytic activity of CuO/ZrO2 catalyst was investigated based on the H2 evolution from oxalic acid solution under simulated sunlight irradiation. The effects of molar ratio of CuO to ZrO2, preparation method, phase change with the calcination temperature and the durability on the photocatalytic activity of the photocatalyst were investigated in detail. It is found that the optimal activity of photocatalytic H2 evolution （2.41 mmol.h i.g-~） can be obtained when CuO/ZrO2 composite photocatalyst is synthesized by sol-gel technique and the mole ratio of CuO to ZrO2 is 40%. The activity of copper oxide supported on monoclinic ZrO2 calcined at higher temperature is much higher than that on tetragonal ZrO2 calcined at lower temperature, and the best calcination temperature is 900 ℃.展开更多
NiS2 is a promising cocatalyst to improve the photocatalytic performance of g-C3N4 for the production of H2.However,the synthesis of the NiS2 cocatalyst usually requires harsh conditions,which risks destroying the mic...NiS2 is a promising cocatalyst to improve the photocatalytic performance of g-C3N4 for the production of H2.However,the synthesis of the NiS2 cocatalyst usually requires harsh conditions,which risks destroying the microstructures of the g-C3N4 photocatalysts.In this study,a facile and low-temperature（80 ℃） impregnation method was developed to prepare NiS2/g-C3N4 photocatalysts.First,the g-C3N4 powders were processed by the hydrothermal method in order to introduce oxygen-containing functional groups（such as-OH and-C0NH-） to the surface of g-C3N4.Then,the Ni^2＋ ions could be adsorbed near the g-C3N4 via strong electrostatic interaction between g-C3N4 and Ni^2＋ ions upon the addition of Ni（NO3）2 solution.Finally,NiS2 nanoparticles were formed on the surface of g-C3N4 upon the addition of TAA.It was found that the NiS2 nanoparticles were solidly and homogeneously grafted on the surface of g-C3N4,resulting in greatly improved photocatalytic H2production.When the amount of NiS2 was 3 wt%,the resultant NiS2/g-C3N4 photocatalyst showed the highest H2 evolution rate（116.343 μmol h^-1 g^-1）,which is significantly higher than that of the pure g-C3N4（3 μmol h^-1 g^-1）.Moreover,the results of a recycling test for the NiS2/g-C3N4（3 wt%）sample showed that this sample could maintain a stable and effective photocatalytic H2-evolution performance under visible-light irradiation.Based on the above results,a possible mechanism of the improved photocatalytic performance was proposed for the presented NiS2/g-C3N4 photocatalysts,in which the photogenerated electrons of g-C3N4 can be rapidly transferred to the NiS2 nanoparticles via the close and continuous contact between them;then,the photogenerated electrons rapidly react with H2O adsorbed on the surface of NiS2,which has a surficial metallic character and high catalytic activity,to produce H2.Considering the mild and facile synthesis method,the presented low-cost and highly efficient NiS2-modified g-C3N4 photocatalysts would have great potential for practical use in photocatalytic H2 production.展开更多
The development of efficient photocatalytic H2-evolution materials requires both rapid electron transfer and an effective interfacial catalysis reaction for H2 production. In addition to the well-known noble metals, l...The development of efficient photocatalytic H2-evolution materials requires both rapid electron transfer and an effective interfacial catalysis reaction for H2 production. In addition to the well-known noble metals, low-cost and earth-abundant non-noble metals can also act as electron- transfer mediators to modify photocatalysts. However, as almost all non-noble metals lack the interfacial catalytic active sites required for the H2-evolution reaction, the enhancement of the photocatalytic performance is limited. Therefore, the development of new interfacial active sites on metal-modified photocatalysts is of considerable importance. In this study, to enhance the photocatalytic evolution of H2 by Ni-modified TiO2, the formation of NiSx as interfacial active sites was promoted on the surface of Ni nanoparticles. Specifically, the co-modified TiO2/Ni-NiSx photocatalysts were prepared via a two-step process involving the photoinduced deposition of Ni on the TiO2 surface and the subsequent formation of NiSx on the Ni surface by a hydrothermal reaction method. It was found that the TiO2/Ni-NiSx photocatalysts exhibited enhanced photocatalytic H2-evolution activity. In particular, TiO2/Ni-NiSx(30%) showed the highest photocatalytic rate (223.74 μmol h.1), which was greater than those of TiO2, TiO2/Ni, and TiO2/NiSx by factors of 22.2, 8.0, and 2.2, respectively. The improved H2-evolution performance of TiO2/Ni-NiSx could be attributed to the excellent synergistic effect of Ni and NiSx, where Ni nanoparticles function as effective mediators to transfer electrons from the TiO2 surface and NiSx serves as interfacial active sites to capture H+ ions from solution and promote the interfacial H2-evolution reaction. The synergistic effect of the non-noble metal cocatalyst and the interfacial active sites may provide new insights for the design of highly efficient photocatalytic materials.展开更多
The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots(QDs)in photocatalysis.Herein,the construction of a novel S-scheme heterojunction between cubic-phase CdS...The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots(QDs)in photocatalysis.Herein,the construction of a novel S-scheme heterojunction between cubic-phase CdS QDs and hollow nanotube In_(2)O_(3)is successfully achieved using an electrostatic self-assembly method.Under visible light irradiation,all CdS-In_(2)O_(3)composites exhibit higher hydrogen evolution efficiency compared to pure CdS QDs.Notably,the photocatalytic H_(2)evolution rate of the optimal CdS-7%In_(2)O_(3)composite is determined to be 2258.59μmol g^(−1)h^(−1),approximately 12.3 times higher than that of pure CdS.The cyclic test indicates that the CdS-In_(2)O_(3)composite maintains considerable activity even after 5 cycles,indicating its excellent stability.In situ X-ray photoelectron spectroscopy and density functional theory calculations confirm that carrier migration in CdS-In_(2)O_(3)composites adheres to a typical S-scheme heterojunction mechanism.Additionally,a series of characterizations demonstrate that the formation of S-scheme heterojunctions between In_(2)O_(3)and CdS inhibits charge recombination and accelerates the separation and migration of photogenerated carriers in the CdS QDs,thus achieving enhanced photocatalytic performance.This work elucidates the pivotal role of S-scheme heterojunctions in photocatalytic H_(2)production and offers novel insights into the construction of effective composite photocatalysts.展开更多
Small-sized Cd_(x) Zn_(1-x) S solid solution nanomaterial is an important candidate for efficient photocatalytic hydrogen evolution(PHE),but it still suffers from easy agglomeration,severe photo corrosion,and fast pho...Small-sized Cd_(x) Zn_(1-x) S solid solution nanomaterial is an important candidate for efficient photocatalytic hydrogen evolution(PHE),but it still suffers from easy agglomeration,severe photo corrosion,and fast photogenerated electron-hole recombination.To tackle these issues,herein,we propose a new strategy to modify Cd_(x) Zn_(1-x) S nanoreactors by the simultaneous utilization of ionic-liquid-assisted morphology engineering and MXene-incorporating method.That is,we designed and synthesized a novel hierarchi-cal Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) Schottky junction composite through the in-situ deposition of ultrathin Cd_(0.8) Zn_(0.2) S nanosheets on unique IL-modified Ti_(3) C_(2) MXenes by a one-pot solvothermal method for efficiently PHE.The unique construction strategy tailors the thickness of ultrathin Cd_(0.8) Zn_(0.2) S nanosheets and prevents them from stacking and agglomeration,and especially,optimizes their charge transfer pathways during the photocatalytic process.Compared with pristine Cd_(0.8) Zn_(0.2) S nanosheets,Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) has abun-dant photogenerated electrons available on the Ti_(3) C_(2) surface for proton reduction reaction,owing to the absence of deep-trapped electrons,suppression of electron-hole recombination in Cd_(0.8) Zn_(0.2) S and high-efficiency charge separation at the Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) Schottky junction interface.Moreover,the hy-drophilicity,electrical conductivity,visible-light absorption capacity,and surficial hydrogen desorption of Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) heterostructure are significantly improved.As a result,the heterostructure exhibits out-standing photocatalytic stability and super high apparent quantum efficiency,being rendered as one of the best noble-metal-free Cd-Zn-S-based photocatalysts.This work illustrates the mechanisms of mor-phology control and heterojunction construction in controlling the catalytic behavior of photocatalysts and highlights the great potential of the IL-assisted route in the synthesis of high-performance MXene-based heterostructures for photocatalytic hydrogen evolution.展开更多
I.r.bands at 1559.0, 1441 .0, 1378 .9, 13603, 1031. 1,981 .4 and 947.3 cm -1 due tovarious types of dissociative adsorption of H2 over ZrO2 with changing temperatore wereobserved by in situ FT-IR spectroscopy.
