Rational design of photocatalyst to maximize the use of sunlight is one of the issues to be solved in photocatalysis technology.In this study,the CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S(CFO@C/CZS)S-scheme photocatalyst with...Rational design of photocatalyst to maximize the use of sunlight is one of the issues to be solved in photocatalysis technology.In this study,the CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S(CFO@C/CZS)S-scheme photocatalyst with photothermal effect was synthesized by ultrasonic self-assembly combined with calcination.The dark CFO@C absorbed visible light and partly converted into heat to promote the hydrogen evolution reaction.The presence of heterojunctions inhibited the photogenerated electron-hole recombination.The graphite-carbon layer provided a stable channel for electron transfer,and the presence of magnetic CFO made recycle easier.Under the action of photothermal assistance and heterojunction,the hydrogen evolution rate of the optimal CFO@C/CZS was 80.79 mmol g^(-1) h^(-1),which was 2.55 times and 260.61 times of that of pure CZS and CFO@C,respectively.Notably,the composite samples also exhibit excellent stability and a wide range of environmental adaptability.Through experimental tests and first-principles simulation calculation methods,the plausible mechanism of photoactivity enhancement was proposed.This work provided a feasible strategy of photothermal assistance for the development of heterojunction photocatalysts with distinctive hydrogen evolution.展开更多
Photothermal catalytic CO_(2) conversion provides an effective solution targeting carbon neutrality by synergistic utilization of photon and heat.However,the C-C coupling initiated by photothermal catalysis is still a...Photothermal catalytic CO_(2) conversion provides an effective solution targeting carbon neutrality by synergistic utilization of photon and heat.However,the C-C coupling initiated by photothermal catalysis is still a big challenge.Herein,a three-dimensional(3D)hierarchical W_(18)O_(49)/WTe_(2) hollow nanosphere is constructed through in-situ embodying of oxygen vacancy and tellurium on the scaffold of WO_(3).The light absorption towards near-infrared spectral region and CO_(2) adsorption are enhanced by the formation of half-metal WTe_(2) and the unique hierarchical hollow architecture.Combining with the generation of oxygen vacancy with strengthened CO_(2) capture,the photothermal effect on the samples can be sufficiently exploited for activating the CO_(2) molecules.In particular,the close contact between W_(18)O_(49)and WTe_(2) largely promotes the photoinduced charge separation and mass transfer,and thus the~*CHO intermediate formation and fixedness are facilitated.As a result,the C-C coupling can be evoked between tungsten and tellurium atoms on WTe_(2).The ethylene production by optimized W_(18)O_(49)/WTe_(2) reaches 147.6μmol g^(-1)with the selectivity of 80%.The in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and density functional theory(DFT)calculations are performed to unveil the presence and significance of aldehyde intermediate groups in C-C coupling.The half-metallic WTe_(2) cocatalyst proposes a new approach for efficient CO_(2) conversion with solar energy,and may especially create a new platform for the generation of multi-carbon products.展开更多
3D flower-like hierarchical mesoporous Bi_(4)O_(5)I_(2)/MoS_(2)Z-scheme layered heterojunction photocatalyst was fabricated by oil bath and hydrothermal methods.The heterojunction with narrow band gap of~1.95 eV exten...3D flower-like hierarchical mesoporous Bi_(4)O_(5)I_(2)/MoS_(2)Z-scheme layered heterojunction photocatalyst was fabricated by oil bath and hydrothermal methods.The heterojunction with narrow band gap of~1.95 eV extended the photoresponse to near-infrared region,which showed obvious photothermal effect due to the introduction of MoS_(2) with broad spectrum response.MoS_(2) nanosheets were anchored onto the surface of flower-like hierarchical mesoporous Bi_(4)O_(5)I_(2) nanosheets,thereby forming efficient layered heterojunctions,the solar-driven photocatalytic efficiency in degradation of highly toxic dichlorophenol and reduction of hexavalent chromium was improved to 98.5%and 99.2%,which was~4 and 7 times higher than that of the pristine Bi_(4)O_(5)I_(2),respectively.In addition,the photocatalytic hydrogen production rate reached 496.78 μmol h^(-1)g^(-1),which was~6 times higher than that of the pristine Bi_(4)O_(5)I_(2).The excellent photocatalytic performance can be ascribed to the promoted photothermal effect,as well as,the formation of compact Z-scheme layered heterojunctions.The 3D flower-like hierarchical mesoporous structure provided adequate surface active-sites,which was conducive to the mass transfer.Moreover,the high stability of the prepared photocatalyst further promoted its potential practical application.This strategy also provides new insights for fabricating layered Zscheme heterojunctions photocatalysts with highly photothermal-photocatalytic efficiency.展开更多
Thermal and photothermal catalytic selec-tive oxidation of isobutane to methacrylic acid(MAA)are comparatively studied over a keggin-type Cs2.9Cu0.34V0.49PMo12O40 het-eropolyacid acid.An introduction of light was obse...Thermal and photothermal catalytic selec-tive oxidation of isobutane to methacrylic acid(MAA)are comparatively studied over a keggin-type Cs2.9Cu0.34V0.49PMo12O40 het-eropolyacid acid.An introduction of light was observed to enhance both the i-C4H10 conversion and the MAA selectivity,and consequently the MAA formate rate,particularly at low temperatures.Characterization re-sults show that oxidation of methacrolein(MAL)to MAA is the rate-limiting step while UV light illumination promotes the oxidation ofσ-bonded MAL with OH groups toσ-bonded MAA on the catalyst surface.These results demonstrate a synergistic effect of thermal cataly-sis and photocatalysis in selective oxidation of isobutane to MAA,which suggests photother-mal catalysis as a promising strategy to catalyze the selective oxidation of higher hydrocar-bons at relative mild reaction conditions.展开更多
The higher capacity of CO_(2)adsorption on the surface of magnesium oxide(MgO)with low-coordination O^(2-)sites would effectively enhance the catalytic reduction of CO_(2).Herein,a series of copper oxide(CuO)and MgO c...The higher capacity of CO_(2)adsorption on the surface of magnesium oxide(MgO)with low-coordination O^(2-)sites would effectively enhance the catalytic reduction of CO_(2).Herein,a series of copper oxide(CuO)and MgO composites with different mass ratios have been prepared by hydrothermal method and used for photothermal synergistic catalytic reduction of CO_(2)to ethanol.The catalyst with CuO mass ratio of 1.6% shows the best yield(15.17μmol·g^(-1)·h^(-1))under 3 h Xenon lamp illumination.The improved performance is attributable to the loose nano-sheet structure,uniform dispersion of active sites,the increased specific surface area,medium-strength basicity,the high separation efficiency of electrons and holes,and the formation of Mg-O-Cu species.The synthesized CuO and MgO composites with loose nano-sheet structure facilitate the diffusion of reactants CO_(2),so an excellent CO_(2)adsorption performance can be obtained.Meanwhile,the introduction of CuO in the form of bivalence provides higher specific surface area and porosity,thus obtaining more active sites.More importantly,the Mg-O-Cu species make the donation of electrons from MgO to CO_(2)easier,resulting in the breaking of the old Mg-O bond and the formation of C-O bond,thus promoting the adsorption and conversion of CO_(2)to ethanol.展开更多
