Fabrication of superior catalytic performance palladium-based catalysts with affordable cost is the key to develop direct ethanol fuel cell.Herein,Pd-decorated three-dimensional(3D)porous constructed from graphene oxi...Fabrication of superior catalytic performance palladium-based catalysts with affordable cost is the key to develop direct ethanol fuel cell.Herein,Pd-decorated three-dimensional(3D)porous constructed from graphene oxide(GO)and MXene combining with polystyrene(PS)particles as sacrificial templates(Pd/GO-MXene-PS)to elevate the catalytic performance for ethanol oxidation was proposed.The 3D porous interconnected structure of Pd/GO-MXene-PS was characterized by scanning electron microscope(SEM),transmission electron microscope(TEM)and Brunner−Emmet−Teller(BET).By optimizing the doping ratio of MXene to GO,the mass activity of Pd/GO_(5)-MXene_(5)-PS(2944.0 mA·mg^(−1))was 3.0 times higher than that of commercial Pd/C(950.4 mA·mg^(−1))toward ethanol oxidation in base solution.Meanwhile,the rotating disk electrode(RDE)results demonstrated that Pd/GO5-MXene5-PS had a faster kinetics of ethanol oxidation.The enhanced ethanol oxidation over Pd/GO5-MXene5-PS could attribute to the excellent 3D interconnected porous structure,large surface area,good conductivity and homogeneous Pd distribution.This work provided a new idea for creating 3D porous MXene composite materials in electrocatalysis.展开更多
Hierarchical Si C nanowire-supported Pd nanoparticles showed high photocatalytic activity for the C–X(X = Br, I) borylation of aryl halides at 30 °C. The Si C/Pd Mott-Schottky contact enhances the rapid transfer...Hierarchical Si C nanowire-supported Pd nanoparticles showed high photocatalytic activity for the C–X(X = Br, I) borylation of aryl halides at 30 °C. The Si C/Pd Mott-Schottky contact enhances the rapid transfer of the photogenerated electrons from Si C to the Pd nanoparticles. As a result, the concentrated energetic electrons in the Pd nanoparticles can facilitate the cleavage of C–I or C–Br bonds, which normally requires high-temperature thermal processes. We show that the present Pd/Si C photocatalyst is capable of catalyzing the transformation of a large variety of aryl halides to their corresponding boronate esters under visible light irradiation, with excellent yields.展开更多
Size-controlled Pd nanoparticles （PdNPs） were synthesized in aqueous solution, using sodium car-boxymethyl cellulose as the stabilizer. Size-controlled PdNPs were supported onα-Al2O3 by the incipient wetness impreg...Size-controlled Pd nanoparticles （PdNPs） were synthesized in aqueous solution, using sodium car-boxymethyl cellulose as the stabilizer. Size-controlled PdNPs were supported onα-Al2O3 by the incipient wetness impregnation method. The PdNPs onα-Al2O3 support were in a narrow particle size distribution in the range of 1-6 nm. A series of PdNPs/α-Al2O3 catalysts were used for the selective hydrogenation of acetylene in ethylene-rich stream. The results show that PdNPs/α-Al2O3 catalyst with 0.03%（by mass） Pd loading is a very effective and sta-ble catalyst. With promoter Ag added, ethylene selectivity is increased from 41.0%to 63.8%at 100 ＆#176;C. Comparing with conventional Pd-Ag/α-Al2O3 catalyst, PdNPs-Ag/α-Al2O3 catalyst has better catalytic performance in acety-lene hydrogenation and shows good prospects for industrial application.展开更多