Doping engineering is an effective strategy for graphitic carbon nitride(g-C_(3)N_(4))to improve its photocat-alytic hydrogen evolution reaction(HER)performance.In this work,a novel nitrogen and sulfur co-doped g-C_(3...Doping engineering is an effective strategy for graphitic carbon nitride(g-C_(3)N_(4))to improve its photocat-alytic hydrogen evolution reaction(HER)performance.In this work,a novel nitrogen and sulfur co-doped g-C_(3)N_(4)(N,S-g-C_(3)N_(4))is elaborately designed on the basis of theoretical predictions of first-principle density functional theory(DFT).The calculated Gibbs free energy of adsorbed hydrogen(ΔGH∗)for N,S-g-C_(3)N_(4) at the N-doping active sites is extremely close to zero(0.01 eV).Inspired by the theoretical predictions,the N,S-g-C_(3)N_(4) is successfully fabricated through ammonia-rich pyrolysis synthesis strategy,in which ammonia is in-situ obtained by pyrolyzing melamine.Subsequent characterizations indicate that the N,S-g-C_(3)N_(4) possesses high specific surface area,outstanding light utilization,good hydrophilicity,and efficient carrier transfer efficiency.Consequently,the N,S-g-C_(3)N_(4) displays an extremely high H2 evolution rate of 8269.9μmol g−1 h−1,achieves an apparent quantum efficiency(AQE)of 3.24%,and also possesses outsatnding durability.Theoretical calculations further demonstrate that N and S dopants can not only introduce doping energy level to reduce the band gap,but also induce charge redistribution to facilitate hydrogen adsorption,thus promoting the photocatalytic HER process.Moreover,femtosecond transient absorption(fs-TA)spectroscopy further corroborates the efficient photogenerated carrier transport of N,S-g-C_(3)N_(4).This research highlights a promising and reliable strategy to achieve superior photocatalytic activity,and exhibits significant guidance for precise designing high-efficiency photocatalysts.展开更多
Subject Code:B01 Photocatalytic hydrogen evolution by water-splitting has been recognized as one of the most promising solutions to the global energy and environment crisis,owing to its renewable solar energy source a...Subject Code:B01 Photocatalytic hydrogen evolution by water-splitting has been recognized as one of the most promising solutions to the global energy and environment crisis,owing to its renewable solar energy source and clean chemical fuel product.Cadmium sulfide(CdS)and TiO2(or related polyoxo-titanium clusters)are two展开更多
Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics,superstable and efficient cocatalysts have rarely bee...Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics,superstable and efficient cocatalysts have rarely been produced through the modulation of their structure and composition.In this study,a series of bimetallic nickel-iron phosphide(Ni_(x)Fe_(2-x)P,where 0<x<2)cocatalysts with controllable structures and overpotentials were designed by adjusting the atomic ratio of Ni/Fe onto nonmetallic elemental red phosphorus(RP)for the photocatalytic selective oxidation of benzyl alcohol(BA)coupled with hydrogen production.The catalysts exhibited an outstanding photocatalytic activity for benzaldehyde and a high H_(2)yield.The RP regulated by bimetallic phosphide cocatalysts(Ni_(x)Fe_(2-x)P)demonstrated higher photocatalytic oxidation-reduction activity than that regulated by monometallic phosphide cocatalysts(Ni_(2)P and Fe2P).In particular,the RP regulated by Ni_(1.25)Fe_(0.75)P exhibited the best photocatalytic performance.In addition,experimental and theoretical calculations further illustrated that Ni_(1.25)Fe_(0.75)P,with the optimized electronic structure,possessed good electrical conductivity and provided strong adsorption and abundant active sites,thereby accelerating electron migration and lowering the reaction energy barrier of RP.This finding offers valuable insights into the rational design of highly effective cocatalysts aimed at optimizing the photocatalytic activity of composite photocatalysts.展开更多
The development of highly active, durable, and low-cost electrocatalysts is crucial for electrocatalytic hydrogen production. Ultrathin two-dimensional (2D) nanomaterials have extremely large specific surface areas, m...The development of highly active, durable, and low-cost electrocatalysts is crucial for electrocatalytic hydrogen production. Ultrathin two-dimensional (2D) nanomaterials have extremely large specific surface areas, making them highly desirable electrocatalyst morphologies. Medium-entropy alloys (MEAs) exhibit compositional tunability and entropy-driven structural stability, making them ideal electrocatalyst candidates. In this study, MoCoNi MEA with ultrathin 2D morphology was successfully developed using a facile ionic lay-er epitaxial method. The ultrathin 2D MoCoNi MEA showed an excellent oxygen evolution reaction (OER) electrocatalytic performance, with a low overpotential of 167 mV at a current density of 10 mA/cm^(2) and small Tafel slope of 33.2 mV/dec. At the overpotential of 167 mV, the ultrathin 2D MoCoNi MEA exhibited ultrahigh mass activity of 3359.6 A/g, which is three orders of magnitude higher than that of the commercial noble metal oxide RuO_(2) (1.15 A/g). This excellent electrocatalytic performance was attributed to the synergy of multiple active metal-induced medium entropies, as well as the ultrathin thickness, which considerably shortened the charge-transfer dis-tance and thus significantly promoted charge transfer. Owing to the natural entropy-stabilizing effect, the ultrathin 2D MoCoNi MEA maintained 90% of the initial current after a continuous OER electrocatalytic test for 134 h, showing impressive electrocatalytic stability. This study opens new avenues for the development of high-performance and low-cost electrocatalyst materials by creating MEAs with ultrathin 2D morphology.展开更多
As one of the most important industrially viable methods for carbon dioxide(CO_(2))utilization,methanol synthesis serves as a platform for production of green fuels and commodity chemicals.For sustainable methanol syn...As one of the most important industrially viable methods for carbon dioxide(CO_(2))utilization,methanol synthesis serves as a platform for production of green fuels and commodity chemicals.For sustainable methanol synthesis,In_(2)O_(3)is an ideal catalyst and has garnered significant attention.Herein,cubic In_(2)O_(3)nanoparticles were prepared via the precipitation method and evaluated for CO_(2)hydrogenation to produce methanol.During the initial 10 h of reaction,CO_(2)conversion gradually increased,accompanied by a slow decrease of methanol selectivity,and the reaction reached equilibrium after 10-20 h on stream.This activation and induction stage may be attributed to the sintering of In_(2)O_(3)nanoparticles and the creation of more oxygen vacancies on In_(2)O_(3)surfaces.Further experimental studies demonstrate that hydrogen induction created additional oxygen vacancies during the catalyst activation stage,enhancing the performance of In_(2)O_(3)catalyst for CO_(2)hydrogenation.Density functional theory calculations and microkinetic simulations further demonstrated that surfaces with higher oxygen vacancy coverages or hydroxylated surfaces formed during this induction period can enhance the reaction rate and increase the CO_(2)conversion.However,they predominantly promote the formation of CO instead of methanol,leading to reduced methanol selectivity.These predictions align well with the above-mentioned experimental observations.Our work thus provides an in-depth analysis of the induction stage of the CO_(2)hydrogenation process on In_(2)O_(3)nano-catalyst,and offers valuable insights for significantly improving the CO_(2)reactivity of In_(2)O_(3)-based catalysts while maintaining long-term stability.展开更多
