Engineering nanomaterials at single-atomic sites could enable unprecedented catalytic properties for broad applications,yet it remains challenging to do so on the surface of multimetallic nanocrystals.Herein,we presen...Engineering nanomaterials at single-atomic sites could enable unprecedented catalytic properties for broad applications,yet it remains challenging to do so on the surface of multimetallic nanocrystals.Herein,we present the multifactorial engineering(size,shape,phase,and composition)of the fully ordered PtBi nanoplates at atomic level,achieving a unique catalyst surface where the face-centered cubic(fcc)Pt edges are modified by the isolated Pd atoms and BiO_(x)adatoms.This Pd_(1)/Pt-BiO_(x)electrocatalyst exhibits an ultrahigh mass activity of 16.01 A mg^(-1)Pt+Pd toward ethanol oxidation in alkaline electrolyte and enables a direct ethanol fuel cell of peak power density of 56.7 mW cm^(−2).The surrounding BiO_(x)adatoms are critical for mitigating CO-poisoning on the Pt surface,and the Pd_(1)/Pt single-atom alloy further facilitates the electrooxidation of CH_(3)CH_(2)OH.This work offers new insights into the rational design and construction of sophisticated catalyst surface at single-atomic sites for highly efficient electrocatalysis.展开更多
By integrating photocatalytic H_(2)O_(2) production with furfuryl alcohol(FAL)oxidation,this coupled process establishes an atom-economical pathway for sustainable chemical synthesis,simultaneously achieving energy st...By integrating photocatalytic H_(2)O_(2) production with furfuryl alcohol(FAL)oxidation,this coupled process establishes an atom-economical pathway for sustainable chemical synthesis,simultaneously achieving energy storage and biomass valorization.This study introduces a meticulously engineered MOF@MOF hierarchical photocatalytic architecture,specifically the PCN-134@MOF-525(PM-X series)composite,designed for synergistic catalysis of these processes.By strategically integrating two distinct MOF materials,we circumvent the limitations of single-component systems,such as facile charge carrier recombination,and establish a redox dualactive site catalytic system.This rational design transcends simple additivity,yielding emergent catalytic behaviors driven by precise control over interfacial electric fields and dynamic structural modulation.The resultant hierarchical organization enhances light harvesting,promotes efficient charge separation,and accelerates charge transfer kinetics.Mechanistic insights,derived from photoelectrochemical,spectroscopic,and in-situ IR analyses,reveal a synergistic interplay that suppresses electron-hole recombination and spatially segregates redox processes.PM-3 demonstrates a significant enhancement in catalytic efficiency(the highest value reported),exhibiting a 4.5-fold increase in both H_(2)O_(2) production and FAL oxidation rates compared to the individual MOF components,achieving near-quantitative FAL conversion and exceptional selectivity.This work provides a potent design blueprint,emphasizing interfacial engineering and structural synergy for unprecedented efficiency and selectivity in sustainable chemical transformations.展开更多
The structural modulation of metal-based heterostructure plays a vital role in achieving enhanced performances for highly efficient electrocatalysis.Here we design submonolayered Ru-modified Pd mesoporous nanosheets(P...The structural modulation of metal-based heterostructure plays a vital role in achieving enhanced performances for highly efficient electrocatalysis.Here we design submonolayered Ru-modified Pd mesoporous nanosheets(Pd-Ru MNSs)with the exposure of both Pd and Ru active sites as well as the high atomic utilization of two-dimensional structure.The obtained Pd-Ru MNSs can act as a highly efficient multifunctional catalyst for hydrogen evolution reaction(HER)and alcohol oxidation reactions including ethylene glycol oxidation(EGOR)and ethanol oxidation(EOR),offering new opportunities towards the alcohol oxidation assisted hydrogen production.Specifically,Pd-Ru MNSs demonstrate excellent HER performance in alkaline electrolyte,requiring an overpotential of only 16mV to reach 10mAcm^(−2),significantly outperforming Pd mesoporous nanosheets and commercial catalysts.Density functional theory calculations reveal that the Ru sites in Pd-Ru MNSs could facilitate the water adsorption,accelerate the water dissociation,and optimize the hydrogen desorption,leading to the superior HER activity.Pd-Ru MNSs also exhibit high mass activities of 11.19 A mg^(−1)Pd for EGOR and 8.84 A mg^(−1)Pd for EOR,which is 7.8 and 9.6 times than that of commercial Pd/C,respectively.The EGOR reaction pathway over Pd-Ru MNSs was further investigated by using in situ Fourier-transform infrared spectroscopy.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
Platinum group alloys have an excellent electronic structure for oxidation of alcohols,but the active sites are more susceptible to deactivation by CO adsorbates(CO_(ads)).The precise integration of single-atom and al...Platinum group alloys have an excellent electronic structure for oxidation of alcohols,but the active sites are more susceptible to deactivation by CO adsorbates(CO_(ads)).The precise integration of single-atom and alloy structures is highly attractive for energy conversion but still a challenge.Here,we report an ionexchange coupled in situ reduction strategy to fabricate hollow PtPdTe alloy nanoreactors loaded with atomically dispersed Cu sites(Cu_(SA)/h-PtPdTe NRs).The planted oxyphilic Cu single sites and resulted compressive strains are conductive to modulating the electronic structure of the active sites,which changes the rate-determining step of the reaction while inhibiting the formation of CO_(ads)and modulating the adsorption of intermediates,resulting in the improved activity and stability.Specifically,the obtained Cu_(SA)/h-PtPdTe NRs exhibit an excellent oxidation performance of multiple alcohols,especially for methanol and ethanol,with 8.0 and 10.3 times of the mass activity higher than Pt/C,and the activity could be recovered by refreshing the electrolyte and could be sustained for 72,000 and 36,000 s,respectively.Meanwhile,Cu_(SA)/h-PtPdTe NRs show superior oxidation performance and durability to ethylene glycol and glycerol.This work pioneers the realization of precise modulation of catalytic sites using single atoms and provides an encouraging pathway for the design of efficient and stable electrocatalysts for the oxidation of multiple alcohols,which could broaden the range of options and sources of fuel cells.展开更多