Nanozymes are nanomaterials with enzyme-like properties that have attracted significant interest owing to their high stability,easy preparation,and tunable catalytic properties,especially in the field of cancer therap...Nanozymes are nanomaterials with enzyme-like properties that have attracted significant interest owing to their high stability,easy preparation,and tunable catalytic properties,especially in the field of cancer therapy.However,the unfavorable catalytic effects of nanozymes in the acidic tumor microenvironment have limited their applications.Herein,we developed a biomimetic erythrocyte membrane-camouflaged ultrasmall black phosphorus quantum dots(BPQDs)nanozymes that simultaneously exhibited an exceptional near-infrared(NIR)photothermal property and dramatically photothermal-enhanced glucose oxidase(GOx)-like activity in the acidic tumor microenvironment.We demonstrated the engineered BPQDs gave a photothermal conversion efficiency of 28.9%that could rapidly heat the tumor up to 50℃ while effectively localized into tumors via homing peptide iRGD leading after intravenously injection.Meanwhile,the significantly enhanced GOx-like activity of BPQDs under NIR irradiation was capable of catalytical generating massive toxic reactive oxygen species via using cellular glucose.By combining the intrinsic photothermal property and the unique photothermal-enhanced GOx-like catalytic activity,the developed BPQDs were demonstrated to be an effective therapeutic strategy for inhibiting tumor growth in vivo.We believe that this work will provide a novel perspective for the development of nanozymes in tumor catalytic therapy.展开更多
Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent year...Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.展开更多
The artificial photosynthesis technology has been recognized as a promising solution for CO_(2) utilization.Photothermal catalysis has been proposed as a novel strategy to promote the efficiency of artificial photosyn...The artificial photosynthesis technology has been recognized as a promising solution for CO_(2) utilization.Photothermal catalysis has been proposed as a novel strategy to promote the efficiency of artificial photosynthesis by coupling both photochemistry and thermochemistry.However,strategies for maximizing the use of solar spectra with different frequencies in photothermal catalysis are urgently needed.Here,a hierarchical full-spectrum solar light utilization strategy is proposed.Based on this strategy,a Cu@hollow titanium silicalite-1 zeolite(TS-1)nanoreactor with spatially separated photo/thermal catalytic sites is designed to realize high-efficiency photothermal catalytic artificial photosynthesis.The space-time yield of alcohol products over the optimal catalyst reached 64.4μmol g−1 h−1,with the selectivity of CH3CH2OH of 69.5%.This rationally designed hierarchical utilization strategy for solar light can be summarized as follows:(1)high-energy ultraviolet light is utilized to drive the initial and difficult CO_(2) activation step on the TS-1 shell;(2)visible light can induce the localized surface plasmon resonance effect on plasmonic Cu to generate hot electrons for H2O dissociation and subsequent reaction steps;and(3)low-energy near-infrared light is converted into heat by the simulated greenhouse effect by cavities to accelerate the carrier dynamics.This work provides some scientific and experimental bases for research on novel,highly efficient photothermal catalysts for artificial photosynthesis.展开更多
With the continuous advancement of communication technology,the escalating demand for electromagnetic shielding interference(EMI)materials with multifunctional and wideband EMI performance has become urgent.Controllin...With the continuous advancement of communication technology,the escalating demand for electromagnetic shielding interference(EMI)materials with multifunctional and wideband EMI performance has become urgent.Controlling the electrical and magnetic components and designing the EMI material structure have attracted extensive interest,but remain a huge challenge.Herein,we reported the alternating electromagnetic structure composite films composed of hollow metal-organic frameworks/layered MXene/nanocellulose(HMN)by alternating vacuum-assisted filtration process.The HMN composite films exhibit excellent EMI shielding effectiveness performance in the GHz frequency(66.8 dB at Kaband)and THz frequency(114.6 dB at 0.1-4.0 THz).Besides,the HMN composite films also exhibit a high reflection loss of 39.7 dB at 0.7 THz with an effective absorption bandwidth up to 2.1 THz.Moreover,HMN composite films show remarkable photothermal conversion performance,which can reach 104.6℃under 2.0 Sun and 235.4℃under 0.8 W cm^(−2),respectively.The unique micro-and macrostructural design structures will absorb more incident electromagnetic waves via interfacial polarization/multiple scattering and produce more heat energy via the local surface plasmon resonance effect.These features make the HMN composite film a promising candidate for advanced EMI devices for future 6G communication and the protection of electronic equipment in cold environments.展开更多
Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safet...Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safety compared with inorganic PTMs. However, so far, only a few NIR-Ⅱresponsive organic PTMs was explored, and their photothermal conversion efficiencies(PCEs) still remain relatively low. Herein, donor–acceptor conjugated diradical polymers with open-shell characteristics are explored for synergistically photothermal immunotherapy of metastatic tumors in the NIR-Ⅱ window. By employing side-chain regulation, the conjugated diradical polymer TTB-2 with obvious NIR-Ⅱ absorption was developed, and its nanoparticles realize a record-breaking PCE of 87.7% upon NIR-Ⅱ light illustration. In vitro and in vivo experiments demonstrate that TTB-2 nanoparticles show good tumor photoablation with navigation of photoacoustic imaging in the NIR-Ⅱ window, without any side-effect. Moreover, by combining with PD-1 antibody,the pulmonary metastasis of breast cancer is high-effectively prevented by the efficient photo-immunity effect. Thus, this study explores superior PTMs for cancer metastasis theranostics in the NIR-Ⅱ window, offering a new horizon in developing radical-characteristic NIR-Ⅱ photothermal materials.展开更多
The transformation of aldose to ketose or common sugars into rare saccharides,including rare ketoses and aldoses,is of great value and interest to the food industry and for saccharidic biomass utilization,medicine,and...The transformation of aldose to ketose or common sugars into rare saccharides,including rare ketoses and aldoses,is of great value and interest to the food industry and for saccharidic biomass utilization,medicine,and the synthesis of drugs.Nowadays,high-fructose corn syrup(HFCS)is industrially produced in more than 10 million tons annually using immobilized glucose isomerase.Some low-calorie saccharides such as tagatose and psicose,which are becoming popular sweeteners,have also been produced on a pilot scale in order to replace sucrose and HFCS.However,current catalysts and catalytic processes are still difficult to utilize in biomass conversion and also have strong substrate dependence in producing high-value,rare sugars.Considering the specific reaction properties of saccharides and catalysts,since the pioneering discovery by Fischer,various catalysts and catalytic systems have been discovered or developed in attempts to extend the reaction pathways,improve the reaction efficiency,and to potentially produce commercial products.In this review,we trace the history of sugar isomerization/epimerization reactions and summarize the important breakthroughs for each reaction as well as the difficulties that remain unresolved to date.展开更多