Solar-driven hydrogen(H_(2))evolution and contaminant degradation offer a promising pathway to address the global energy and environmental crisis.However,the inadequate separation of carriers and light absorption rema...Solar-driven hydrogen(H_(2))evolution and contaminant degradation offer a promising pathway to address the global energy and environmental crisis.However,the inadequate separation of carriers and light absorption remain significant challenges in the advancement of photocatalysis.In this work,a general in situ ion exchange strategy has been employed to integrate palladium single atoms(Pd SAs)into hollow cadmium sulfide(CdS-H)spheres,creating a multifunctional photocatalyst for both photocatalytic H_(2)evolution and organic degradation.The hollow structure enhances light refraction,and Pd SAs act as charge transfer channels,leading to a significant enhancement in the spatial separation efficiency of photocatalytic charge carries pairs and light utilization in the synthesized Pd SAs/CdS-H.Consequently,the optimized 0.3Pd SAs/CdS-H demonstrates an exceptional photocatalytic H_(2) evolution efficiency of 22.23 mmol h^(-1)g^(-1)and an organic pollutant removal rate of 99.2%.Experimental analyses and density functional theory calculations reveal that the Pd SAs lower the work function of CdS-H and enhance the interfacial charge transport,which is crucial for improving photocatalytic performance.Moreover,both superoxide radicals and holes contribute to the removal of organic dyes,as directly confirmed by in situ radical capture experiments.Based on these characterization results,the photocatalytic mechanism for photocatalytic H_(2) evolution and pollutant degradation is proposed,respectively.This work establishes a dual-functional photocatalyst design strategy for sustainable energy generation and environmental remediation.展开更多
The intrinsic symmetrical electron distribution in crystalline metal sulfides usually causes an improper electronic configuration between catalytic S atoms and H intermediates(H_(ad))to form strong S-H_(ad) bonds,resu...The intrinsic symmetrical electron distribution in crystalline metal sulfides usually causes an improper electronic configuration between catalytic S atoms and H intermediates(H_(ad))to form strong S-H_(ad) bonds,resulting in a low photocatalytic H_(2) evolution activity.Herein,a cobalt-induced asymmetric electronic distribution is justified as an effective strategy to optimize the electronic configuration of catalytic S sites in NiCoS cocatalysts for highly active photocatalytic H_(2) evolution.To this end,Co atoms are uniformly incorporated in NiS nanoparticles to fabricate homogeneous NiCoS cocatalyst on TiO_(2) surface by a facile photosynthesis strategy.It is revealed that the incorporated Co atoms break the electron distribution symmetry in NiS,thus essentially increasing the electron density of S atoms to form active electron-enriched S^(2+δ)–sites.The electron-enriched S^(2+δ)–sites could interact with Had via an increased antibonding orbital occupancy,which weakens S–Had bonds for efficient H_(ad) adsorption and desorption,endowing the NiCoS cocatalysts with a highly active H_(2) evolution process.Consequently,the optimized NiCoS/TiO_(2)(1:2)photocatalyst displays the highest H_(2) production performance,outperforming the NiS/TiO_(2) and CoS/TiO_(2) samples by factors of 2.1 and 2.5,respectively.This work provides novel insights on breaking electron distribution symmetry to optimize catalytic efficiency of active sites.展开更多
Constructing heterojunctions have received significant attention in photocatalysis because of their effi-cient separation of photogenerated carriers and improving light utilization efficiency.Bimetallic sulfides(e.g.N...Constructing heterojunctions have received significant attention in photocatalysis because of their effi-cient separation of photogenerated carriers and improving light utilization efficiency.Bimetallic sulfides(e.g.NiCo_(2)S_(4))are applied in electrocatalysis and supercapacitors that can be coupled with TiO_(2)to form a heterojunction.Owing to the staggered energy band arrangement between TiO_(2)and NiCo_(2)S_(4),the es-tablishing of a Z-scheme heterojunction between them is expected to enhance the carrier separation effi-ciency and reduce the sulfide photo-corrosion.However,the application of NiCo_(2)S_(4)in photocatalysis and studies on the mechanism of the TiO_(2)/NiCo_(2)S_(4)Z-scheme heterojunction have seldom been reported.In this work,we obtained a hollow core-shell TiO_(2)/NiCo_(2)S_(4)Z-scheme photocatalyst through a solvothermal method for photocatalytic hydrogen evolution(PHE).The PHE rate of the optimized TiO_(2)/NiCo_(2)S_(4)-0.3 is 8.55 mmol g^(−1)h^(−1),approximately 34 times higher than pure TiO_(2),94 times higher than pure NiCo_(2)S_(4).The remarkable photocatalytic activity can be ascribed to the hollow structure and the in-situ constructed Z-scheme heterojunction.The photogenerated charge transfer mechanism is revealed by hydroxyl radical trapping experiments and electron paramagnetic resonance(EPR)characterization.The in-situ construc-tion of the Z-scheme heterojunction not only enhances the efficiency of separating the photogenerated carriers but also reduces the photo-corrosion of NiCo_(2)S_(4).This study proposes an effective strategy for the design of TiO_(2)-based Z-scheme heterojunctions and the application of NiCo_(2)S_(4)in photocatalysis.展开更多
The synergistic effects of piezoelectric catalysis and plasmonic photocatalysis hold significant promise for achieving high-efficiency solar energy conversion.Herein,SnFe_(2)O_(4)@ZnIn_(2)S_(4)(SFO@ZIS)composites were...The synergistic effects of piezoelectric catalysis and plasmonic photocatalysis hold significant promise for achieving high-efficiency solar energy conversion.Herein,SnFe_(2)O_(4)@ZnIn_(2)S_(4)(SFO@ZIS)composites were prepared by a facile low-temperature water bath method,and an efficient and stable near-infrared(NIR)photothermal-assisted piezoelectric photocatalytic system was successfully constructed.The system achieved a synergistic effect of ultrasonic vibration and NIR illumination,driving a photocatalytic hydrogen(H_(2))production rate of 17.9μmol g^(-1)h^(-1).Related photothermal test results demonstrate that the localized surface plasmon(LSPR)resonance effect of SFO not only significantly broadens the NIR light absorption of ZIS,but also improves the reaction temperature and reduces the activation energy of the reaction by efficiently converting the light energy into heat energy.In addition,photoelectrochemical analyses revealed that the SFO with excellent piezoelectric activity effectively facilitated carrier separation by transferring the energetic hot electrons generated by the LSPR effect to the conduction band of ZIS under external mechanical pressure.This study presents an effective design strategy and theoretical basis for constructing an efficient and robust NIR-driven photothermally assisted piezoelectric photo-catalytic system.展开更多