Stabilizing gold nanoparticles（AuNPs） within a desired size range is critical to realize their promising catalytic performance in many important reactions.Herein,we investigate the anti-sintering properties of cubic...Stabilizing gold nanoparticles（AuNPs） within a desired size range is critical to realize their promising catalytic performance in many important reactions.Herein,we investigate the anti-sintering properties of cubic mesoporous silica（FDU-12） as a function of pore entrance size.Simple adjustments to the type of organic template and reaction temperature enable the successful synthesis of FDU-12 with controllable entrance sizes（ 3,3-5 and 7 nm）.Excellent anti-sintering properties are observed for FDU-12 with a sub-5-nm entrance size（3-5 nm） over a wide loading concentration（1.0-8.3 wt%） and the AuNPs can be stabilized within a 4.5-5.0-nm range after calcination at 550 ℃in air for 5 h.Smaller entrance size（ 3 nm） prevents ingress of 3-nm AuNPs to the mesopores and results in low loading capacity and sintering.Conversely,FDU-12 possessing a larger entrance size（7 nm） shows promising anti-sintering properties at high loading concentrations,although catalytic performance is significantly lost at lower concentrations（e.g.2.1 wt%,14.2 ± 5.5 nm）.Different anti-sintering mechanisms are proposed for each of the different FDU-12 entrance sizes.Additionally,catalytic data indicates that the obtained 4.5-nm AuNPs supported on FDU-12 with a sub-5-nm entrance size exhibit excellent mass-specific activity（1544 mmol g_（Au）^（-1） h^（-1）） and selectivity（ 99%）at 230 ℃ for the gas-phase selective oxidation of cyclohexanol.展开更多
lmprovement of the charge separation of titanosilicate molecular sieves is critical to their use asphotocatalysts for oxidative organic transformations.In this work,MFI TS-1 molecular sievenanosheets(TS-1 NS)were synt...lmprovement of the charge separation of titanosilicate molecular sieves is critical to their use asphotocatalysts for oxidative organic transformations.In this work,MFI TS-1 molecular sievenanosheets(TS-1 NS)were synthesized by a low-temperature hydrothermal method using a tai-lored diquaternary ammonium surfactant as the structure-directing agent.Introducing Ni^2+cationsat the ion-exchange sites of the TS-1 NS framework significantly enhanced its photoactivity in aero-bic alcohol oxidation.The optimized Ni cation-functionalized TS-1 NS(Ni/TS-1 NS)provide impres-sive photoactivity,with a benzyl alcohol(BA)conversion of 78.9%and benzyl aldehyde(BAD)se-lectivity of 98.8%using O as the only oxidant under full light irradiation;this BAD yield is approx-imately six times greater than that obtained for bulk TS-1,and is maintained for five runs.The ex-cellent photoactivity of Ni/TS-1 NS is attributed to the significantly enlarged surface area of thetwo-dimensional morphology TS-1 NS,extra mesopores,and greatly improved charge separation.Compared with bulk TS-1,Ni/TS-1 NS has a much shorter charge transfer distance.Theas-introduced Ni species could capture the photoelectrons to further improve the charge separa-tion.This work opens the way to a class of highly selective,robust,and low-cost titanosilicate mo-lecular sieve-based photocatalysts with industrial potential for selective oxidative transformationsand pollutant degradation.展开更多
Selective aerobic oxidation of alcohols under mild conditions is of great importance yet challenging,with the activation of molecular oxygen(O2)as a crucial capability of the catalysts.Herein,we demonstrate that an Al...Selective aerobic oxidation of alcohols under mild conditions is of great importance yet challenging,with the activation of molecular oxygen(O2)as a crucial capability of the catalysts.Herein,we demonstrate that an Al2O3-supported Pd single-atom catalyst leads to higher activity and selectivity compared to Pd nanoparticles for the oxidation of cinnamyl alcohol.The Al2O3 support used in this study is rich in coordinately unsaturated Al3+sites,which are apt for binding to Pd atoms through oxygen bridges and present a distinct metal-support interaction(MSI).The suitable MSI then leads to a unique electronic characteristic of the Pd single atoms,which can be confirmed via X-ray photoelectron spectroscopy,normalized X-ray absorption near-edge structure,and diffuse reflectance Fourier transform infrared spectroscopy.Moreover,this unique electronic state is proposed to be responsible for its high catalytic activity.With the help of in-situ UV-vis spectra and electron spin resonance spectra,a specific alcohol oxidation route with O2 activation mechanism is then identified.Active oxygen species behaving chemically like singlet-O2 are generated from the interaction of O2 with Pd1/Al2O3,and then oxidize the partially dehydrogenated intermediates produced by the adsorbed allylic alcohols and Pd atoms to the desired alkenyl aldehyde.This work provides a promising path for the design and development of high-activity catalysts for aerobic oxidation reactions.展开更多
Efficient catalytic system with low energy consumption exhibits increasing importance due to the upcoming energy crisis.Given this situation,it should be an admirable strategy for reducing energy input by effectively ...Efficient catalytic system with low energy consumption exhibits increasing importance due to the upcoming energy crisis.Given this situation,it should be an admirable strategy for reducing energy input by effectively utilizing incident solar energy as a heat source during catalytic reactions.Herein,aza-fused7 r-conjugated microporous polymer(aza-CMP)with broad light absorption and high photothermal conversion efficiency was synthesized and utilized as a support for bimetallic AuPd nanocatalysts in light-driven benzyl alcohol oxidation.The AuPd nanoparticles anchored on aza-CMP(aza-CM P/Au_xPdy)exhibited excellent catalytic performance for benzyl alcohol oxidation under 50 mW/cm^2 light irradiation.The improved catalytic performance by the aza-CMP/Au_xPdy is attributed to the unique photothermal effect induced by aza-CMP,which can promote the catalytic benzyl alcohol oxidation occurring at Au Pd.This work presents a novel approach to effectively utilize solar energy for conventional catalytic reactions through photothermal effect.展开更多
Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity,abundant surface active sites,and efficient charge separation.Nevertheless,the roles...Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity,abundant surface active sites,and efficient charge separation.Nevertheless,the roles of different forms of atomically-dispersed metals(i.e.,single-atoms and atomic clusters)in photocatalytic reactions remain ambiguous.Herein,we developed an ethylenediamine(EDA)-assisted reduction method to controllably synthesize atomically dispersed Au in the forms of Au single atoms(Au_(SA)),Au clusters(Au_(C)),and a mixed-phase of Au_(SA)and Au_(C)(Au_(SA+C))on CdS.In addition,we elucidate the synergistic effect of Au_(SA)and Au_(C)in enhancing the photocatalytic performance of CdS substrates for simultaneous CO_(2)reduction and aryl alcohol oxidation.Specifically,Au_(SA)can effectively lower the energy barrier for the CO_(2)→*COOH conversion,while Au_(C)can enhance the adsorption of alcohols and reduce the energy barrier for dehydrogenation.As a result,the Au_(SA)and Au_(C)co-loaded CdS show impressive overall photocatalytic CO_(2)conversion performance,achieving remarkable CO and BAD production rates of 4.43 and 4.71 mmol g^(−1)h^(−1),with the selectivities of 93%and 99%,respectively.More importantly,the solar-to-chemical conversion efficiency of Au_(SA+C)/CdS reaches 0.57%,which is over fivefold higher than the typical solar-to-biomass conversion efficiency found in nature(ca.0.1%).This study comprehensively describes the roles of different forms of atomically-dispersed metals and their synergistic effects in photocatalytic reactions,which is anticipated to pave a new avenue in energy and environmental applications.展开更多
Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electro...Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.展开更多
The development of efficient photocatalysts for selective organic transformations under visible light remains a major challenge in sustainable chemistry.In this study,we present a straightforward solvothermal strategy...The development of efficient photocatalysts for selective organic transformations under visible light remains a major challenge in sustainable chemistry.In this study,we present a straightforward solvothermal strategy for fabricating a defect-engineered ZrO_(2)/UiO-66-NH_(2)hybrid material with abundant oxygen vacancies,enabling the visible-light-driven oxidation of benzyl alcohol to benzaldehyde.By optimizing the solvothermal treatment duration,the composite(UiO-66-NH_(2)-2h)achieves a 74.1%conversion of benzyl alcohol with>99%selectivity toward benzaldehyde under mild conditions,substantially out-performing pristine UiO-66-NH_(2).Structural and mechanistic studies reveal that the solvothermal process induces the in situ formation of ultrasmall,uniformly dispersed ZrO_(2)nanoparticles(~2.3 nm)within the MOF matrix,while simultaneously generating abundant oxygen vacancies,as confirmed by XPS,EPR,and HRTEM analyses.The defect-mediated electronic structure of the ZrO_(2)/UiO-66-NH_(2)hybrid enhances visible-light absorption,facilitates charge carrier separation,and pro-motes efficient activation of O_(2)into superoxide radicals(·O_(2)^(−)),the primary reactive species.Transient photocurrent measure-ments and electrochemical impedance spectroscopy further verify the improved charge separation efficiency.The synergistic interplay between oxygen vacancies and the intimate ZrO_(2)/UiO-66-NH_(2)interface provides a unique defect-mediated charge transfer pathway,distinguishing this system from conventional heterojunctions.This study demonstrates a facile,one-step approach to integrate defect engineering with interfacial hybridization in MOF-based photocatalysts,off ering a scalable route for solar-driven organic synthesis.展开更多
Photocatalytic H_(2) production has been regarded as a charming strategy for harvesting solar energy to chemical energy yet remains a great challenge due to the weak light absorption in visible range,low charge transf...Photocatalytic H_(2) production has been regarded as a charming strategy for harvesting solar energy to chemical energy yet remains a great challenge due to the weak light absorption in visible range,low charge transfer,and fast recombination of photogenerated carriers.Here,we integrate solar-driven water splitting with benzyl alcohol(BA)oxidation,a typical platform chemical from biomass,for producing H_(2) and benzaldehyde(BAD)over ZnIn_(2)S_(4) nanosheets doped with Ni and N(Ni-N/ZIS).Mechanism studies show that Ni-N/ZIS provides a fast charge channel(i.e.,Ni-N)for separating photogenerated electrons and holes,as a result of significantly enhanced photocatalytic performance.Impressively,Ni-N/ZIS displays a H_(2) productivity of 18.7 mmol g^(-1) h^(-1) with an apparent quantum yield(AQE)of 29.1% at 420 nm,which is 37.4,10.6 and 2.8 times higher than that of pristine ZIS,N/ZIS and Ni/ZIS,surpassing all the reported noble metal-free catalysts.Besides,the productivity of BAD reaches 17.5 mmol g^(-1) h^(-1) under the irradiation of visible light(λ≥420 nm).This work integrates two significant processes(i.e.,solar-driven water splitting with benzyl alcohol oxidation)for producing H_(2) and BAD,respectively,which will contribute to alleviating the current energy and environmental crisis.展开更多
Metal-organic frameworks(MOFs)would be as one of the highly promising candidates for the electrocatalytic oxidation of small organic molecules and electrochemical sensing due to their adjustable structures and abundan...Metal-organic frameworks(MOFs)would be as one of the highly promising candidates for the electrocatalytic oxidation of small organic molecules and electrochemical sensing due to their adjustable structures and abundant redox-active sites.The development of new chiral MOFs constructed from chiral ligands and the exploration of their applications in electrocatalysis and electrochemical sensing are still relatively lacking.Herein,three new chiral Ni(Ⅱ)-MOFs,namely[Ni_(2)(tda)_(2)(bib)(H_(2)O)_(4)](CTGU-53),[Ni_(2)(tda)_(2)(py)_(2)](CTGU-54)and[Ni_(2)(tda)_(2)(4,4′-bpy)_(2)](CTGU-55)have been prepared with tetrahydrothiazole-2,4-dicarboxylic acid)(H_(2)tda),Ni(NO_(3))_(2) and the auxiliary ligands such as 1,1′-benzene-1,4-diylbis(1H-imidazole(bib),pyridine(py)and 4,4′-bipyridine(4,4′-bpy)under solvothermal condition.The electrocatalytic and electrochemical sensing activities towards alcohol oxidation reaction(AOR)and glucose(Glu)detection of these MOFs were systematically investigated.Notably,CTGU-53 exhibits electrocatalytic performance for methanol oxidation(MOR)and ethanol oxidation(EOR),achieving high peak current densities of 31.02 and 31.88 mA·cm^(−2),and an excellent mass specific peak current of 219.0 and 225.1 mA·mg^(−1),respectively.In contrast,CTGU-55 emerges as a superior non-enzymatic glucose sensor,exhibiting remarkable sensitivity of 2066.1μA·cm^(−2)·mM^(−1),a wide linear range(10−1000μM),and an ultralow detection limit value(LOD=0.09μM,S/N=3),surpassing most reported MOF-based Glu sensors.CTGU-55 also features a fast response time,excellent selectivity against common interferents,and good cyclic stability.This work highlights chiral Ni-MOFs,particularly CTGU-53 and CTGU-55,as highly efficient electrocatalysts for AOR and ultrasensitive electrochemical probes for glucose monitoring,demonstrating significant potential for practical electrochemical applications.展开更多
Solar-driven CO_(2) photoreduction holds promise for sustainable fuel and chemical productions,but the complex proton-coupled multi-electron transfer processes and sluggish oxidation half-reaction kinetics substantial...Solar-driven CO_(2) photoreduction holds promise for sustainable fuel and chemical productions,but the complex proton-coupled multi-electron transfer processes and sluggish oxidation half-reaction kinetics substantially hinder its efficiency.Here,we devised a rational catalyst design to address these challenges by fabricating ferrocene carboxylic acid-functionalized Cs_(3)Sb_(2)Br_(9) nanocrystals(CSB-Fc NCs),which facilitate simultaneous benzyl alcohol oxidation and CO_(2) reduction reactions under visible-light irradiation.The synchronized proton-coupled electron transfer processes between the reduction and oxidation half-reactions on CSB-Fc NCs resulted in a 5-fold increase in the CO_(2) reduction rate(45.56μmol g^(-1) h^(-1),97.9%CO selectivity)and a 5.8-fold enhancement in benzyl alcohol conversion(97.7% selectivity for benzaldehyde)compared to the CSB.In situ Raman and ultraviolet-visible diffuse reflectance spectra revealed that the dynamic Fe^(2+)/Fe^(3+)redox loop within the Fc unit serves as the actual active site,facilitating the activation of substrate molecules.More importantly,in situ attenuated total reflection Fourier transform infrared spectroscopy and gas chromatography-mass spectrometry spectroscopy,with isotope labeling of Deuteron-benzyl alcohol and ^(13)CO_(2),confirmed that proton transfer from the hydroxyl group generates reactive protons at the Fe^(2+)/Fe^(3+)site,enabling efficient CO_(2) photoreduction through subsequent protonation steps.This work offers a cost-effective and efficient approach for synergetic CO_(2) photoreduction driven by organic synthesis,advancing solar energy utilization.展开更多