A novel electrode material based on chemically modified graphene （CMG） with aminophenyl groups is covalently functionalized by a nucleophilic ring-opening reaction between the epoxy groups of graphene oxide and the ...A novel electrode material based on chemically modified graphene （CMG） with aminophenyl groups is covalently functionalized by a nucleophilic ring-opening reaction between the epoxy groups of graphene oxide and the aminophenyl groups of p-phenylenediamine. Palladium nanoparticles with an average diameter of 4.2 nm are deposited on the CMG by a liquid-phase borohydride reduction. The electrocatalytic activity and stability of the Pd/CMG composite towards formic acid oxidation are found to be higher than those of reduced graphene oxide and commercial carbon materials such as Vulcan XC-72 supported Pd electrocatalysts.展开更多
Palladium nanoparticles generated in situ for Suzuki coupling reactions and aerobic alcohol oxidation in water were recovered completely using linear polystyrene. The resultant polystyrene-stabilized palladium nanopar...Palladium nanoparticles generated in situ for Suzuki coupling reactions and aerobic alcohol oxidation in water were recovered completely using linear polystyrene. The resultant polystyrene-stabilized palladium nanoparticles were shown to be reusable without any loss of activity.展开更多
Modulating electronic structures of single-atom metal cocatalysts is vital for highly active photoreduction of CO_(2),and it's especially challenging to develop a facile method to modify the dispersion of atomical...Modulating electronic structures of single-atom metal cocatalysts is vital for highly active photoreduction of CO_(2),and it's especially challenging to develop a facile method to modify the dispersion of atomical photocatalytic sites.We herein report an ion-loading pyrolysis route to in-situ anchor Pd single atoms as well as twinned Pd nanoparticles on ultra-thin graphitic carbon nitride nanosheets(PdTP/Pd_(SA)-CN)for high-efficiency photoreduction of CO_(2).The anchored Pd twinned nanoparticles donate electrons to adjacent single Pd–N_(4) sites through the carbon nitride networks,and the optimized PdTP/Pd_(SA)-CN photocatalyst exhibits a CO evolution rate up to 46.5μmol g^(-1) h^(-1) with nearly 100%selectivity.As revealed by spectroscopic and theoretical analyses,the superior photocatalytic activity is attributed to the lowered desorption barrier of carbonyl species at electron-enriched Pd single atoms,together with the improved efficiencies of light-harvesting and charge separation/transport.This work has demonstrated the engineering of the electron density of single active sites with twinned metal nanoparticles assisted by strong electronic interaction with the support of the atomic metal,and unveiled the underlying mechanism for expedited photocatalytic efficiency.展开更多
A highly active heterogeneous catalyst,Pd nanoparticles@g-C_(3)N_(4)/SiO_(2) with tunable band structure,was successfully fabricated by a sol–gel method.The nanocomposite catalyst exhibits an extraordinary hydrogen p...A highly active heterogeneous catalyst,Pd nanoparticles@g-C_(3)N_(4)/SiO_(2) with tunable band structure,was successfully fabricated by a sol–gel method.The nanocomposite catalyst exhibits an extraordinary hydrogen production rate from formic acid which leads to a high turnover frequency(TOF)of around 306 mol H_(2) per mole Pd per h after 10 min.The characterization analysis shows that the bandgap of the g-C_(3)N_(4)/SiO_(2) support widens with decreasing synthesis temperature,which in turn allows tuning of the band structure by simply controlling the synthesis temperature.After Pd nanoparticles were embedded,the nanocomposite Pd@g-C_(3)N_(4)/SiO_(2) showed excellent catalytic performance in the dehydrogenation of formic acid at 303.15 K,and the lower the synthesis temperature of the catalyst,the higher its performance.展开更多