High performance composite photocatalyst is a hotspot in the photocatalysis researches.In this study,a cutting-edge CeO_(2)/rutile composite photocatalyst with tiny CeO_(2)concentration of 1.28 wt%was synthesized via ...High performance composite photocatalyst is a hotspot in the photocatalysis researches.In this study,a cutting-edge CeO_(2)/rutile composite photocatalyst with tiny CeO_(2)concentration of 1.28 wt%was synthesized via a simple photocatalytic method.This as-obtained CeO_(2)/rutile catalyst(CeO_(2)/TiO_(2)-1:1)exhibited an enhanced wastewater degradation and improved water splitting H_(2)evolution ability,with 95.83%removal ratio for methylene blue(MB),72.84%for tetracycline(TC)and 87.57μmol/g H_(2)evolution capacity.Light irradiation and 2-coordinated oxygen vacancies(OV_(2C))on rutile surface promoted the Ce^(3+)adsorption on the rutile(110)facet as DFT results shown.The CeO_(2)/rutile type-Ⅱ heterojunction was evidenced to promote the migration of e^(−)/h^(+)and generation of·OH/·O_(2)^(−)and H_(2),which rapidly boosted the whole photocatalytic performance.This as-prepared CeO_(2)/TiO_(2)photocatalyst can provide useful inspirations and new thoughts about the photosynthesis process,and offer a novel strategy for heterojunction photocatalysts preparation.展开更多
Effective separation of bulk phase and surface charges is crucial for maximizing charge utilization in the process of photocatalytic energy conversion.In this study,SnS_(2) nanoflowers and twinned Mn_(0.5) Cd_(0.5) S ...Effective separation of bulk phase and surface charges is crucial for maximizing charge utilization in the process of photocatalytic energy conversion.In this study,SnS_(2) nanoflowers and twinned Mn_(0.5) Cd_(0.5) S solid solution(T-MCS)nanoparticles were fabricated by a one-step solvothermal method respectively,fol-lowed by the formation of SnS_(2)/T-MCS nanohybrids through a facile physical solvent evaporation process for high-efficiency photocatalytic hydrogen(H_(2))production.The T-MCS crystal structure consists of alter-nating wurtzite Mn_(0.5) Cd_(0.5) S(WZ-MCS)and zinc blende Mn_(0.5) Cd_(0.5) S(ZB-MCS),forming a twin structure within the semiconductor.The charge migration mechanism between WZ-MCS and ZB-MCS follows the S-scheme pathway owing to slight differences in energy levels within their respective crystal structures,resulting in exceptional bulk phase charge separation capacity of T-MCS.Additionally,SnS_(2) enhances the electrochemical performance of the catalysts by providing more active sites,reducing charge transfer re-sistance and H_(2) production overpotential,thereby facilitating faster reaction kinetics.The photoelectro-chemical tests,radical trapping experiments,density functional theory(DFT),and electron paramagnetic resonance spectroscopy(EPR)confirm that the charge transfer path between SnS_(2) and T-MCS follows an S-type route that accelerates interfacial photo-induced electrons and holes separation while preserving useful charges.The synergistic impact of twinned homojunction and S-type heterojunction in 10 wt.%SnS_(2)/T-MCS composite contributes to a remarkable H_(2) production rate of 182.82 mmol h^(-1) g^(-1),which is 761.8 times higher than that achieved with SnS_(2) alone(0.24 mmol h^(-1) g^(-1)),as well as 5.8 times higher than that achieved with T-MCS alone(31.54 mmol h^(-1) g^(-1)).This study offers novel insights into design-ing highly efficient sulfide photocatalysts specifically targeting solar-driven H_(2) evolution through a dual S-scheme transfer pathway.展开更多
Heterojunctions constructed by traditional methods often result in random stacking of materials, leading to lattice mismatch, which adversely affects the extraction and transfer of photo-generated carriers and, in tur...Heterojunctions constructed by traditional methods often result in random stacking of materials, leading to lattice mismatch, which adversely affects the extraction and transfer of photo-generated carriers and, in turn, hampers light utilization efficiency. In this work, we report a novel heterojunction comprising alternating S-doped g-C_(3)N_(4) (SCN) and N-doped MoS_(2) (NMS), bridged by Mo–N covalent bonds within hierarchical periodic macroporous (HPM) walls. This heterojunction is synthesized by co-pyrolyzing dicyandiamide, thiourea, and ammonium molybdate. Transient reflectance photoluminescence measurements reveal that the Mo–N covalent bonds serve as “fast tracks” for electron transfer from SCN to NMS, significantly enhancing the charge separation efficiency. Additionally, the well-defined spatial separation of photo-induced carriers, coupled with the efficient mass transfer within the HPM structure, promotes superior carrier utilization. Thanks to the synergistic effect of HPM structures and the bridged Mo–N bonds, the optimized HPM NMS/SCN-1.3 sample exhibits a remarkable H_(2) evolution rate of 473.3 µmol g^(−1) h^(−1) under visible light irradiation, which is approximately 163 and 19 times higher than bulk g-C_(3)N_(4) (BCN) and HPM SCN, respectively. This work offers valuable insights into the design of HPM heterojunctions composed of co-catalysts and host catalysts, paving the way for enhanced photocatalytic H₂ evolution.展开更多
Hydrogen peroxide(H_(2)O_(2)),an environmentally friendly chemical with high value,is extensively used in industrial production and daily life.However,the traditional anthraquinone method for H_(2)O_(2) production is ...Hydrogen peroxide(H_(2)O_(2)),an environmentally friendly chemical with high value,is extensively used in industrial production and daily life.However,the traditional anthraquinone method for H_(2)O_(2) production is associated with a highly energy-consuming and heavily polluting process.Solor-driven photocatalytic evolution of H_(2)O_(2) is a promising,eco-friendly,and energy-efficient strategy that holds great potential to substitute the traditional approach.Here,a ternary photocatalyst,NiS/CdS/Halloysite nanotubes(NiS/CdS/HNTs)is designed and prepared with an earth-abundant clay mineral HNTs as the support and NiS as a co-catalyst.The pivotal roles of HNTs and NiS in the photocatalytic process are elucidated by experiments and theoretical calculations.HNTs serve as the carrier,which allows CdS to be uniformly dispersed onto its surface as small particles,increasing effective contact with H_(2)O and O_(2) for H_(2)O_(2) formation.Simultaneously,it resulted in the formation of a Schottky junction between NiS and CdS,which not only favors photogenerated charges separating efficiently but also provides a unidirectional path to transfer electrons.Consequently,the optimized NiS/CdS/HNTs composite demonstrates an H_(2)O_(2) evolution rate of 380.5μmol·g^(-1)·h^(-1) without adding any sacrificial agent or extra O_(2),nearly 5.0 times that of pure CdS.This work suggests a feasible idea for designing and developing highly active and low-cost solar energy catalytic composite materials.展开更多
基金supported by the National Natural Science Foundation of China(51572295,21273285,21003157)the Beijing Nova Program(2008B76)the Science Foundation of China University of Petroleum Beijing(KYJJ2012-06-20 and 2462016YXBS05)~~
文摘PtPd bimetallic alloy nanoparticle (NP)-modified graphitic carbon nitride (g-C3N4) nanosheet photocatalysts were synthesized via chemical deposition precipitation. Characterization of the photocatalytic H2 evolution of the g-C3N4 nanosheets shows that it was significantly enhanced when PtPd alloy NPs were introduced as a co-catalyst. The 0.2 wt% PtPd/g-C3N4 composite photocatalyst gave a maximum H2 production rate of 1600.8 μmol g^–1 h^–1. Furthermore, when K2HPO4 was added to the reaction system, the H2 production rate increased to 2885.0 μmol g^–1 h^–1. The PtPd/g-C3N4 photocatalyst showed satisfactory photocatalytic stability and was able to maintain most of its photocatalytic activity after four experimental photocatalytic cycles. In addition, a possible mechanism for the enhanced photocatalytic activity was proposed and verified by various photoelectric techniques. These results demonstrate that the synergistic effect between PtPd and g-C3N4 helps to greatly improve the photocatalytic activity of the composite photocatalyst.