Pristine phase change materials(PCMs)suffer from inherent deficiencies of poor solar absorption and photothermal conversion.Herein,we proposed a strategy of co-incorporation of zero-dimensional(OD)metal nanoparticles ...Pristine phase change materials(PCMs)suffer from inherent deficiencies of poor solar absorption and photothermal conversion.Herein,we proposed a strategy of co-incorporation of zero-dimensional(OD)metal nanoparticles and two-dimensional(2D)photothermal materials in PCMs for efficient capture and conversion of solar energy into thermal energy.Highly scattered Co-anchored MoS_(2)nanoflower cluster serving as photon and phonon triggers was prepared by in-situ hydrothermal growth of ZIF67 polyhedron on 2D MoS_(2)and subsequent high-temperature carbonization.After encapsulating thermal storage unit(paraffin wax),the obtained composite PCMs integrated high-performance photothermal conversion and thermal energy storage capability.Benefiting from the synergistic enhancement of OD Co nanoparticles with localized surface plasmon resonance effect,carbon layer with the conjugation effect and 2D MoS_(2)with strong solar absorption,composite PCMs exhibited a high photothermal conversion efficiency of 95.19%,Additionally,the resulting composite PCMs also demonstrated long-term thermal sto rage stability and durable structu ral stability after 300 thermal cycles.The proposed collabo rative co-incorporation strategy provides some innovative references for developing next-generation photothermal PCMs in solar energy utilization.展开更多
A novel ultra-stable zeolite, NSZ, rich in secondary pores was developed through the combination of gas-phase andmild hydrothermal methods. This zeolite was successfully tested in an industrial setting for the first t...A novel ultra-stable zeolite, NSZ, rich in secondary pores was developed through the combination of gas-phase andmild hydrothermal methods. This zeolite was successfully tested in an industrial setting for the first time in the world. The porestructure characteristics of the NSZ zeolite prepared for industrial use were analyzed and characterized using BET. The resultsindicate a significant increase in the secondary pore volume of NSZ zeolite compared to the existing ultra-stable zeolite HSZ-5, which is produced through a conventional gas-phase method. The average secondary pore volume to total pore volume ratioin NSZ zeolite was found to be 58.96% higher. The catalytic cracking performance of NSZ zeolite was evaluated. The resultsshowed that the NSC-LTA catalyst, with NSZ as the active component, outperformed the HSC-LTA catalyst with HSZ-5 zeolitein terms of obtaining more high-value products (gasoline and liquefied petroleum gas) during the hydrogenated light cycle oilprocessing. Additionally, the NSC-LTA catalyst showed a significant improvement in coke selectivity.展开更多
ZSM-5 with hierarchical pore structure was synthesized by a simple two-step hydrothermal crystallization from silica fume without using any organic ammonium templates.The synthesized ZSM-5 were oval shaped particles w...ZSM-5 with hierarchical pore structure was synthesized by a simple two-step hydrothermal crystallization from silica fume without using any organic ammonium templates.The synthesized ZSM-5 were oval shaped particles with a particle size about 2.0 μm and weak acid-dominated with proper Brønsted(B)and Lewis(L)acid sites.The ZSM-5 was used for catalytic co-cracking of n-octane and guaiacol,lowdensity polyethylene(LDPE)and alkali lignin(AL)to enhance the production of benzene,toluene,ethylbenzene and xylene(BTEX).The most significant synergistic effect occurred at n-octane/guaiacol at 1:1 and LDPE/AL at 1:3,under the condition,the achieved BTEX selectivity were 24%and 33%(mass)higher than the calculated values(weighted average).The highest BTEX selectivity reached 88.5%,which was 3.7%and 54.2%higher than those from individual cracking LDPE and AL.The synthesized ZSM-5 exhibited superior catalytic performance compared to the commercial ZSM-5,indicating potential application prospect.展开更多
Background:Treatment of methicillin-resistant Staphylococcus aureus(MRSA)biofilm infections in implant placement surgery is limited by the lack of antimicrobial activity of titanium(Ti)implants.There is a need to expl...Background:Treatment of methicillin-resistant Staphylococcus aureus(MRSA)biofilm infections in implant placement surgery is limited by the lack of antimicrobial activity of titanium(Ti)implants.There is a need to explore more effective approaches for the treatment of MRSA biofilm infections.Methods:Herein,an interfacial functionalization strategy is proposed by the integration of mesoporous polydopamine nanoparticles(PDA),nitric oxide(NO)release donor sodium nitroprusside(SNP)and osteogenic growth peptide(OGP)onto Ti implants,denoted as Ti-PDA@SNP-OGP.The physical and chemical properties of Ti-PDA@SNP-OGP were assessed by scanning electron microscopy,X-ray photoelectron spectroscope,water contact angle,photothermal property and NO release behavior.The synergistic antibacterial effect and elimination of the MRSA biofilms were evaluated by 2′,7′-dichlorofluorescein diacetate probe,1-N-phenylnaphthylamine assay,adenosine triphosphate intensity,O-nitrophenyl-β-D-galactopyranoside hydrolysis activity,bicinchoninic acid leakage.Fluorescence staining,assays for alkaline phosphatase activity,collagen secretion and extracellular matrix mineralization,quantitative real‑time reverse transcription‑polymerase chain reaction,and enzyme-linked immunosorbent assay(ELISA)were used to evaluate the inflammatory response and osteogenic ability in bone marrow stromal cells(MSCs),RAW264.7 cells and their co-culture system.Giemsa staining,ELISA,micro-CT,hematoxylin and eosin,Masson's trichrome and immunohistochemistry staining were used to evaluate the eradication of MRSA biofilms,inhibition of inflammatory response,and promotion of osseointegration of Ti-PDA@SNP-OGP in vivo.Results:Ti-PDA@SNP-OGP displayed a synergistic photothermal and NO-dependent antibacterial effect against MRSA following near-infrared light(NIR)irradiation,and effectively eliminated the formed MRSA biofilms by inducing reactive oxygen species(ROS)-mediated oxidative stress,destroying bacterial membrane integrity and causing leakage of intracellular components(P<0.01).In vitro experiments revealed that Ti-PDA@SNP-OGP not only facilitated osteogenic differentiation of MSCs,but also promoted the polarization of pro-inflammatory M1 macrophages to the anti-inflammatory M2-phenotype(P<0.05 or P<0.01).The favorable osteo-immune microenvironment further facilitated osteogenesis of MSCs and the anti-inflammation of RAW264.7 cells via multiple paracrine signaling pathways(P<0.01).In vivo evaluation confirmed the aforementioned results and revealed that Ti-PDA@SNP-OGP induced ameliorative osseointegration in an MRSA-infected femoral defect implantation model(P<0.01).Conclusions:Ti-PDA@SNP-OGP is a promising multi-functional material for the high-efficient treatment of MRSA infections in implant replacement surgeries.展开更多
High-temperature treatment is key to the preparation of zeolite catalysts.Herein,the effects of hightemperature treatment on the property and performance of HZSM-5 zeolites were studied in this work.X-Ray diffraction,...High-temperature treatment is key to the preparation of zeolite catalysts.Herein,the effects of hightemperature treatment on the property and performance of HZSM-5 zeolites were studied in this work.X-Ray diffraction,N2physisorption,27Al magic angle spinning nuclear magnetic resonance(MAS NMR),and temperature-programmed desorption of ammonia results indicated that the hightemperature treatment at 650℃ hardly affected the inherent crystal and texture of HZSM-5zeolites but facilitated the conversion of framework Al to extra-framework Al,reducing the acid site and enhancing the acid strength.Moreover,the high-temperature treatment improved the performance of HZSM-5 zeolites in n-heptane catalytic cracking,promoting the conversion and light olefins yield while inhibiting coke formation.Based on the kinetic and mechanism analysis,the improvement of HZSM-5 performance caused by high-temperature treatment has been attributed to the formation of extra-framework Al,which enhanced the acid strength,facilitated the bimolecular reaction,and promoted the entropy change to overcome a higher energy barrier in n-heptane catalytic cracking.展开更多