Two cobalt（Ⅱ） complexes 1 and 2 of Schiff bases derived from amino acids were synthesized and used for oxidation of benzyl alcohol with molecular oxygen at different conditions of pH,solvent,temperature and complex...Two cobalt（Ⅱ） complexes 1 and 2 of Schiff bases derived from amino acids were synthesized and used for oxidation of benzyl alcohol with molecular oxygen at different conditions of pH,solvent,temperature and complex/alcohol molar ratio to optimize reaction conditions and to evaluate the catalytic efficiency of new cobalt Schiff base complexes.Under obtained optimum conditions,various alcohols were oxidized to corresponding aldehydes and ketones.展开更多
Building a covalently connected structure with accelerated photo-induced electrons and charge-carrier separation between semiconductors could enhance the photocatalytic performance.In this work,we report a facile and ...Building a covalently connected structure with accelerated photo-induced electrons and charge-carrier separation between semiconductors could enhance the photocatalytic performance.In this work,we report a facile and novel seed growth method to coat NH2-MIL-125 MOFs with crystalline and porous covalent organic frameworks(COFs)materials and form a range of NH2-MIL-125@TAPB-PDA nanocomposites with different thicknesses of COF shell.The introduction of appropriate content of COF could not only modify the intrinsic electronic and optical properties,but also enhance the photocatalytic activity distinctly.Especially,NH2-MIL-125@TAPB-PDA-3 with COF shell thickness of around 20nm exhibited the highest yield(94.7%)of benzaldehyde which is approximately 2.5 and 15.5 times as that of parental NH2-MIL-125 and COF,respectively.The promoted photocatalytic performance of hybrid materials was mainly owing to the enhanced photo-induced charge carriers transfer between the MOF and COF through the covalent bond.In addition,a possible mechanism to elucidate the process of photocatalysis was explored.Therefore,this kind of MOF-based photocatalysts possesses great potentials in future green organic synthesis.展开更多
Traditional conversion of alcohols into carbonyl compounds exists a few drawbacks such as harsh reaction conditions,production of large amounts of hazardous wastes,and poor selectivity.The newly emerging conversion ap...Traditional conversion of alcohols into carbonyl compounds exists a few drawbacks such as harsh reaction conditions,production of large amounts of hazardous wastes,and poor selectivity.The newly emerging conversion approaches via photo-,electro-,and photoelectro-catalysis to oxidize alcohols into high value-added corresponding carbonyl compounds as well as the possible simultaneous production of clean fuel hydrogen(H_(2))under mild conditions are promising to substitute the traditional approach to form greener and sustainable reaction systems and thus have aroused tremendous investigations.In this review,the state-of-the-art photocatalytic,electrocatalytic,and photoelectrocatalytic strategies for selective oxidation of different types of alcohols(aromatic and aliphatic alcohols,single alcohol,and polyols,etc.)as well as the simultaneous production of H_(2) in certain systems are discussed.The design of photocatalysts,electrocatalysts,and photoelectrocatalysts as well as reaction mechanism is summarized and discussed in detail.In the end,current challenges and future research directions are proposed.It is expected that this review will not only deepen the understanding of environmentally friendly catalytic systems for alcohol conversion as well as H_(2) production,but also enlighten significance and inspirations for the follow-up study of selective oxidation of various types of organic molecules to value-added chemicals.展开更多
MnFe1.4Ru0.45Cu0.15O4 was an effective heterogeneous catalyst for the oxidation of various types of alcohols to the corresponding carbonyl compounds using atmospheric pressure of oxygen under mild conditions. Further...MnFe1.4Ru0.45Cu0.15O4 was an effective heterogeneous catalyst for the oxidation of various types of alcohols to the corresponding carbonyl compounds using atmospheric pressure of oxygen under mild conditions. Furthermore, this catalyst was also effective towards alcohol oxidation using water as solvent instead of toluene.展开更多
Metallenes are an emerging class of two-dimensional(2D)material with outstanding potential in electrocatalysis.Herein,we present a new PdMoSb trimetallene produced by a facile wet-chemistry procedure and tested for th...Metallenes are an emerging class of two-dimensional(2D)material with outstanding potential in electrocatalysis.Herein,we present a new PdMoSb trimetallene produced by a facile wet-chemistry procedure and tested for the alcohol oxidation reaction.PdMoSb shows an extremely high Pd utilization and superior performance toward ethanol,methanol,and glycerol electro-oxidation compared with PdMo and commercial Pd/C catalysts.Experimental results and density functional theory calculations reveal that the enhanced activity relies not only on the high surface area that characterizes the ultrathin 2D metallene structure,but also on the particular electronic configuration of Sb.Sb facilitates OH−adsorption in the reactive-intermediate pathway and strongly enhances the CO tolerance in the poisoning-intermediate pathway for alcohol oxidation.The excellent alcohol oxidation performance of PdMoSb trimetallene demonstrates the high potential of multimetallenes in the field of electrocatalysis.展开更多
基金supported by the National Natural Science Foundation of China(NSFC)(Grant Nos.22475132 and 52101259)the Shenzhen Science and Technology Innovation Committee(Grant No.JCYJ20210324105008022)financially supported by the Shenzhen Science and Technology Innovation Program(Nos.KQTD20190929173914967 and ZDSYS20220527171401003).
文摘Engineering nanomaterials at single-atomic sites could enable unprecedented catalytic properties for broad applications,yet it remains challenging to do so on the surface of multimetallic nanocrystals.Herein,we present the multifactorial engineering(size,shape,phase,and composition)of the fully ordered PtBi nanoplates at atomic level,achieving a unique catalyst surface where the face-centered cubic(fcc)Pt edges are modified by the isolated Pd atoms and BiO_(x)adatoms.This Pd_(1)/Pt-BiO_(x)electrocatalyst exhibits an ultrahigh mass activity of 16.01 A mg^(-1)Pt+Pd toward ethanol oxidation in alkaline electrolyte and enables a direct ethanol fuel cell of peak power density of 56.7 mW cm^(−2).The surrounding BiO_(x)adatoms are critical for mitigating CO-poisoning on the Pt surface,and the Pd_(1)/Pt single-atom alloy further facilitates the electrooxidation of CH_(3)CH_(2)OH.This work offers new insights into the rational design and construction of sophisticated catalyst surface at single-atomic sites for highly efficient electrocatalysis.