基金Project(20876039) supported by the National Natural Science Foundation of ChinaProject(09JJ3023) supported by the Natural Science Foundation of Hunan Province,China
文摘Zirconia-supported CuO （CuO/ZrO2） composite photocatalysts were successfully synthesized via citric acid-assisted sol-gel technique. For comparison, CuO/ZrO2 materials were also prepared by solid state reaction and co-precipitation method. The as-prepared powders were characterized by X-ray diffractometry （XRD）, transmission electron microscopy （TEM）, and thermogravimetric-differential thermal analysis （TG-DTA）. The photocatalytic activity of CuO/ZrO2 catalyst was investigated based on the H2 evolution from oxalic acid solution under simulated sunlight irradiation. The effects of molar ratio of CuO to ZrO2, preparation method, phase change with the calcination temperature and the durability on the photocatalytic activity of the photocatalyst were investigated in detail. It is found that the optimal activity of photocatalytic H2 evolution （2.41 mmol.h i.g-~） can be obtained when CuO/ZrO2 composite photocatalyst is synthesized by sol-gel technique and the mole ratio of CuO to ZrO2 is 40%. The activity of copper oxide supported on monoclinic ZrO2 calcined at higher temperature is much higher than that on tetragonal ZrO2 calcined at lower temperature, and the best calcination temperature is 900 ℃.
基金supported by the National Natural Science Foundation of China (21277107, 21477094, 51672203, 51472192)the Program for New Century Excellent Talents in University (NCET-13-0944)the Fundamental Research Funds for the Central Universities (WUT 2015IB002)~~
文摘NiS2 is a promising cocatalyst to improve the photocatalytic performance of g-C3N4 for the production of H2.However,the synthesis of the NiS2 cocatalyst usually requires harsh conditions,which risks destroying the microstructures of the g-C3N4 photocatalysts.In this study,a facile and low-temperature（80 ℃） impregnation method was developed to prepare NiS2/g-C3N4 photocatalysts.First,the g-C3N4 powders were processed by the hydrothermal method in order to introduce oxygen-containing functional groups（such as-OH and-C0NH-） to the surface of g-C3N4.Then,the Ni^2＋ ions could be adsorbed near the g-C3N4 via strong electrostatic interaction between g-C3N4 and Ni^2＋ ions upon the addition of Ni（NO3）2 solution.Finally,NiS2 nanoparticles were formed on the surface of g-C3N4 upon the addition of TAA.It was found that the NiS2 nanoparticles were solidly and homogeneously grafted on the surface of g-C3N4,resulting in greatly improved photocatalytic H2production.When the amount of NiS2 was 3 wt%,the resultant NiS2/g-C3N4 photocatalyst showed the highest H2 evolution rate（116.343 μmol h^-1 g^-1）,which is significantly higher than that of the pure g-C3N4（3 μmol h^-1 g^-1）.Moreover,the results of a recycling test for the NiS2/g-C3N4（3 wt%）sample showed that this sample could maintain a stable and effective photocatalytic H2-evolution performance under visible-light irradiation.Based on the above results,a possible mechanism of the improved photocatalytic performance was proposed for the presented NiS2/g-C3N4 photocatalysts,in which the photogenerated electrons of g-C3N4 can be rapidly transferred to the NiS2 nanoparticles via the close and continuous contact between them;then,the photogenerated electrons rapidly react with H2O adsorbed on the surface of NiS2,which has a surficial metallic character and high catalytic activity,to produce H2.Considering the mild and facile synthesis method,the presented low-cost and highly efficient NiS2-modified g-C3N4 photocatalysts would have great potential for practical use in photocatalytic H2 production.
基金supported by the National Natural Science Foundation of China(21477094)the Fundamental Research Funds for the Central Universities(WUT 2017IB002)~~
文摘The development of efficient photocatalytic H2-evolution materials requires both rapid electron transfer and an effective interfacial catalysis reaction for H2 production. In addition to the well-known noble metals, low-cost and earth-abundant non-noble metals can also act as electron- transfer mediators to modify photocatalysts. However, as almost all non-noble metals lack the interfacial catalytic active sites required for the H2-evolution reaction, the enhancement of the photocatalytic performance is limited. Therefore, the development of new interfacial active sites on metal-modified photocatalysts is of considerable importance. In this study, to enhance the photocatalytic evolution of H2 by Ni-modified TiO2, the formation of NiSx as interfacial active sites was promoted on the surface of Ni nanoparticles. Specifically, the co-modified TiO2/Ni-NiSx photocatalysts were prepared via a two-step process involving the photoinduced deposition of Ni on the TiO2 surface and the subsequent formation of NiSx on the Ni surface by a hydrothermal reaction method. It was found that the TiO2/Ni-NiSx photocatalysts exhibited enhanced photocatalytic H2-evolution activity. In particular, TiO2/Ni-NiSx(30%) showed the highest photocatalytic rate (223.74 μmol h.1), which was greater than those of TiO2, TiO2/Ni, and TiO2/NiSx by factors of 22.2, 8.0, and 2.2, respectively. The improved H2-evolution performance of TiO2/Ni-NiSx could be attributed to the excellent synergistic effect of Ni and NiSx, where Ni nanoparticles function as effective mediators to transfer electrons from the TiO2 surface and NiSx serves as interfacial active sites to capture H+ ions from solution and promote the interfacial H2-evolution reaction. The synergistic effect of the non-noble metal cocatalyst and the interfacial active sites may provide new insights for the design of highly efficient photocatalytic materials.
文摘The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots(QDs)in photocatalysis.Herein,the construction of a novel S-scheme heterojunction between cubic-phase CdS QDs and hollow nanotube In_(2)O_(3)is successfully achieved using an electrostatic self-assembly method.Under visible light irradiation,all CdS-In_(2)O_(3)composites exhibit higher hydrogen evolution efficiency compared to pure CdS QDs.Notably,the photocatalytic H_(2)evolution rate of the optimal CdS-7%In_(2)O_(3)composite is determined to be 2258.59μmol g^(−1)h^(−1),approximately 12.3 times higher than that of pure CdS.The cyclic test indicates that the CdS-In_(2)O_(3)composite maintains considerable activity even after 5 cycles,indicating its excellent stability.In situ X-ray photoelectron spectroscopy and density functional theory calculations confirm that carrier migration in CdS-In_(2)O_(3)composites adheres to a typical S-scheme heterojunction mechanism.Additionally,a series of characterizations demonstrate that the formation of S-scheme heterojunctions between In_(2)O_(3)and CdS inhibits charge recombination and accelerates the separation and migration of photogenerated carriers in the CdS QDs,thus achieving enhanced photocatalytic performance.This work elucidates the pivotal role of S-scheme heterojunctions in photocatalytic H_(2)production and offers novel insights into the construction of effective composite photocatalysts.
基金financial supports pro-vided by the National Natural Science Foundation of China(No.21905279)the Natural Science Foundation of Fujian Province(No.2020J05086).