Catalytic cracking oil slurry is a by-product of catalytic cracking projects,and the efficient conversion and sustainable utilization of this material are issues of continuous concern in the petroleum refining industr...Catalytic cracking oil slurry is a by-product of catalytic cracking projects,and the efficient conversion and sustainable utilization of this material are issues of continuous concern in the petroleum refining industry.In this study,oxygen-enriched activated carbon is prepared using a one-step KOH activation method with catalytic cracking oil slurry as the raw material.The as-prepared oil slurry-based activated carbon exhibits a high specific surface area of 2102 m^(2)/g,welldefined micropores with an average diameter of 2 nm,and a rich oxygen doping content of 32.97%.The electrochemical performance of the nitrogen-doped porous carbon is tested in a three-electrode system using a 6 mol/L KOH solution as the electrolyte.It achieves a specific capacitance of up to 230 F/g at a current density of 1 A/g.Moreover,the capacitance retention rate exceeds 89%after 10000 charge and discharge cycles,demonstrating excellent cycle stability.This method not only improves the utilization efficiency of industrial fuel waste but also reduces the production cost of supercapacitor electrode materials,thereby providing a simple and effective strategy for the resource utilization of catalytic cracking oil slurries.展开更多
In this study,the perovskite nanocomposite PrFe_(x)Co_(1-x)O_(3)(Pr(S))was successfully synthesized by the sol-gel method;PrFe_(x)Co_(1-x)O_(3)/Al-pillared montmorillonite(Pr(S)/Mt)catalysts were prepared by impregnat...In this study,the perovskite nanocomposite PrFe_(x)Co_(1-x)O_(3)(Pr(S))was successfully synthesized by the sol-gel method;PrFe_(x)Co_(1-x)O_(3)/Al-pillared montmorillonite(Pr(S)/Mt)catalysts were prepared by impregnation(D)method and solid-melting(G)method,respectively,with Pr(S)as the active component and Al-pillared montmorillonite as the carrier.The catalysts were applied to treat the 2-hydroxybenzoic acid(2-HA)-simulated wastewater by catalytic wet peroxide oxidation(CWPO)technique,and the chemical oxygen demand(COD)removal rate and the 2-HA degradation rate were used as indicators to evaluate the catalytic performance.The results of the experiment indicated that the solid-melting method was more conducive to preparing the catalyst when the Co/Fe molar ratio of 7:3 and the optimal structural properties of the catalysts were achieved.The influence of operating parameters,including reaction temperature,catalyst dosage,H_(2)O_(2)dosage,pH,and initial 2-HA concentration,were optimized for the degradation of 2-HA by CWPO.The results showed that 97.64%of 2-HA degradation and 75.23%of COD removal rate were achieved under more suitable experimental conditions.In addition,after the catalyst was used five times,the degradation rate of 2-HA could still reach 76.93%,which implied the high stability and reusability of the catalyst.The high catalytic activity of the catalyst was due to the doping of Co into PrFeO_(3),which could promote the generation of HO·,and the high stability could be attributed to the loading of Pr(S)onto Al-Mt,which reduced the leaching of reactive metals.The study of reaction mechanism and kinetics showed that the whole degradation process conformed to the pseudo-firstorder kinetic equation,and the Langmuir-Hinshelwood method was applied to demonstrate that catalysis was dominant in the degradation process.展开更多
Electrochemical water splitting has long been considered an effective energy conversion technology for trans-ferring intermittent renewable electricity into hydrogen fuel,and the exploration of cost-effective and high...Electrochemical water splitting has long been considered an effective energy conversion technology for trans-ferring intermittent renewable electricity into hydrogen fuel,and the exploration of cost-effective and high-performance electrocatalysts is crucial in making electrolyzed water technology commercially viable.Cobalt phosphide(Co-P)has emerged as a catalyst of high potential owing to its high catalytic activity and durability in water splitting.This paper systematically reviews the latest advances in the development of Co-P-based materials for use in water splitting.The essential effects of P in enhancing the catalytic performance of the hydrogen evolution reaction and oxygen evolution reaction are first outlined.Then,versatile synthesis techniques for Co-P electrocatalysts are summarized,followed by advanced strategies to enhance the electrocatalytic performance of Co-P materials,including heteroatom doping,composite construction,integration with well-conductive sub-strates,and structure control from the viewpoint of experiment.Along with these optimization strategies,the understanding of the inherent mechanism of enhanced catalytic performance is also discussed.Finally,some existing challenges in the development of highly active and stable Co-P-based materials are clarified,and pro-spective directions for prompting the wide commercialization of water electrolysis technology are proposed.展开更多
Zirconium-based metal-organic framework UiO-66 was successfully prepared by solvothermal method,and UiO-66 was modified by adding regulators such as formic acid,acetic acid,and hydrochloric acid.The NH_(3)-SCR reactiv...Zirconium-based metal-organic framework UiO-66 was successfully prepared by solvothermal method,and UiO-66 was modified by adding regulators such as formic acid,acetic acid,and hydrochloric acid.The NH_(3)-SCR reactivity of the samples was evaluated by the denitration activity evaluation system,and the UiO-66 and the regulator-modified UiO-66 were characterized by XRD,SEM,BET,FTIR,TG,NH_(3)-TPD,etc.,the effects of regulator types on the structure and properties of UiO-66 were investigated.The experimental results show that,after adding the modifier,the morphology of UiO-66 changes from irregular quadrilateral with serious agglomeration to particles with regular crystal shape and good dispersibility,and the crystal morphology of the catalyst is improved.In addition,after adding the modifier,UiO-66 has a larger specific surface area and stronger surface acidity,which optimizes the catalytic performance of UiO-66.The catalytic performance test results of NH_(3)-SCR show that the low-temperature activity of UiO-66 is poor,and it only shows a certain catalytic activity at higher temperatures.The catalytic activity of UiO-66 was significantly improved after adding the regulator.Among them,the UiO-66-HCl modified with hydrochloric acid had the best catalytic activity,and the denitration rate reached 70%when the denitration temperature was 380℃.展开更多
基金supported by the Shandong Provincial Natural Science Foundation(ZR2022ME179,ZR2021QE086)the Shandong Provincial Key Research and Development Program(Public Welfare Science and Technology Research)(2019GGX103010)+2 种基金the Science and Technology Planning Project of Higher School in Shandong Province(J18KA243)the Liaocheng Key Research and Development Program(Policy guidance category)(2022YDSF90)the Liaocheng University High-level Talents&PhD Research Startup Foundation(318051619)。
文摘Rational design of photocatalyst to maximize the use of sunlight is one of the issues to be solved in photocatalysis technology.In this study,the CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S(CFO@C/CZS)S-scheme photocatalyst with photothermal effect was synthesized by ultrasonic self-assembly combined with calcination.The dark CFO@C absorbed visible light and partly converted into heat to promote the hydrogen evolution reaction.The presence of heterojunctions inhibited the photogenerated electron-hole recombination.The graphite-carbon layer provided a stable channel for electron transfer,and the presence of magnetic CFO made recycle easier.Under the action of photothermal assistance and heterojunction,the hydrogen evolution rate of the optimal CFO@C/CZS was 80.79 mmol g^(-1) h^(-1),which was 2.55 times and 260.61 times of that of pure CZS and CFO@C,respectively.Notably,the composite samples also exhibit excellent stability and a wide range of environmental adaptability.Through experimental tests and first-principles simulation calculation methods,the plausible mechanism of photoactivity enhancement was proposed.This work provided a feasible strategy of photothermal assistance for the development of heterojunction photocatalysts with distinctive hydrogen evolution.