基金supported by National Natural Science Foundation of China(22378219)Project ZR2023QB173 supported by Shandong Provincial Natural Science Foundation and Postdoctoral Application Project of Qingdao(QHBSH20230102024)Prof.H.Tang gratefully acknowledges financial support from Taishan Youth Scholar Program of Shandong Province.
文摘By integrating photocatalytic H_(2)O_(2) production with furfuryl alcohol(FAL)oxidation,this coupled process establishes an atom-economical pathway for sustainable chemical synthesis,simultaneously achieving energy storage and biomass valorization.This study introduces a meticulously engineered MOF@MOF hierarchical photocatalytic architecture,specifically the PCN-134@MOF-525(PM-X series)composite,designed for synergistic catalysis of these processes.By strategically integrating two distinct MOF materials,we circumvent the limitations of single-component systems,such as facile charge carrier recombination,and establish a redox dualactive site catalytic system.This rational design transcends simple additivity,yielding emergent catalytic behaviors driven by precise control over interfacial electric fields and dynamic structural modulation.The resultant hierarchical organization enhances light harvesting,promotes efficient charge separation,and accelerates charge transfer kinetics.Mechanistic insights,derived from photoelectrochemical,spectroscopic,and in-situ IR analyses,reveal a synergistic interplay that suppresses electron-hole recombination and spatially segregates redox processes.PM-3 demonstrates a significant enhancement in catalytic efficiency(the highest value reported),exhibiting a 4.5-fold increase in both H_(2)O_(2) production and FAL oxidation rates compared to the individual MOF components,achieving near-quantitative FAL conversion and exceptional selectivity.This work provides a potent design blueprint,emphasizing interfacial engineering and structural synergy for unprecedented efficiency and selectivity in sustainable chemical transformations.
基金financial support from the National Natural Science Foundation of China(No.52471219)the Fundamental Research Funds for the Central Universities(No.00007838)+5 种基金financial support from the National Natural Science Foundation of China(No.52471220 and U2441264)the Guangdong Basic and Applied Basic Research Foundation(No.2022A1515140051)financial support from the National Natural Science Foundation of China(No.92163209)Beijing Natural Science Foundation(No.JQ22004)financial support from the National Natural Science Foundation of China(No.52476146)Guangdong Basic and Applied Basic Research Foundation(2023A1515140059,2025A1515011255).
文摘The structural modulation of metal-based heterostructure plays a vital role in achieving enhanced performances for highly efficient electrocatalysis.Here we design submonolayered Ru-modified Pd mesoporous nanosheets(Pd-Ru MNSs)with the exposure of both Pd and Ru active sites as well as the high atomic utilization of two-dimensional structure.The obtained Pd-Ru MNSs can act as a highly efficient multifunctional catalyst for hydrogen evolution reaction(HER)and alcohol oxidation reactions including ethylene glycol oxidation(EGOR)and ethanol oxidation(EOR),offering new opportunities towards the alcohol oxidation assisted hydrogen production.Specifically,Pd-Ru MNSs demonstrate excellent HER performance in alkaline electrolyte,requiring an overpotential of only 16mV to reach 10mAcm^(−2),significantly outperforming Pd mesoporous nanosheets and commercial catalysts.Density functional theory calculations reveal that the Ru sites in Pd-Ru MNSs could facilitate the water adsorption,accelerate the water dissociation,and optimize the hydrogen desorption,leading to the superior HER activity.Pd-Ru MNSs also exhibit high mass activities of 11.19 A mg^(−1)Pd for EGOR and 8.84 A mg^(−1)Pd for EOR,which is 7.8 and 9.6 times than that of commercial Pd/C,respectively.The EGOR reaction pathway over Pd-Ru MNSs was further investigated by using in situ Fourier-transform infrared spectroscopy.
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 National Natural Science Foundation of China(22102132)the Funds for Basic Scientific Research in Central Universities+2 种基金the Scientific Research Foundation of Qingdao UniversityTaishan Scholar Program(NO.tsqnz20231213)sponsored by the Innovation Foundation for Doctor Dissertation of Northwestern Polytechnical University(CX2024101)。
文摘Platinum group alloys have an excellent electronic structure for oxidation of alcohols,but the active sites are more susceptible to deactivation by CO adsorbates(CO_(ads)).The precise integration of single-atom and alloy structures is highly attractive for energy conversion but still a challenge.Here,we report an ionexchange coupled in situ reduction strategy to fabricate hollow PtPdTe alloy nanoreactors loaded with atomically dispersed Cu sites(Cu_(SA)/h-PtPdTe NRs).The planted oxyphilic Cu single sites and resulted compressive strains are conductive to modulating the electronic structure of the active sites,which changes the rate-determining step of the reaction while inhibiting the formation of CO_(ads)and modulating the adsorption of intermediates,resulting in the improved activity and stability.Specifically,the obtained Cu_(SA)/h-PtPdTe NRs exhibit an excellent oxidation performance of multiple alcohols,especially for methanol and ethanol,with 8.0 and 10.3 times of the mass activity higher than Pt/C,and the activity could be recovered by refreshing the electrolyte and could be sustained for 72,000 and 36,000 s,respectively.Meanwhile,Cu_(SA)/h-PtPdTe NRs show superior oxidation performance and durability to ethylene glycol and glycerol.This work pioneers the realization of precise modulation of catalytic sites using single atoms and provides an encouraging pathway for the design of efficient and stable electrocatalysts for the oxidation of multiple alcohols,which could broaden the range of options and sources of fuel cells.