Nitrile hydrogenation represents an atom-economical and green approach to yield the highly valueadded primary amines,which suffers from harsh conditions and serious selectivity challenges.Herein,we demonstrated Pd nan...Nitrile hydrogenation represents an atom-economical and green approach to yield the highly valueadded primary amines,which suffers from harsh conditions and serious selectivity challenges.Herein,we demonstrated Pd nanoparticles anchored on ultrathin plate-like porous magnesium hydrate(Mg(OH)_(2))supports for the highly selective synthesis of benzylamine from benzonitrile hydrogenation in the absence of additives at 30℃.展开更多
The electrochemical CO_(2) reduction reaction(CO_(2)RR)offers a promising pathway to convert CO_(2) into value-added chemicals,with CO production being a primary target.While the conversion of CO_(2) to CO hinges on t...The electrochemical CO_(2) reduction reaction(CO_(2)RR)offers a promising pathway to convert CO_(2) into value-added chemicals,with CO production being a primary target.While the conversion of CO_(2) to CO hinges on the delicate balance of*COOH and*CO binding energies,this study introduces a series of Pdbased hybrid catalysts,Me_(10)CB[5]-M/Pd(M=Sr,Ca,and Cd),to address this challenge.The catalysts were synthesized via thermal treatment of supramolecular precursors formed by Me_(10)CB[5],M^(2+),and[PdCl_(4)]^(2-)ions.Notably,Me_(10)CB[5]-Sr/Pd exhibited exceptional CO selectivity(91.3%FECO at-0.7 V vs.RHE)and long-term stability.The incorporation of Me_(10)CB[5]-Sr into the Pd catalyst system enhanced CO_(2) adsorption,modulated the electronic structure of Pd,and optimized the adsorption/desorption energies of critical intermediates,ultimately leading to superior CO_(2)RR performance.This work underscores the potential of supramolecular engineering in designing high-performance electrocatalysts for CO_(2) conversion.展开更多
This study demonstrates that the integration of plasmonic palladium(Pd)nanoparticles between a bismuth vanadate(BVO)coating and an electrode interface can significantly improve solar-driven glycerol oxidation.Pd nanop...This study demonstrates that the integration of plasmonic palladium(Pd)nanoparticles between a bismuth vanadate(BVO)coating and an electrode interface can significantly improve solar-driven glycerol oxidation.Pd nanoparticles of controllable shape,size and coverage were produced using a novel aerosol-assisted chemical vapour deposition(AACVD)synthetic route and then coated with BVO using the same technique.The nanoparticles enhanced visible light absorption and crystallinity.At 1.23 VRHE,the photocurrent density of bare BVO increased from 0.62 mA cm^(-2) in the absence of glycerol to 1.20 mA cm^(-2) with 0.5 M glycerol.When Pd nanoparticles were incorporated beneath BVO,the photocurrent further increased from 0.86 mA cm^(-2) without glycerol to 1.58 mA cm^(-2) with 0.5 M glycerol,and the incident photon-to-current conversion efficiency(IPCE)boosted from~15%to~40%at 400 nm.Ultra-fast transient absorption spectroscopy suggests that the addition of Pd nanoparticles introduces additional charge transfer pathways,including hot electron injection and plasmon-coupled states,which prolong carrier lifetimes and suppress recombination.These combined effects provide a promising strategy to improve the efficiency and durability of photoelectrochemical devices for sustainable fuel generation and selective organic oxidation reactions.展开更多
In recent years,there has been growing interest in direct formic acid fuel cells and direct methanol fuel cells due to the diminishing energy resources and escalating environmental concerns,which stimulates the rapid ...In recent years,there has been growing interest in direct formic acid fuel cells and direct methanol fuel cells due to the diminishing energy resources and escalating environmental concerns,which stimulates the rapid development of advanced anode catalysts towards formic acid and methanol oxidation reactions.This study outlines an efficient bottom-up approach for the controllable fabrication of