基金the National Natural Science Foundation of China(51303083)the National Natural Science Foundation of China for Excellent Young Scholars(51922050)+1 种基金the Natural Science Foundation of Jiangsu Province(BK20191293)the Fundamental Research Funds for the Central Universities(30920021123)。
文摘Photothermal catalytic CO_(2) conversion provides an effective solution targeting carbon neutrality by synergistic utilization of photon and heat.However,the C-C coupling initiated by photothermal catalysis is still a big challenge.Herein,a three-dimensional(3D)hierarchical W_(18)O_(49)/WTe_(2) hollow nanosphere is constructed through in-situ embodying of oxygen vacancy and tellurium on the scaffold of WO_(3).The light absorption towards near-infrared spectral region and CO_(2) adsorption are enhanced by the formation of half-metal WTe_(2) and the unique hierarchical hollow architecture.Combining with the generation of oxygen vacancy with strengthened CO_(2) capture,the photothermal effect on the samples can be sufficiently exploited for activating the CO_(2) molecules.In particular,the close contact between W_(18)O_(49)and WTe_(2) largely promotes the photoinduced charge separation and mass transfer,and thus the~*CHO intermediate formation and fixedness are facilitated.As a result,the C-C coupling can be evoked between tungsten and tellurium atoms on WTe_(2).The ethylene production by optimized W_(18)O_(49)/WTe_(2) reaches 147.6μmol g^(-1)with the selectivity of 80%.The in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and density functional theory(DFT)calculations are performed to unveil the presence and significance of aldehyde intermediate groups in C-C coupling.The half-metallic WTe_(2) cocatalyst proposes a new approach for efficient CO_(2) conversion with solar energy,and may especially create a new platform for the generation of multi-carbon products.
基金support of this research by the National Natural Science Foundation of China(21871078)the Natural Science Foundation of Heilongjiang Province(JQ2019B001 and B2018010)+3 种基金the Heilongjiang Postdoctoral Startup Fund(LBH-Q14135)the Heilongjiang University Science Fund for Distinguished Young Scholars(JCL201802)the Heilongjiang Provincial Institutions of Higher Learning Basic Research Funds Basic Research Projects(KJCX201909)the Heilongjiang Touyan Innovation Team Program.
文摘3D flower-like hierarchical mesoporous Bi_(4)O_(5)I_(2)/MoS_(2)Z-scheme layered heterojunction photocatalyst was fabricated by oil bath and hydrothermal methods.The heterojunction with narrow band gap of~1.95 eV extended the photoresponse to near-infrared region,which showed obvious photothermal effect due to the introduction of MoS_(2) with broad spectrum response.MoS_(2) nanosheets were anchored onto the surface of flower-like hierarchical mesoporous Bi_(4)O_(5)I_(2) nanosheets,thereby forming efficient layered heterojunctions,the solar-driven photocatalytic efficiency in degradation of highly toxic dichlorophenol and reduction of hexavalent chromium was improved to 98.5%and 99.2%,which was~4 and 7 times higher than that of the pristine Bi_(4)O_(5)I_(2),respectively.In addition,the photocatalytic hydrogen production rate reached 496.78 μmol h^(-1)g^(-1),which was~6 times higher than that of the pristine Bi_(4)O_(5)I_(2).The excellent photocatalytic performance can be ascribed to the promoted photothermal effect,as well as,the formation of compact Z-scheme layered heterojunctions.The 3D flower-like hierarchical mesoporous structure provided adequate surface active-sites,which was conducive to the mass transfer.Moreover,the high stability of the prepared photocatalyst further promoted its potential practical application.This strategy also provides new insights for fabricating layered Zscheme heterojunctions photocatalysts with highly photothermal-photocatalytic efficiency.
基金supported by the Shaanxi Yancheng Petroleum(Group)Co.,Ltd.,the National Natural Science Foundation of China(No.22202189)the Changjiang Scholars Program of the Ministry of Education of China.
文摘Thermal and photothermal catalytic selec-tive oxidation of isobutane to methacrylic acid(MAA)are comparatively studied over a keggin-type Cs2.9Cu0.34V0.49PMo12O40 het-eropolyacid acid.An introduction of light was observed to enhance both the i-C4H10 conversion and the MAA selectivity,and consequently the MAA formate rate,particularly at low temperatures.Characterization re-sults show that oxidation of methacrolein(MAL)to MAA is the rate-limiting step while UV light illumination promotes the oxidation ofσ-bonded MAL with OH groups toσ-bonded MAA on the catalyst surface.These results demonstrate a synergistic effect of thermal cataly-sis and photocatalysis in selective oxidation of isobutane to MAA,which suggests photother-mal catalysis as a promising strategy to catalyze the selective oxidation of higher hydrocar-bons at relative mild reaction conditions.
基金Financial supports by National Natural Science Foundation of China(21908052)the Key Program of Natural Science Foundation of Hebei Province(B2020209017)+1 种基金the Project of Science and Technology Innovation Team,Tang shan(20130203D)Youth Program of Natural Science of Hebei Province(B2020209065)。
文摘The higher capacity of CO_(2)adsorption on the surface of magnesium oxide(MgO)with low-coordination O^(2-)sites would effectively enhance the catalytic reduction of CO_(2).Herein,a series of copper oxide(CuO)and MgO composites with different mass ratios have been prepared by hydrothermal method and used for photothermal synergistic catalytic reduction of CO_(2)to ethanol.The catalyst with CuO mass ratio of 1.6% shows the best yield(15.17μmol·g^(-1)·h^(-1))under 3 h Xenon lamp illumination.The improved performance is attributable to the loose nano-sheet structure,uniform dispersion of active sites,the increased specific surface area,medium-strength basicity,the high separation efficiency of electrons and holes,and the formation of Mg-O-Cu species.The synthesized CuO and MgO composites with loose nano-sheet structure facilitate the diffusion of reactants CO_(2),so an excellent CO_(2)adsorption performance can be obtained.Meanwhile,the introduction of CuO in the form of bivalence provides higher specific surface area and porosity,thus obtaining more active sites.More importantly,the Mg-O-Cu species make the donation of electrons from MgO to CO_(2)easier,resulting in the breaking of the old Mg-O bond and the formation of C-O bond,thus promoting the adsorption and conversion of CO_(2)to ethanol.
基金supported by the National Key Research and Development Program of China(Nos.2020YFC1316900 and 2020YFC1316901)China Postdoctoral Science Foundation(Nos.2019T120754 and 2018M633229)+5 种基金Sanming Project of Medicine in Shenzhen(No.SZSM201612031)National Natural Science Foundation of China(Nos.82003303 and 81722024)National Key R&D Program of China(No.2017YFA0205501)Natural Science Foundation of Guangdong Province of China(Nos.2018A030310665 and 2018A0303130295)Shenzhen Science and Technology Innovation Committee(Nos.JSGG20191129144225464,JCYJ20190806163814395,ZDSYS201707281114196,JCYJ20170306091657539,JCYJ-20170413162242627,JCYJ20170306091452714,and GJHZ-20170313172439851)Development and Reform Commission of Shenzhen Municipality(No.S2016005470013).