基金supported by the National Natural Science Foundation of China(21222307,21373181,21403197,91545113,21503189)the Fundamental Research Funds for the Central Universities(2014XZZX003-02)+1 种基金Zhejiang Provincial Natural Science Foundation(LY15B030009)China Postdoctoral Science Foundation(2014M550333,2015T80636)~~
文摘Stabilizing gold nanoparticles（AuNPs） within a desired size range is critical to realize their promising catalytic performance in many important reactions.Herein,we investigate the anti-sintering properties of cubic mesoporous silica（FDU-12） as a function of pore entrance size.Simple adjustments to the type of organic template and reaction temperature enable the successful synthesis of FDU-12 with controllable entrance sizes（ 3,3-5 and 7 nm）.Excellent anti-sintering properties are observed for FDU-12 with a sub-5-nm entrance size（3-5 nm） over a wide loading concentration（1.0-8.3 wt%） and the AuNPs can be stabilized within a 4.5-5.0-nm range after calcination at 550 ℃in air for 5 h.Smaller entrance size（ 3 nm） prevents ingress of 3-nm AuNPs to the mesopores and results in low loading capacity and sintering.Conversely,FDU-12 possessing a larger entrance size（7 nm） shows promising anti-sintering properties at high loading concentrations,although catalytic performance is significantly lost at lower concentrations（e.g.2.1 wt%,14.2 ± 5.5 nm）.Different anti-sintering mechanisms are proposed for each of the different FDU-12 entrance sizes.Additionally,catalytic data indicates that the obtained 4.5-nm AuNPs supported on FDU-12 with a sub-5-nm entrance size exhibit excellent mass-specific activity（1544 mmol g_（Au）^（-1） h^（-1）） and selectivity（ 99%）at 230 ℃ for the gas-phase selective oxidation of cyclohexanol.
文摘lmprovement of the charge separation of titanosilicate molecular sieves is critical to their use asphotocatalysts for oxidative organic transformations.In this work,MFI TS-1 molecular sievenanosheets(TS-1 NS)were synthesized by a low-temperature hydrothermal method using a tai-lored diquaternary ammonium surfactant as the structure-directing agent.Introducing Ni^2+cationsat the ion-exchange sites of the TS-1 NS framework significantly enhanced its photoactivity in aero-bic alcohol oxidation.The optimized Ni cation-functionalized TS-1 NS(Ni/TS-1 NS)provide impres-sive photoactivity,with a benzyl alcohol(BA)conversion of 78.9%and benzyl aldehyde(BAD)se-lectivity of 98.8%using O as the only oxidant under full light irradiation;this BAD yield is approx-imately six times greater than that obtained for bulk TS-1,and is maintained for five runs.The ex-cellent photoactivity of Ni/TS-1 NS is attributed to the significantly enlarged surface area of thetwo-dimensional morphology TS-1 NS,extra mesopores,and greatly improved charge separation.Compared with bulk TS-1,Ni/TS-1 NS has a much shorter charge transfer distance.Theas-introduced Ni species could capture the photoelectrons to further improve the charge separa-tion.This work opens the way to a class of highly selective,robust,and low-cost titanosilicate mo-lecular sieve-based photocatalysts with industrial potential for selective oxidative transformationsand pollutant degradation.
文摘Selective aerobic oxidation of alcohols under mild conditions is of great importance yet challenging,with the activation of molecular oxygen(O2)as a crucial capability of the catalysts.Herein,we demonstrate that an Al2O3-supported Pd single-atom catalyst leads to higher activity and selectivity compared to Pd nanoparticles for the oxidation of cinnamyl alcohol.The Al2O3 support used in this study is rich in coordinately unsaturated Al3+sites,which are apt for binding to Pd atoms through oxygen bridges and present a distinct metal-support interaction(MSI).The suitable MSI then leads to a unique electronic characteristic of the Pd single atoms,which can be confirmed via X-ray photoelectron spectroscopy,normalized X-ray absorption near-edge structure,and diffuse reflectance Fourier transform infrared spectroscopy.Moreover,this unique electronic state is proposed to be responsible for its high catalytic activity.With the help of in-situ UV-vis spectra and electron spin resonance spectra,a specific alcohol oxidation route with O2 activation mechanism is then identified.Active oxygen species behaving chemically like singlet-O2 are generated from the interaction of O2 with Pd1/Al2O3,and then oxidize the partially dehydrogenated intermediates produced by the adsorbed allylic alcohols and Pd atoms to the desired alkenyl aldehyde.This work provides a promising path for the design and development of high-activity catalysts for aerobic oxidation reactions.
基金supported by National Key R&D Program of China (Nos.2017YFA0207301,2017YFA0207302)the National Natural Science Foundation of China (NSFC,Nos.21725102,21601173, U1832156,21881240040,21573212)+3 种基金CAS Key Research Program of Frontier Sciences (No.QYZDB-SSW-SLH018)CAS Interdisciplinary Innovation Team,and Chinese Universities Scientific Fund (No. WK2310000067)funded by Chinese Academy of Sciences President’s International Fellowship Initiative (No. 2019PC0114)support from USTC Center for Microand Nanoscale Research and Fabrication
文摘Efficient catalytic system with low energy consumption exhibits increasing importance due to the upcoming energy crisis.Given this situation,it should be an admirable strategy for reducing energy input by effectively utilizing incident solar energy as a heat source during catalytic reactions.Herein,aza-fused7 r-conjugated microporous polymer(aza-CMP)with broad light absorption and high photothermal conversion efficiency was synthesized and utilized as a support for bimetallic AuPd nanocatalysts in light-driven benzyl alcohol oxidation.The AuPd nanoparticles anchored on aza-CMP(aza-CM P/Au_xPdy)exhibited excellent catalytic performance for benzyl alcohol oxidation under 50 mW/cm^2 light irradiation.The improved catalytic performance by the aza-CMP/Au_xPdy is attributed to the unique photothermal effect induced by aza-CMP,which can promote the catalytic benzyl alcohol oxidation occurring at Au Pd.This work presents a novel approach to effectively utilize solar energy for conventional catalytic reactions through photothermal effect.
文摘Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity,abundant surface active sites,and efficient charge separation.Nevertheless,the roles of different forms of atomically-dispersed metals(i.e.,single-atoms and atomic clusters)in photocatalytic reactions remain ambiguous.Herein,we developed an ethylenediamine(EDA)-assisted reduction method to controllably synthesize atomically dispersed Au in the forms of Au single atoms(Au_(SA)),Au clusters(Au_(C)),and a mixed-phase of Au_(SA)and Au_(C)(Au_(SA+C))on CdS.In addition,we elucidate the synergistic effect of Au_(SA)and Au_(C)in enhancing the photocatalytic performance of CdS substrates for simultaneous CO_(2)reduction and aryl alcohol oxidation.Specifically,Au_(SA)can effectively lower the energy barrier for the CO_(2)→*COOH conversion,while Au_(C)can enhance the adsorption of alcohols and reduce the energy barrier for dehydrogenation.As a result,the Au_(SA)and Au_(C)co-loaded CdS show impressive overall photocatalytic CO_(2)conversion performance,achieving remarkable CO and BAD production rates of 4.43 and 4.71 mmol g^(−1)h^(−1),with the selectivities of 93%and 99%,respectively.More importantly,the solar-to-chemical conversion efficiency of Au_(SA+C)/CdS reaches 0.57%,which is over fivefold higher than the typical solar-to-biomass conversion efficiency found in nature(ca.0.1%).This study comprehensively describes the roles of different forms of atomically-dispersed metals and their synergistic effects in photocatalytic reactions,which is anticipated to pave a new avenue in energy and environmental applications.