文摘Small-sized Cd_(x) Zn_(1-x) S solid solution nanomaterial is an important candidate for efficient photocatalytic hydrogen evolution(PHE),but it still suffers from easy agglomeration,severe photo corrosion,and fast photogenerated electron-hole recombination.To tackle these issues,herein,we propose a new strategy to modify Cd_(x) Zn_(1-x) S nanoreactors by the simultaneous utilization of ionic-liquid-assisted morphology engineering and MXene-incorporating method.That is,we designed and synthesized a novel hierarchi-cal Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) Schottky junction composite through the in-situ deposition of ultrathin Cd_(0.8) Zn_(0.2) S nanosheets on unique IL-modified Ti_(3) C_(2) MXenes by a one-pot solvothermal method for efficiently PHE.The unique construction strategy tailors the thickness of ultrathin Cd_(0.8) Zn_(0.2) S nanosheets and prevents them from stacking and agglomeration,and especially,optimizes their charge transfer pathways during the photocatalytic process.Compared with pristine Cd_(0.8) Zn_(0.2) S nanosheets,Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) has abun-dant photogenerated electrons available on the Ti_(3) C_(2) surface for proton reduction reaction,owing to the absence of deep-trapped electrons,suppression of electron-hole recombination in Cd_(0.8) Zn_(0.2) S and high-efficiency charge separation at the Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) Schottky junction interface.Moreover,the hy-drophilicity,electrical conductivity,visible-light absorption capacity,and surficial hydrogen desorption of Cd_(0.8) Zn_(0.2) S/Ti_(3) C_(2) heterostructure are significantly improved.As a result,the heterostructure exhibits out-standing photocatalytic stability and super high apparent quantum efficiency,being rendered as one of the best noble-metal-free Cd-Zn-S-based photocatalysts.This work illustrates the mechanisms of mor-phology control and heterojunction construction in controlling the catalytic behavior of photocatalysts and highlights the great potential of the IL-assisted route in the synthesis of high-performance MXene-based heterostructures for photocatalytic hydrogen evolution.
文摘I.r.bands at 1559.0, 1441 .0, 1378 .9, 13603, 1031. 1,981 .4 and 947.3 cm -1 due tovarious types of dissociative adsorption of H2 over ZrO2 with changing temperatore wereobserved by in situ FT-IR spectroscopy.
基金supported by the National Natural Science Foun-dation of China(No.62004143)the Key R&D Program of Hubei Province(No.2022BAA084)the Natural Science Foundation of Hubei Province(No.2021CFB133).
文摘Doping engineering is an effective strategy for graphitic carbon nitride(g-C_(3)N_(4))to improve its photocat-alytic hydrogen evolution reaction(HER)performance.In this work,a novel nitrogen and sulfur co-doped g-C_(3)N_(4)(N,S-g-C_(3)N_(4))is elaborately designed on the basis of theoretical predictions of first-principle density functional theory(DFT).The calculated Gibbs free energy of adsorbed hydrogen(ΔGH∗)for N,S-g-C_(3)N_(4) at the N-doping active sites is extremely close to zero(0.01 eV).Inspired by the theoretical predictions,the N,S-g-C_(3)N_(4) is successfully fabricated through ammonia-rich pyrolysis synthesis strategy,in which ammonia is in-situ obtained by pyrolyzing melamine.Subsequent characterizations indicate that the N,S-g-C_(3)N_(4) possesses high specific surface area,outstanding light utilization,good hydrophilicity,and efficient carrier transfer efficiency.Consequently,the N,S-g-C_(3)N_(4) displays an extremely high H2 evolution rate of 8269.9μmol g−1 h−1,achieves an apparent quantum efficiency(AQE)of 3.24%,and also possesses outsatnding durability.Theoretical calculations further demonstrate that N and S dopants can not only introduce doping energy level to reduce the band gap,but also induce charge redistribution to facilitate hydrogen adsorption,thus promoting the photocatalytic HER process.Moreover,femtosecond transient absorption(fs-TA)spectroscopy further corroborates the efficient photogenerated carrier transport of N,S-g-C_(3)N_(4).This research highlights a promising and reliable strategy to achieve superior photocatalytic activity,and exhibits significant guidance for precise designing high-efficiency photocatalysts.
文摘Subject Code:B01 Photocatalytic hydrogen evolution by water-splitting has been recognized as one of the most promising solutions to the global energy and environment crisis,owing to its renewable solar energy source and clean chemical fuel product.Cadmium sulfide(CdS)and TiO2(or related polyoxo-titanium clusters)are two
文摘Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics,superstable and efficient cocatalysts have rarely been produced through the modulation of their structure and composition.In this study,a series of bimetallic nickel-iron phosphide(Ni_(x)Fe_(2-x)P,where 0<x<2)cocatalysts with controllable structures and overpotentials were designed by adjusting the atomic ratio of Ni/Fe onto nonmetallic elemental red phosphorus(RP)for the photocatalytic selective oxidation of benzyl alcohol(BA)coupled with hydrogen production.The catalysts exhibited an outstanding photocatalytic activity for benzaldehyde and a high H_(2)yield.The RP regulated by bimetallic phosphide cocatalysts(Ni_(x)Fe_(2-x)P)demonstrated higher photocatalytic oxidation-reduction activity than that regulated by monometallic phosphide cocatalysts(Ni_(2)P and Fe2P).In particular,the RP regulated by Ni_(1.25)Fe_(0.75)P exhibited the best photocatalytic performance.In addition,experimental and theoretical calculations further illustrated that Ni_(1.25)Fe_(0.75)P,with the optimized electronic structure,possessed good electrical conductivity and provided strong adsorption and abundant active sites,thereby accelerating electron migration and lowering the reaction energy barrier of RP.This finding offers valuable insights into the rational design of highly effective cocatalysts aimed at optimizing the photocatalytic activity of composite photocatalysts.
基金supported by the Fundamental Research Funds for the Central Universities(No.2024JBZY008)National Natural Science Foundation of China(No.52401031)+1 种基金the Talent Fund of Beijing Jiaotong University,China(No.2024XKRC064)the National College Students Innovative Entrepreneurial Training Program(No.202510004157).
文摘The development of highly active, durable, and low-cost electrocatalysts is crucial for electrocatalytic hydrogen production. Ultrathin two-dimensional (2D) nanomaterials have extremely large specific surface areas, making them highly desirable electrocatalyst morphologies. Medium-entropy alloys (MEAs) exhibit compositional tunability and entropy-driven structural stability, making them ideal electrocatalyst candidates. In this study, MoCoNi MEA with ultrathin 2D morphology was successfully developed using a facile ionic lay-er epitaxial method. The ultrathin 2D MoCoNi MEA showed an excellent oxygen evolution reaction (OER) electrocatalytic performance, with a low overpotential of 167 mV at a current density of 10 mA/cm^(2) and small Tafel slope of 33.2 mV/dec. At the overpotential of 167 mV, the ultrathin 2D MoCoNi MEA exhibited ultrahigh mass activity of 3359.6 A/g, which is three orders of magnitude higher than that of the commercial noble metal oxide RuO_(2) (1.15 A/g). This excellent electrocatalytic performance was attributed to the synergy of multiple active metal-induced medium entropies, as well as the ultrathin thickness, which considerably shortened the charge-transfer dis-tance and thus significantly promoted charge transfer. Owing to the natural entropy-stabilizing effect, the ultrathin 2D MoCoNi MEA maintained 90% of the initial current after a continuous OER electrocatalytic test for 134 h, showing impressive electrocatalytic stability. This study opens new avenues for the development of high-performance and low-cost electrocatalyst materials by creating MEAs with ultrathin 2D morphology.