文摘Nanozymes are nanomaterials with enzyme-like properties that have attracted significant interest owing to their high stability,easy preparation,and tunable catalytic properties,especially in the field of cancer therapy.However,the unfavorable catalytic effects of nanozymes in the acidic tumor microenvironment have limited their applications.Herein,we developed a biomimetic erythrocyte membrane-camouflaged ultrasmall black phosphorus quantum dots(BPQDs)nanozymes that simultaneously exhibited an exceptional near-infrared(NIR)photothermal property and dramatically photothermal-enhanced glucose oxidase(GOx)-like activity in the acidic tumor microenvironment.We demonstrated the engineered BPQDs gave a photothermal conversion efficiency of 28.9%that could rapidly heat the tumor up to 50℃ while effectively localized into tumors via homing peptide iRGD leading after intravenously injection.Meanwhile,the significantly enhanced GOx-like activity of BPQDs under NIR irradiation was capable of catalytical generating massive toxic reactive oxygen species via using cellular glucose.By combining the intrinsic photothermal property and the unique photothermal-enhanced GOx-like catalytic activity,the developed BPQDs were demonstrated to be an effective therapeutic strategy for inhibiting tumor growth in vivo.We believe that this work will provide a novel perspective for the development of nanozymes in tumor catalytic therapy.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.51902101 and 21875203)the Natural Science Foundation of Hunan Province(Nos.2021JJ40044 and 2023JJ50287)Natural Science Foundation of Jiangsu Province(No.BK20201381).
文摘Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.
基金supported by the National Natural Science Foundation of China(Grant Nos.21908052 and 22108200)the Key Program of the Natural Science Foundation of Hebei Province(Grant No.B2020209017)+2 种基金the Project of Science and Technology Innovation Team,Tangshan(Grant No.20130203D)the Natural Science Foundation of Zhejiang Province(Grant No.LQ22B060013)and the Science and Technology Project of Hebei Education Department(Grant No.QN2021113).
文摘The artificial photosynthesis technology has been recognized as a promising solution for CO_(2) utilization.Photothermal catalysis has been proposed as a novel strategy to promote the efficiency of artificial photosynthesis by coupling both photochemistry and thermochemistry.However,strategies for maximizing the use of solar spectra with different frequencies in photothermal catalysis are urgently needed.Here,a hierarchical full-spectrum solar light utilization strategy is proposed.Based on this strategy,a Cu@hollow titanium silicalite-1 zeolite(TS-1)nanoreactor with spatially separated photo/thermal catalytic sites is designed to realize high-efficiency photothermal catalytic artificial photosynthesis.The space-time yield of alcohol products over the optimal catalyst reached 64.4μmol g−1 h−1,with the selectivity of CH3CH2OH of 69.5%.This rationally designed hierarchical utilization strategy for solar light can be summarized as follows:(1)high-energy ultraviolet light is utilized to drive the initial and difficult CO_(2) activation step on the TS-1 shell;(2)visible light can induce the localized surface plasmon resonance effect on plasmonic Cu to generate hot electrons for H2O dissociation and subsequent reaction steps;and(3)low-energy near-infrared light is converted into heat by the simulated greenhouse effect by cavities to accelerate the carrier dynamics.This work provides some scientific and experimental bases for research on novel,highly efficient photothermal catalysts for artificial photosynthesis.
基金the Beijing Nova Program(20230484431)Opening Project of State Silica-Based Materials Laboratory of Anhui Province(2022KF12)is gratefully acknowledged.
文摘With the continuous advancement of communication technology,the escalating demand for electromagnetic shielding interference(EMI)materials with multifunctional and wideband EMI performance has become urgent.Controlling the electrical and magnetic components and designing the EMI material structure have attracted extensive interest,but remain a huge challenge.Herein,we reported the alternating electromagnetic structure composite films composed of hollow metal-organic frameworks/layered MXene/nanocellulose(HMN)by alternating vacuum-assisted filtration process.The HMN composite films exhibit excellent EMI shielding effectiveness performance in the GHz frequency(66.8 dB at Kaband)and THz frequency(114.6 dB at 0.1-4.0 THz).Besides,the HMN composite films also exhibit a high reflection loss of 39.7 dB at 0.7 THz with an effective absorption bandwidth up to 2.1 THz.Moreover,HMN composite films show remarkable photothermal conversion performance,which can reach 104.6℃under 2.0 Sun and 235.4℃under 0.8 W cm^(−2),respectively.The unique micro-and macrostructural design structures will absorb more incident electromagnetic waves via interfacial polarization/multiple scattering and produce more heat energy via the local surface plasmon resonance effect.These features make the HMN composite film a promising candidate for advanced EMI devices for future 6G communication and the protection of electronic equipment in cold environments.
基金The work was financially supported by the National Natural Science Foundation of China(No.52173135,22207024)Jiangsu Specially Appointed Professorship,Leading Talents of Innovation and Entrepreneurship of Gusu(ZXL2022496)the Suzhou Science and Technology Program(SKY2022039).
文摘Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safety compared with inorganic PTMs. However, so far, only a few NIR-Ⅱresponsive organic PTMs was explored, and their photothermal conversion efficiencies(PCEs) still remain relatively low. Herein, donor–acceptor conjugated diradical polymers with open-shell characteristics are explored for synergistically photothermal immunotherapy of metastatic tumors in the NIR-Ⅱ window. By employing side-chain regulation, the conjugated diradical polymer TTB-2 with obvious NIR-Ⅱ absorption was developed, and its nanoparticles realize a record-breaking PCE of 87.7% upon NIR-Ⅱ light illustration. In vitro and in vivo experiments demonstrate that TTB-2 nanoparticles show good tumor photoablation with navigation of photoacoustic imaging in the NIR-Ⅱ window, without any side-effect. Moreover, by combining with PD-1 antibody,the pulmonary metastasis of breast cancer is high-effectively prevented by the efficient photo-immunity effect. Thus, this study explores superior PTMs for cancer metastasis theranostics in the NIR-Ⅱ window, offering a new horizon in developing radical-characteristic NIR-Ⅱ photothermal materials.
基金Financial support by Dual Initiative Project of Jiangsu Province and Changzhou University is gratefully acknowledgedSample analysis supported by Analysis and Testing Center,NERC Biomass of Changzhou University was also greatly acknowledged.
文摘The transformation of aldose to ketose or common sugars into rare saccharides,including rare ketoses and aldoses,is of great value and interest to the food industry and for saccharidic biomass utilization,medicine,and the synthesis of drugs.Nowadays,high-fructose corn syrup(HFCS)is industrially produced in more than 10 million tons annually using immobilized glucose isomerase.Some low-calorie saccharides such as tagatose and psicose,which are becoming popular sweeteners,have also been produced on a pilot scale in order to replace sucrose and HFCS.However,current catalysts and catalytic processes are still difficult to utilize in biomass conversion and also have strong substrate dependence in producing high-value,rare sugars.Considering the specific reaction properties of saccharides and catalysts,since the pioneering discovery by Fischer,various catalysts and catalytic systems have been discovered or developed in attempts to extend the reaction pathways,improve the reaction efficiency,and to potentially produce commercial products.In this review,we trace the history of sugar isomerization/epimerization reactions and summarize the important breakthroughs for each reaction as well as the difficulties that remain unresolved to date.