基金the financial support from the National Natural Science Foundation of China(52172110,52472231,52311530113)Shanghai"Science and Technology Innovation Action Plan"intergovernmental international science and technology cooperation project(23520710600)+1 种基金Science and Technology Commission of Shanghai Municipality(22DZ1205600)the Central Guidance on Science and Technology Development Fund of Zhejiang Province(2024ZY01011)。
文摘Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.
基金the National Natural Sci-ence Foundation of China(Nos.22271038,22378038,22172012)C.P.thanks Dalian Science and Technology Innovation Fund(No.2024JJ12CG033)+1 种基金C.P.and Z.S thank State Key Laboratory of Heavy Oil Processing(Nos.WX20230149,SKLHOP202402005)Y.-Y.L.thanks the Guangxi Key Laboratory of Information Materials,Guilin University of Electronic Technology(No.231019-K).
文摘The development of efficient photocatalysts for selective organic transformations under visible light remains a major challenge in sustainable chemistry.In this study,we present a straightforward solvothermal strategy for fabricating a defect-engineered ZrO_(2)/UiO-66-NH_(2)hybrid material with abundant oxygen vacancies,enabling the visible-light-driven oxidation of benzyl alcohol to benzaldehyde.By optimizing the solvothermal treatment duration,the composite(UiO-66-NH_(2)-2h)achieves a 74.1%conversion of benzyl alcohol with>99%selectivity toward benzaldehyde under mild conditions,substantially out-performing pristine UiO-66-NH_(2).Structural and mechanistic studies reveal that the solvothermal process induces the in situ formation of ultrasmall,uniformly dispersed ZrO_(2)nanoparticles(~2.3 nm)within the MOF matrix,while simultaneously generating abundant oxygen vacancies,as confirmed by XPS,EPR,and HRTEM analyses.The defect-mediated electronic structure of the ZrO_(2)/UiO-66-NH_(2)hybrid enhances visible-light absorption,facilitates charge carrier separation,and pro-motes efficient activation of O_(2)into superoxide radicals(·O_(2)^(−)),the primary reactive species.Transient photocurrent measure-ments and electrochemical impedance spectroscopy further verify the improved charge separation efficiency.The synergistic interplay between oxygen vacancies and the intimate ZrO_(2)/UiO-66-NH_(2)interface provides a unique defect-mediated charge transfer pathway,distinguishing this system from conventional heterojunctions.This study demonstrates a facile,one-step approach to integrate defect engineering with interfacial hybridization in MOF-based photocatalysts,off ering a scalable route for solar-driven organic synthesis.
基金supported by the National Key R&D Program of China(2022YFA1504500)National Natural Science Foundation of China(52472310,22025108,U21A20327,and 22121001)+4 种基金Gusu Leading Talent Program(ZXL2024347)Guangdong Provincial Natural Science Fund for Distinguished Young Scholars(2021B1515020081)Pioneer Hundred Talents Program of Chinese Academy of SciencesNatural Science Foundation of the Jiangsu Higher Education Institutions(22KJA430009)Science and Technology Development Plan of Suzhou(ZXL2022176).
文摘Photocatalytic H_(2) production has been regarded as a charming strategy for harvesting solar energy to chemical energy yet remains a great challenge due to the weak light absorption in visible range,low charge transfer,and fast recombination of photogenerated carriers.Here,we integrate solar-driven water splitting with benzyl alcohol(BA)oxidation,a typical platform chemical from biomass,for producing H_(2) and benzaldehyde(BAD)over ZnIn_(2)S_(4) nanosheets doped with Ni and N(Ni-N/ZIS).Mechanism studies show that Ni-N/ZIS provides a fast charge channel(i.e.,Ni-N)for separating photogenerated electrons and holes,as a result of significantly enhanced photocatalytic performance.Impressively,Ni-N/ZIS displays a H_(2) productivity of 18.7 mmol g^(-1) h^(-1) with an apparent quantum yield(AQE)of 29.1% at 420 nm,which is 37.4,10.6 and 2.8 times higher than that of pristine ZIS,N/ZIS and Ni/ZIS,surpassing all the reported noble metal-free catalysts.Besides,the productivity of BAD reaches 17.5 mmol g^(-1) h^(-1) under the irradiation of visible light(λ≥420 nm).This work integrates two significant processes(i.e.,solar-driven water splitting with benzyl alcohol oxidation)for producing H_(2) and BAD,respectively,which will contribute to alleviating the current energy and environmental crisis.
基金the National Natural Science Foundation of China(Nos.22371165 and 22209098)the 111 Project(No.D20015)ITOYMR in the Higher Education Institutions of Hubei Province(No.T201904).
文摘Metal-organic frameworks(MOFs)would be as one of the highly promising candidates for the electrocatalytic oxidation of small organic molecules and electrochemical sensing due to their adjustable structures and abundant redox-active sites.The development of new chiral MOFs constructed from chiral ligands and the exploration of their applications in electrocatalysis and electrochemical sensing are still relatively lacking.Herein,three new chiral Ni(Ⅱ)-MOFs,namely[Ni_(2)(tda)_(2)(bib)(H_(2)O)_(4)](CTGU-53),[Ni_(2)(tda)_(2)(py)_(2)](CTGU-54)and[Ni_(2)(tda)_(2)(4,4′-bpy)_(2)](CTGU-55)have been prepared with tetrahydrothiazole-2,4-dicarboxylic acid)(H_(2)tda),Ni(NO_(3))_(2) and the auxiliary ligands such as 1,1′-benzene-1,4-diylbis(1H-imidazole(bib),pyridine(py)and 4,4′-bipyridine(4,4′-bpy)under solvothermal condition.The electrocatalytic and electrochemical sensing activities towards alcohol oxidation reaction(AOR)and glucose(Glu)detection of these MOFs were systematically investigated.Notably,CTGU-53 exhibits electrocatalytic performance for methanol oxidation(MOR)and ethanol oxidation(EOR),achieving high peak current densities of 31.02 and 31.88 mA·cm^(−2),and an excellent mass specific peak current of 219.0 and 225.1 mA·mg^(−1),respectively.In contrast,CTGU-55 emerges as a superior non-enzymatic glucose sensor,exhibiting remarkable sensitivity of 2066.1μA·cm^(−2)·mM^(−1),a wide linear range(10−1000μM),and an ultralow detection limit value(LOD=0.09μM,S/N=3),surpassing most reported MOF-based Glu sensors.CTGU-55 also features a fast response time,excellent selectivity against common interferents,and good cyclic stability.This work highlights chiral Ni-MOFs,particularly CTGU-53 and CTGU-55,as highly efficient electrocatalysts for AOR and ultrasensitive electrochemical probes for glucose monitoring,demonstrating significant potential for practical electrochemical applications.