文摘As one of the most important industrially viable methods for carbon dioxide(CO_(2))utilization,methanol synthesis serves as a platform for production of green fuels and commodity chemicals.For sustainable methanol synthesis,In_(2)O_(3)is an ideal catalyst and has garnered significant attention.Herein,cubic In_(2)O_(3)nanoparticles were prepared via the precipitation method and evaluated for CO_(2)hydrogenation to produce methanol.During the initial 10 h of reaction,CO_(2)conversion gradually increased,accompanied by a slow decrease of methanol selectivity,and the reaction reached equilibrium after 10-20 h on stream.This activation and induction stage may be attributed to the sintering of In_(2)O_(3)nanoparticles and the creation of more oxygen vacancies on In_(2)O_(3)surfaces.Further experimental studies demonstrate that hydrogen induction created additional oxygen vacancies during the catalyst activation stage,enhancing the performance of In_(2)O_(3)catalyst for CO_(2)hydrogenation.Density functional theory calculations and microkinetic simulations further demonstrated that surfaces with higher oxygen vacancy coverages or hydroxylated surfaces formed during this induction period can enhance the reaction rate and increase the CO_(2)conversion.However,they predominantly promote the formation of CO instead of methanol,leading to reduced methanol selectivity.These predictions align well with the above-mentioned experimental observations.Our work thus provides an in-depth analysis of the induction stage of the CO_(2)hydrogenation process on In_(2)O_(3)nano-catalyst,and offers valuable insights for significantly improving the CO_(2)reactivity of In_(2)O_(3)-based catalysts while maintaining long-term stability.
基金supported by the National Key R&D Program of China(No.2022YFB1903200)the National Natural Science Foundation of China(nos.22372137,U23A2087,22227802,and 22472139)Researchers Supporting Project Number(RSP2025R304),King Saud University,Riyadh,Saudi Arabia。
文摘Solar-driven hydrogen(H_(2))evolution and contaminant degradation offer a promising pathway to address the global energy and environmental crisis.However,the inadequate separation of carriers and light absorption remain significant challenges in the advancement of photocatalysis.In this work,a general in situ ion exchange strategy has been employed to integrate palladium single atoms(Pd SAs)into hollow cadmium sulfide(CdS-H)spheres,creating a multifunctional photocatalyst for both photocatalytic H_(2)evolution and organic degradation.The hollow structure enhances light refraction,and Pd SAs act as charge transfer channels,leading to a significant enhancement in the spatial separation efficiency of photocatalytic charge carries pairs and light utilization in the synthesized Pd SAs/CdS-H.Consequently,the optimized 0.3Pd SAs/CdS-H demonstrates an exceptional photocatalytic H_(2) evolution efficiency of 22.23 mmol h^(-1)g^(-1)and an organic pollutant removal rate of 99.2%.Experimental analyses and density functional theory calculations reveal that the Pd SAs lower the work function of CdS-H and enhance the interfacial charge transport,which is crucial for improving photocatalytic performance.Moreover,both superoxide radicals and holes contribute to the removal of organic dyes,as directly confirmed by in situ radical capture experiments.Based on these characterization results,the photocatalytic mechanism for photocatalytic H_(2) evolution and pollutant degradation is proposed,respectively.This work establishes a dual-functional photocatalyst design strategy for sustainable energy generation and environmental remediation.
文摘The intrinsic symmetrical electron distribution in crystalline metal sulfides usually causes an improper electronic configuration between catalytic S atoms and H intermediates(H_(ad))to form strong S-H_(ad) bonds,resulting in a low photocatalytic H_(2) evolution activity.Herein,a cobalt-induced asymmetric electronic distribution is justified as an effective strategy to optimize the electronic configuration of catalytic S sites in NiCoS cocatalysts for highly active photocatalytic H_(2) evolution.To this end,Co atoms are uniformly incorporated in NiS nanoparticles to fabricate homogeneous NiCoS cocatalyst on TiO_(2) surface by a facile photosynthesis strategy.It is revealed that the incorporated Co atoms break the electron distribution symmetry in NiS,thus essentially increasing the electron density of S atoms to form active electron-enriched S^(2+δ)–sites.The electron-enriched S^(2+δ)–sites could interact with Had via an increased antibonding orbital occupancy,which weakens S–Had bonds for efficient H_(ad) adsorption and desorption,endowing the NiCoS cocatalysts with a highly active H_(2) evolution process.Consequently,the optimized NiCoS/TiO_(2)(1:2)photocatalyst displays the highest H_(2) production performance,outperforming the NiS/TiO_(2) and CoS/TiO_(2) samples by factors of 2.1 and 2.5,respectively.This work provides novel insights on breaking electron distribution symmetry to optimize catalytic efficiency of active sites.
基金supported by the National Key R&D Program of China(Nos.2022YFB3504000,2021YFE0115800)the National Natural Science Foundation of China(Nos.52103285,22275142,22293022,U22B6011)+2 种基金the Program of Introducing Talents of Dis-cipline to Universities-Plan 111 from the Ministry of Science and Technology and the Ministry of Education of China(Grant No.B20002)the Natural Science Foundation of Hubei Province(No.2023AFB605)the Dawning Program from Bureau of Science and Technology of Wuhan(No.2023020201020306).
文摘Constructing heterojunctions have received significant attention in photocatalysis because of their effi-cient separation of photogenerated carriers and improving light utilization efficiency.Bimetallic sulfides(e.g.NiCo_(2)S_(4))are applied in electrocatalysis and supercapacitors that can be coupled with TiO_(2)to form a heterojunction.Owing to the staggered energy band arrangement between TiO_(2)and NiCo_(2)S_(4),the es-tablishing of a Z-scheme heterojunction between them is expected to enhance the carrier separation effi-ciency and reduce the sulfide photo-corrosion.However,the application of NiCo_(2)S_(4)in photocatalysis and studies on the mechanism of the TiO_(2)/NiCo_(2)S_(4)Z-scheme heterojunction have seldom been reported.In this work,we obtained a hollow core-shell TiO_(2)/NiCo_(2)S_(4)Z-scheme photocatalyst through a solvothermal method for photocatalytic hydrogen evolution(PHE).The PHE rate of the optimized TiO_(2)/NiCo_(2)S_(4)-0.3 is 8.55 mmol g^(−1)h^(−1),approximately 34 times higher than pure TiO_(2),94 times higher than pure NiCo_(2)S_(4).The remarkable photocatalytic activity can be ascribed to the hollow structure and the in-situ constructed Z-scheme heterojunction.The photogenerated charge transfer mechanism is revealed by hydroxyl radical trapping experiments and electron paramagnetic resonance(EPR)characterization.The in-situ construc-tion of the Z-scheme heterojunction not only enhances the efficiency of separating the photogenerated carriers but also reduces the photo-corrosion of NiCo_(2)S_(4).This study proposes an effective strategy for the design of TiO_(2)-based Z-scheme heterojunctions and the application of NiCo_(2)S_(4)in photocatalysis.
基金financially supported by the National Natural Science Foundation of China(Nos.21906039 and 22006057)China Postdoctoral Science Foundation(No.2023M743178)+6 种基金Jiangsu Province Industry-University-Research Cooperation Project(No.BY20231482)the Open Fund of the Key Laboratory of Solar Cell electrode Materials in China Petroleum and Chemical Industry(No.2024A093)Key Laboratory of Functional Inorganic Material Chemistry(Heilongjiang University)Ministry of EducationExcellent Youth Fund of Basic Research Project of Universities in Shijiazhuang(No.241790627 A)Outstanding Youth Project of Hebei GEO University in 2024(No.JQ202403)PhD Research Startup Foundation of Hebei GEO University in 2024(No.BQ2024026)the National Pre-research Funds of Hebei GEO University in 2024(No.KY2024YB03)。
文摘The synergistic effects of piezoelectric catalysis and plasmonic photocatalysis hold significant promise for achieving high-efficiency solar energy conversion.Herein,SnFe_(2)O_(4)@ZnIn_(2)S_(4)(SFO@ZIS)composites were prepared by a facile low-temperature water bath method,and an efficient and stable near-infrared(NIR)photothermal-assisted piezoelectric photocatalytic system was successfully constructed.The system achieved a synergistic effect of ultrasonic vibration and NIR illumination,driving a photocatalytic hydrogen(H_(2))production rate of 17.9μmol g^(-1)h^(-1).Related photothermal test results demonstrate that the localized surface plasmon(LSPR)resonance effect of SFO not only significantly broadens the NIR light absorption of ZIS,but also improves the reaction temperature and reduces the activation energy of the reaction by efficiently converting the light energy into heat energy.In addition,photoelectrochemical analyses revealed that the SFO with excellent piezoelectric activity effectively facilitated carrier separation by transferring the energetic hot electrons generated by the LSPR effect to the conduction band of ZIS under external mechanical pressure.This study presents an effective design strategy and theoretical basis for constructing an efficient and robust NIR-driven photothermally assisted piezoelectric photo-catalytic system.