基金financially supported by National Natural Science Foundation of China(No.51902025)。
文摘Pristine phase change materials(PCMs)suffer from inherent deficiencies of poor solar absorption and photothermal conversion.Herein,we proposed a strategy of co-incorporation of zero-dimensional(OD)metal nanoparticles and two-dimensional(2D)photothermal materials in PCMs for efficient capture and conversion of solar energy into thermal energy.Highly scattered Co-anchored MoS_(2)nanoflower cluster serving as photon and phonon triggers was prepared by in-situ hydrothermal growth of ZIF67 polyhedron on 2D MoS_(2)and subsequent high-temperature carbonization.After encapsulating thermal storage unit(paraffin wax),the obtained composite PCMs integrated high-performance photothermal conversion and thermal energy storage capability.Benefiting from the synergistic enhancement of OD Co nanoparticles with localized surface plasmon resonance effect,carbon layer with the conjugation effect and 2D MoS_(2)with strong solar absorption,composite PCMs exhibited a high photothermal conversion efficiency of 95.19%,Additionally,the resulting composite PCMs also demonstrated long-term thermal sto rage stability and durable structu ral stability after 300 thermal cycles.The proposed collabo rative co-incorporation strategy provides some innovative references for developing next-generation photothermal PCMs in solar energy utilization.
基金the National Key R&D Program of China(2022YFA1504404)the SINOPEC Research Program(121036-5).
文摘A novel ultra-stable zeolite, NSZ, rich in secondary pores was developed through the combination of gas-phase andmild hydrothermal methods. This zeolite was successfully tested in an industrial setting for the first time in the world. The porestructure characteristics of the NSZ zeolite prepared for industrial use were analyzed and characterized using BET. The resultsindicate a significant increase in the secondary pore volume of NSZ zeolite compared to the existing ultra-stable zeolite HSZ-5, which is produced through a conventional gas-phase method. The average secondary pore volume to total pore volume ratioin NSZ zeolite was found to be 58.96% higher. The catalytic cracking performance of NSZ zeolite was evaluated. The resultsshowed that the NSC-LTA catalyst, with NSZ as the active component, outperformed the HSC-LTA catalyst with HSZ-5 zeolitein terms of obtaining more high-value products (gasoline and liquefied petroleum gas) during the hydrogenated light cycle oilprocessing. Additionally, the NSC-LTA catalyst showed a significant improvement in coke selectivity.
基金supported by the National Natural Science Foundation of China(22078076)Guangxi Natural Science Foundation(2020GXNSFAA159174)the Opening Project of National Enterprise Technology Center of Guangxi Bossco Environmental Protection Technology Co.,Ltd(GXU-BFY-2020-005).
文摘ZSM-5 with hierarchical pore structure was synthesized by a simple two-step hydrothermal crystallization from silica fume without using any organic ammonium templates.The synthesized ZSM-5 were oval shaped particles with a particle size about 2.0 μm and weak acid-dominated with proper Brønsted(B)and Lewis(L)acid sites.The ZSM-5 was used for catalytic co-cracking of n-octane and guaiacol,lowdensity polyethylene(LDPE)and alkali lignin(AL)to enhance the production of benzene,toluene,ethylbenzene and xylene(BTEX).The most significant synergistic effect occurred at n-octane/guaiacol at 1:1 and LDPE/AL at 1:3,under the condition,the achieved BTEX selectivity were 24%and 33%(mass)higher than the calculated values(weighted average).The highest BTEX selectivity reached 88.5%,which was 3.7%and 54.2%higher than those from individual cracking LDPE and AL.The synthesized ZSM-5 exhibited superior catalytic performance compared to the commercial ZSM-5,indicating potential application prospect.
基金financially supported by the National Natural Science Foundation of China(82101069,82102537,82160411,82002278)the Natural Science Foundation of Chongqing Science and Technology Commission(CSTC2021JCYJ-MSXMX0170,CSTB2022BSXM-JCX0039)+2 种基金the First Affiliated Hospital of Chongqing Medical University Cultivating Fund(PYJJ2021-02)the Beijing Municipal Science&Technology Commission(Z221100007422130)the Youth Incubation Program of Medical Science and Technology of PLA(21QNPY116).
文摘Background:Treatment of methicillin-resistant Staphylococcus aureus(MRSA)biofilm infections in implant placement surgery is limited by the lack of antimicrobial activity of titanium(Ti)implants.There is a need to explore more effective approaches for the treatment of MRSA biofilm infections.Methods:Herein,an interfacial functionalization strategy is proposed by the integration of mesoporous polydopamine nanoparticles(PDA),nitric oxide(NO)release donor sodium nitroprusside(SNP)and osteogenic growth peptide(OGP)onto Ti implants,denoted as Ti-PDA@SNP-OGP.The physical and chemical properties of Ti-PDA@SNP-OGP were assessed by scanning electron microscopy,X-ray photoelectron spectroscope,water contact angle,photothermal property and NO release behavior.The synergistic antibacterial effect and elimination of the MRSA biofilms were evaluated by 2′,7′-dichlorofluorescein diacetate probe,1-N-phenylnaphthylamine assay,adenosine triphosphate intensity,O-nitrophenyl-β-D-galactopyranoside hydrolysis activity,bicinchoninic acid leakage.Fluorescence staining,assays for alkaline phosphatase activity,collagen secretion and extracellular matrix mineralization,quantitative real‑time reverse transcription‑polymerase chain reaction,and enzyme-linked immunosorbent assay(ELISA)were used to evaluate the inflammatory response and osteogenic ability in bone marrow stromal cells(MSCs),RAW264.7 cells and their co-culture system.Giemsa staining,ELISA,micro-CT,hematoxylin and eosin,Masson's trichrome and immunohistochemistry staining were used to evaluate the eradication of MRSA biofilms,inhibition of inflammatory response,and promotion of osseointegration of Ti-PDA@SNP-OGP in vivo.Results:Ti-PDA@SNP-OGP displayed a synergistic photothermal and NO-dependent antibacterial effect against MRSA following near-infrared light(NIR)irradiation,and effectively eliminated the formed MRSA biofilms by inducing reactive oxygen species(ROS)-mediated oxidative stress,destroying bacterial membrane integrity and causing leakage of intracellular components(P<0.01).In vitro experiments revealed that Ti-PDA@SNP-OGP not only facilitated osteogenic differentiation of MSCs,but also promoted the polarization of pro-inflammatory M1 macrophages to the anti-inflammatory M2-phenotype(P<0.05 or P<0.01).The favorable osteo-immune microenvironment further facilitated osteogenesis of MSCs and the anti-inflammation of RAW264.7 cells via multiple paracrine signaling pathways(P<0.01).In vivo evaluation confirmed the aforementioned results and revealed that Ti-PDA@SNP-OGP induced ameliorative osseointegration in an MRSA-infected femoral defect implantation model(P<0.01).Conclusions:Ti-PDA@SNP-OGP is a promising multi-functional material for the high-efficient treatment of MRSA infections in implant replacement surgeries.