基金supported by the National Natural Science Foundation of China(22361142703,22225606,and 22172019).
文摘Solar-driven CO_(2) photoreduction holds promise for sustainable fuel and chemical productions,but the complex proton-coupled multi-electron transfer processes and sluggish oxidation half-reaction kinetics substantially hinder its efficiency.Here,we devised a rational catalyst design to address these challenges by fabricating ferrocene carboxylic acid-functionalized Cs_(3)Sb_(2)Br_(9) nanocrystals(CSB-Fc NCs),which facilitate simultaneous benzyl alcohol oxidation and CO_(2) reduction reactions under visible-light irradiation.The synchronized proton-coupled electron transfer processes between the reduction and oxidation half-reactions on CSB-Fc NCs resulted in a 5-fold increase in the CO_(2) reduction rate(45.56μmol g^(-1) h^(-1),97.9%CO selectivity)and a 5.8-fold enhancement in benzyl alcohol conversion(97.7% selectivity for benzaldehyde)compared to the CSB.In situ Raman and ultraviolet-visible diffuse reflectance spectra revealed that the dynamic Fe^(2+)/Fe^(3+)redox loop within the Fc unit serves as the actual active site,facilitating the activation of substrate molecules.More importantly,in situ attenuated total reflection Fourier transform infrared spectroscopy and gas chromatography-mass spectrometry spectroscopy,with isotope labeling of Deuteron-benzyl alcohol and ^(13)CO_(2),confirmed that proton transfer from the hydroxyl group generates reactive protons at the Fe^(2+)/Fe^(3+)site,enabling efficient CO_(2) photoreduction through subsequent protonation steps.This work offers a cost-effective and efficient approach for synergetic CO_(2) photoreduction driven by organic synthesis,advancing solar energy utilization.
文摘Two cobalt（Ⅱ） complexes 1 and 2 of Schiff bases derived from amino acids were synthesized and used for oxidation of benzyl alcohol with molecular oxygen at different conditions of pH,solvent,temperature and complex/alcohol molar ratio to optimize reaction conditions and to evaluate the catalytic efficiency of new cobalt Schiff base complexes.Under obtained optimum conditions,various alcohols were oxidized to corresponding aldehydes and ketones.
基金the National Key Research and Development Program of China(No.2016YFB0701100)the National Natural Science Foundation of China(Nos.51802015 and 51890893)Fundamental Research Funds for the Central Universities(FRFTP-16-028A1)。
文摘Building a covalently connected structure with accelerated photo-induced electrons and charge-carrier separation between semiconductors could enhance the photocatalytic performance.In this work,we report a facile and novel seed growth method to coat NH2-MIL-125 MOFs with crystalline and porous covalent organic frameworks(COFs)materials and form a range of NH2-MIL-125@TAPB-PDA nanocomposites with different thicknesses of COF shell.The introduction of appropriate content of COF could not only modify the intrinsic electronic and optical properties,but also enhance the photocatalytic activity distinctly.Especially,NH2-MIL-125@TAPB-PDA-3 with COF shell thickness of around 20nm exhibited the highest yield(94.7%)of benzaldehyde which is approximately 2.5 and 15.5 times as that of parental NH2-MIL-125 and COF,respectively.The promoted photocatalytic performance of hybrid materials was mainly owing to the enhanced photo-induced charge carriers transfer between the MOF and COF through the covalent bond.In addition,a possible mechanism to elucidate the process of photocatalysis was explored.Therefore,this kind of MOF-based photocatalysts possesses great potentials in future green organic synthesis.
基金support from the National Natural Science Foundation of China(21976054,22176054)the Fundamental Research Funds for the Central Universities(2020MS036,FRF-TP-20-005A3)+1 种基金the Fundamental Research Funds for the Central Universities and the Youth Teacher International Exchange&Growth Program(QNXM20220026)MOE Key Laboratory of Resources and Environmental System Optimization,College of Environmental Science and Engineering,North China Electric Power University(KLRE-KF202201)。
文摘Traditional conversion of alcohols into carbonyl compounds exists a few drawbacks such as harsh reaction conditions,production of large amounts of hazardous wastes,and poor selectivity.The newly emerging conversion approaches via photo-,electro-,and photoelectro-catalysis to oxidize alcohols into high value-added corresponding carbonyl compounds as well as the possible simultaneous production of clean fuel hydrogen(H_(2))under mild conditions are promising to substitute the traditional approach to form greener and sustainable reaction systems and thus have aroused tremendous investigations.In this review,the state-of-the-art photocatalytic,electrocatalytic,and photoelectrocatalytic strategies for selective oxidation of different types of alcohols(aromatic and aliphatic alcohols,single alcohol,and polyols,etc.)as well as the simultaneous production of H_(2) in certain systems are discussed.The design of photocatalysts,electrocatalysts,and photoelectrocatalysts as well as reaction mechanism is summarized and discussed in detail.In the end,current challenges and future research directions are proposed.It is expected that this review will not only deepen the understanding of environmentally friendly catalytic systems for alcohol conversion as well as H_(2) production,but also enlighten significance and inspirations for the follow-up study of selective oxidation of various types of organic molecules to value-added chemicals.
文摘MnFe1.4Ru0.45Cu0.15O4 was an effective heterogeneous catalyst for the oxidation of various types of alcohols to the corresponding carbonyl compounds using atmospheric pressure of oxygen under mild conditions. Furthermore, this catalyst was also effective towards alcohol oxidation using water as solvent instead of toluene.
基金supported by the National Natural Science Foundation of China(No.22008091)the funding for scientific research startup of Jiangsu University(No.19JDG044)the Jiangsu Provincial Program for High-Level Innovative and Entrepreneurial Talents Introduction.A.C.thanks support from the project COMBENERGY(No.PID2019-105490RB-C32)of the Spanish Ministerio de Ciencia e Innovación.
文摘Metallenes are an emerging class of two-dimensional(2D)material with outstanding potential in electrocatalysis.Herein,we present a new PdMoSb trimetallene produced by a facile wet-chemistry procedure and tested for the alcohol oxidation reaction.PdMoSb shows an extremely high Pd utilization and superior performance toward ethanol,methanol,and glycerol electro-oxidation compared with PdMo and commercial Pd/C catalysts.Experimental results and density functional theory calculations reveal that the enhanced activity relies not only on the high surface area that characterizes the ultrathin 2D metallene structure,but also on the particular electronic configuration of Sb.Sb facilitates OH−adsorption in the reactive-intermediate pathway and strongly enhances the CO tolerance in the poisoning-intermediate pathway for alcohol oxidation.The excellent alcohol oxidation performance of PdMoSb trimetallene demonstrates the high potential of multimetallenes in the field of electrocatalysis.