基金Project([2023]04)supported by the Science and Technology Innovation Team of Guizhou University,ChinaProject([2019]30)supported by the Cultivation Project of Guizhou University,ChinaProject(2022Z072)supported by the Ningbo 2025 Science and Technology Innovation Major Project Computing Support of the State Key Laboratory of Public Big Data,Guizhou University,China。
文摘High performance composite photocatalyst is a hotspot in the photocatalysis researches.In this study,a cutting-edge CeO_(2)/rutile composite photocatalyst with tiny CeO_(2)concentration of 1.28 wt%was synthesized via a simple photocatalytic method.This as-obtained CeO_(2)/rutile catalyst(CeO_(2)/TiO_(2)-1:1)exhibited an enhanced wastewater degradation and improved water splitting H_(2)evolution ability,with 95.83%removal ratio for methylene blue(MB),72.84%for tetracycline(TC)and 87.57μmol/g H_(2)evolution capacity.Light irradiation and 2-coordinated oxygen vacancies(OV_(2C))on rutile surface promoted the Ce^(3+)adsorption on the rutile(110)facet as DFT results shown.The CeO_(2)/rutile type-Ⅱ heterojunction was evidenced to promote the migration of e^(−)/h^(+)and generation of·OH/·O_(2)^(−)and H_(2),which rapidly boosted the whole photocatalytic performance.This as-prepared CeO_(2)/TiO_(2)photocatalyst can provide useful inspirations and new thoughts about the photosynthesis process,and offer a novel strategy for heterojunction photocatalysts preparation.
基金supported by the National Natural Science Foundation of China(Nos.22378326,11974276,and 22078261)the Northwest University Graduate Student Innovation Project(No.CX2023155)+3 种基金the Natural Science Basic Research Program of Shaanxi Province(No.2023-JC-YB-115)the Shaanxi Key Science and Technology Innovation Team Project(No.2022TD-33)Qin Chuangyuan project of Shaanxi Province(No.QCYRCXM-2022-213)The Key Research and Development Program of Shaanxi Province(No.2024GX-YBXM-449).
文摘Effective separation of bulk phase and surface charges is crucial for maximizing charge utilization in the process of photocatalytic energy conversion.In this study,SnS_(2) nanoflowers and twinned Mn_(0.5) Cd_(0.5) S solid solution(T-MCS)nanoparticles were fabricated by a one-step solvothermal method respectively,fol-lowed by the formation of SnS_(2)/T-MCS nanohybrids through a facile physical solvent evaporation process for high-efficiency photocatalytic hydrogen(H_(2))production.The T-MCS crystal structure consists of alter-nating wurtzite Mn_(0.5) Cd_(0.5) S(WZ-MCS)and zinc blende Mn_(0.5) Cd_(0.5) S(ZB-MCS),forming a twin structure within the semiconductor.The charge migration mechanism between WZ-MCS and ZB-MCS follows the S-scheme pathway owing to slight differences in energy levels within their respective crystal structures,resulting in exceptional bulk phase charge separation capacity of T-MCS.Additionally,SnS_(2) enhances the electrochemical performance of the catalysts by providing more active sites,reducing charge transfer re-sistance and H_(2) production overpotential,thereby facilitating faster reaction kinetics.The photoelectro-chemical tests,radical trapping experiments,density functional theory(DFT),and electron paramagnetic resonance spectroscopy(EPR)confirm that the charge transfer path between SnS_(2) and T-MCS follows an S-type route that accelerates interfacial photo-induced electrons and holes separation while preserving useful charges.The synergistic impact of twinned homojunction and S-type heterojunction in 10 wt.%SnS_(2)/T-MCS composite contributes to a remarkable H_(2) production rate of 182.82 mmol h^(-1) g^(-1),which is 761.8 times higher than that achieved with SnS_(2) alone(0.24 mmol h^(-1) g^(-1)),as well as 5.8 times higher than that achieved with T-MCS alone(31.54 mmol h^(-1) g^(-1)).This study offers novel insights into design-ing highly efficient sulfide photocatalysts specifically targeting solar-driven H_(2) evolution through a dual S-scheme transfer pathway.
基金support of the National Natural Science Foundation of China(Nos.52174238,22378103,52204307,and 22409128)Natural Science Foundation of Changsha(No.kq2208425)the Research Foundation Bureau of Hunan Province(No.24B0787).
文摘Heterojunctions constructed by traditional methods often result in random stacking of materials, leading to lattice mismatch, which adversely affects the extraction and transfer of photo-generated carriers and, in turn, hampers light utilization efficiency. In this work, we report a novel heterojunction comprising alternating S-doped g-C_(3)N_(4) (SCN) and N-doped MoS_(2) (NMS), bridged by Mo–N covalent bonds within hierarchical periodic macroporous (HPM) walls. This heterojunction is synthesized by co-pyrolyzing dicyandiamide, thiourea, and ammonium molybdate. Transient reflectance photoluminescence measurements reveal that the Mo–N covalent bonds serve as “fast tracks” for electron transfer from SCN to NMS, significantly enhancing the charge separation efficiency. Additionally, the well-defined spatial separation of photo-induced carriers, coupled with the efficient mass transfer within the HPM structure, promotes superior carrier utilization. Thanks to the synergistic effect of HPM structures and the bridged Mo–N bonds, the optimized HPM NMS/SCN-1.3 sample exhibits a remarkable H_(2) evolution rate of 473.3 µmol g^(−1) h^(−1) under visible light irradiation, which is approximately 163 and 19 times higher than bulk g-C_(3)N_(4) (BCN) and HPM SCN, respectively. This work offers valuable insights into the design of HPM heterojunctions composed of co-catalysts and host catalysts, paving the way for enhanced photocatalytic H₂ evolution.
文摘Hydrogen peroxide(H_(2)O_(2)),an environmentally friendly chemical with high value,is extensively used in industrial production and daily life.However,the traditional anthraquinone method for H_(2)O_(2) production is associated with a highly energy-consuming and heavily polluting process.Solor-driven photocatalytic evolution of H_(2)O_(2) is a promising,eco-friendly,and energy-efficient strategy that holds great potential to substitute the traditional approach.Here,a ternary photocatalyst,NiS/CdS/Halloysite nanotubes(NiS/CdS/HNTs)is designed and prepared with an earth-abundant clay mineral HNTs as the support and NiS as a co-catalyst.The pivotal roles of HNTs and NiS in the photocatalytic process are elucidated by experiments and theoretical calculations.HNTs serve as the carrier,which allows CdS to be uniformly dispersed onto its surface as small particles,increasing effective contact with H_(2)O and O_(2) for H_(2)O_(2) formation.Simultaneously,it resulted in the formation of a Schottky junction between NiS and CdS,which not only favors photogenerated charges separating efficiently but also provides a unidirectional path to transfer electrons.Consequently,the optimized NiS/CdS/HNTs composite demonstrates an H_(2)O_(2) evolution rate of 380.5μmol·g^(-1)·h^(-1) without adding any sacrificial agent or extra O_(2),nearly 5.0 times that of pure CdS.This work suggests a feasible idea for designing and developing highly active and low-cost solar energy catalytic composite materials.