基金the financial support from the National Natural Science Foundation of China(21908010)Jilin Provincial Department of Science and Technology(20220101089JC)the Education Department of Jilin Province(JJKH20220694KJ)。
文摘High-temperature treatment is key to the preparation of zeolite catalysts.Herein,the effects of hightemperature treatment on the property and performance of HZSM-5 zeolites were studied in this work.X-Ray diffraction,N2physisorption,27Al magic angle spinning nuclear magnetic resonance(MAS NMR),and temperature-programmed desorption of ammonia results indicated that the hightemperature treatment at 650℃ hardly affected the inherent crystal and texture of HZSM-5zeolites but facilitated the conversion of framework Al to extra-framework Al,reducing the acid site and enhancing the acid strength.Moreover,the high-temperature treatment improved the performance of HZSM-5 zeolites in n-heptane catalytic cracking,promoting the conversion and light olefins yield while inhibiting coke formation.Based on the kinetic and mechanism analysis,the improvement of HZSM-5 performance caused by high-temperature treatment has been attributed to the formation of extra-framework Al,which enhanced the acid strength,facilitated the bimolecular reaction,and promoted the entropy change to overcome a higher energy barrier in n-heptane catalytic cracking.
基金the National Natural Science Foundation of China(52206262)Small and Medium-sized Sci-tech Enterprises Innovation Capability Improvement Project of Shandong Province,China(2022TSGC2248,2023TSGC0579)+1 种基金Talent Research Project of Qilu University of Technology(Shandong Academy of Sciences)(2023RCKY170)Natural Science Foundation of Shandong Province,China(ZR2020ME191).
文摘Catalytic cracking oil slurry is a by-product of catalytic cracking projects,and the efficient conversion and sustainable utilization of this material are issues of continuous concern in the petroleum refining industry.In this study,oxygen-enriched activated carbon is prepared using a one-step KOH activation method with catalytic cracking oil slurry as the raw material.The as-prepared oil slurry-based activated carbon exhibits a high specific surface area of 2102 m^(2)/g,welldefined micropores with an average diameter of 2 nm,and a rich oxygen doping content of 32.97%.The electrochemical performance of the nitrogen-doped porous carbon is tested in a three-electrode system using a 6 mol/L KOH solution as the electrolyte.It achieves a specific capacitance of up to 230 F/g at a current density of 1 A/g.Moreover,the capacitance retention rate exceeds 89%after 10000 charge and discharge cycles,demonstrating excellent cycle stability.This method not only improves the utilization efficiency of industrial fuel waste but also reduces the production cost of supercapacitor electrode materials,thereby providing a simple and effective strategy for the resource utilization of catalytic cracking oil slurries.
基金supported by the Key Research and Development Program of Shaanxi,China(2018GY-067).
文摘In this study,the perovskite nanocomposite PrFe_(x)Co_(1-x)O_(3)(Pr(S))was successfully synthesized by the sol-gel method;PrFe_(x)Co_(1-x)O_(3)/Al-pillared montmorillonite(Pr(S)/Mt)catalysts were prepared by impregnation(D)method and solid-melting(G)method,respectively,with Pr(S)as the active component and Al-pillared montmorillonite as the carrier.The catalysts were applied to treat the 2-hydroxybenzoic acid(2-HA)-simulated wastewater by catalytic wet peroxide oxidation(CWPO)technique,and the chemical oxygen demand(COD)removal rate and the 2-HA degradation rate were used as indicators to evaluate the catalytic performance.The results of the experiment indicated that the solid-melting method was more conducive to preparing the catalyst when the Co/Fe molar ratio of 7:3 and the optimal structural properties of the catalysts were achieved.The influence of operating parameters,including reaction temperature,catalyst dosage,H_(2)O_(2)dosage,pH,and initial 2-HA concentration,were optimized for the degradation of 2-HA by CWPO.The results showed that 97.64%of 2-HA degradation and 75.23%of COD removal rate were achieved under more suitable experimental conditions.In addition,after the catalyst was used five times,the degradation rate of 2-HA could still reach 76.93%,which implied the high stability and reusability of the catalyst.The high catalytic activity of the catalyst was due to the doping of Co into PrFeO_(3),which could promote the generation of HO·,and the high stability could be attributed to the loading of Pr(S)onto Al-Mt,which reduced the leaching of reactive metals.The study of reaction mechanism and kinetics showed that the whole degradation process conformed to the pseudo-firstorder kinetic equation,and the Langmuir-Hinshelwood method was applied to demonstrate that catalysis was dominant in the degradation process.
基金the National Natural Science Foundation of China(21962008)Yunnan Province Excellent Youth Fund Project(202001AW070005)+1 种基金Candidate Talents Training Fund of Yunnan Province(2017PY269SQ,2018HB007)Yunnan Ten Thousand Talents Plan Young&Elite Talents Project(YNWR-QNBJ-2018-346).
文摘Electrochemical water splitting has long been considered an effective energy conversion technology for trans-ferring intermittent renewable electricity into hydrogen fuel,and the exploration of cost-effective and high-performance electrocatalysts is crucial in making electrolyzed water technology commercially viable.Cobalt phosphide(Co-P)has emerged as a catalyst of high potential owing to its high catalytic activity and durability in water splitting.This paper systematically reviews the latest advances in the development of Co-P-based materials for use in water splitting.The essential effects of P in enhancing the catalytic performance of the hydrogen evolution reaction and oxygen evolution reaction are first outlined.Then,versatile synthesis techniques for Co-P electrocatalysts are summarized,followed by advanced strategies to enhance the electrocatalytic performance of Co-P materials,including heteroatom doping,composite construction,integration with well-conductive sub-strates,and structure control from the viewpoint of experiment.Along with these optimization strategies,the understanding of the inherent mechanism of enhanced catalytic performance is also discussed.Finally,some existing challenges in the development of highly active and stable Co-P-based materials are clarified,and pro-spective directions for prompting the wide commercialization of water electrolysis technology are proposed.
基金Funded by the National Key Research and Development Program of China(No.2016YFC0209302)。
文摘Zirconium-based metal-organic framework UiO-66 was successfully prepared by solvothermal method,and UiO-66 was modified by adding regulators such as formic acid,acetic acid,and hydrochloric acid.The NH_(3)-SCR reactivity of the samples was evaluated by the denitration activity evaluation system,and the UiO-66 and the regulator-modified UiO-66 were characterized by XRD,SEM,BET,FTIR,TG,NH_(3)-TPD,etc.,the effects of regulator types on the structure and properties of UiO-66 were investigated.The experimental results show that,after adding the modifier,the morphology of UiO-66 changes from irregular quadrilateral with serious agglomeration to particles with regular crystal shape and good dispersibility,and the crystal morphology of the catalyst is improved.In addition,after adding the modifier,UiO-66 has a larger specific surface area and stronger surface acidity,which optimizes the catalytic performance of UiO-66.The catalytic performance test results of NH_(3)-SCR show that the low-temperature activity of UiO-66 is poor,and it only shows a certain catalytic activity at higher temperatures.The catalytic activity of UiO-66 was significantly improved after adding the regulator.Among them,the UiO-66-HCl modified with hydrochloric acid had the best catalytic activity,and the denitration rate reached 70%when the denitration temperature was 380℃.