threedimensional(3D)crosslinked CeO_(2)nanosheet/graphene architectures anchored with Pd nanoparticles(Pd/CeO_(2)–G)via a solvothermal co-building process.The existence of 3D graphene skeletons introduces numerous pore channels for the fast transportation of reactants and electrons,while the incorporation of CeO_(2)nanosheets provides abundant oxygen vacancies to stabilize Pd species as well as reduce CO adsorption on active surfaces.As a result,the as-synthesized Pd/CeO_(2)–G architectures exhibit impressive electrocatalytic formic acid and methanol oxidation properties including mass activities of 681.0 and 2143.5 mA mg^(−1)and ECSA values of 107.9 and 115.8 m^(−2)g^(−1)in acidic and alkaline electrolytes,respectively.This makes them more competitive than traditional Pd catalysts supported by carbon black,carbon nanotubes,and graphene matrices.展开更多
The Ullmann coupling reaction of aromatic halides is the most challenging C–C coupling reaction.Both MOF-based and MOF-deriffed types of catalysts haffe recently proffided useful nanocatalysts for a ffariety of react...The Ullmann coupling reaction of aromatic halides is the most challenging C–C coupling reaction.Both MOF-based and MOF-deriffed types of catalysts haffe recently proffided useful nanocatalysts for a ffariety of reactions,but they haffe rarely been compared.Herein,the Ullmann-type aryl iodide homocoupling is effciently catalyzed by gold and palladium nanoparticles(NPs)loaded on ZIF-8 before(ZIF-8-based nanocatalyst:M@ZIF-8)and after calcination(ZIF-8-deriffed catalyst:M@CN).The nanocatalysts M@ZIF-8(M=Pd,Au)are found to be more effcient than the catalysts M@CN.Pd@ZIF-8 exhibits better perform ances than those of Au@ZIF-8 for a series of aryl iodides,but in the case of 4-nitro-iodobenzene,deshy droiodination was obserffed besides the coupling product.Mechanisms are proposed and discussed for both Au(0)and Pd(0)nanocatalysts.展开更多
Efficient catalytic aerial oxidation of biomass-derived 5-hydroxymethyl-2-furfural(5-HMF)to the industrially important furan-2,5-dicarboxylic acid(FDCA)was achieved over bimetallic M0.90-Pd0.10(M=Ni,Co or Cu)alloy nan...Efficient catalytic aerial oxidation of biomass-derived 5-hydroxymethyl-2-furfural(5-HMF)to the industrially important furan-2,5-dicarboxylic acid(FDCA)was achieved over bimetallic M0.90-Pd0.10(M=Ni,Co or Cu)alloy nanoparticles supported on in situ prepared Mg(OH)_(2)nanoflakes.In comparison to Co-and Cu-based bimetallic nanoparticles,Ni_(0.90)Pd_(0.10)/Mg(OH)_(2)exhibited superior catalytic performance.Catalytic reactions performed using Ni_(1-x)Pd_(x)/Mg(OH)_(2)(x=0.10 to 1)and a physical mixture of Ni/Mg(OH)_(2)and Pd/Mg(OH)_(2)revealed that the significant synergistic cooperation between Ni and Pd plays a crucial role in the observed high catalytic activity of Ni_(0.90)Pd_(0.10)/Mg(OH)_(2)for the oxidation of 5-HMF to FDCA.Experiments performed with Ni_(0.90)Pd_(0.10)on different supports(SiO_(2),Al_(2)O_(3),ZnO and Mg(OH)_(2))revealed that the basicity of the support is advantageous for efficient oxidation of 5-HMF,and it avoids the use of an external base additive.Moreover,the Ni_(0.90)Pd_(0.10)/Mg(OH)_(2)catalytic system can be scaled to gram-level oxidation of 5-HMF to FDCA.Subsequently,the synthesized FDCA was employed for the synthesis of various furan diesters(bis(2-hydroxyethyl),dimethyl,diethyl,dipropyl and dibutyl furan-2,5-dicarboxylate)as precursors for biomass-derived plastics.Moreover,structural and chemical identification of the highly active Ni_(0.90)Pd_(0.10)/Mg(OH)_(2)was established by P-XRD,SEM,TEM,EDS,elemental mapping and ICP-AES analysis.展开更多
Active-phase engineering is regularly utilized to tune the selectivity of metal nanoparticles （NPs） in heterogeneous catalysis. However, the lack of understanding of the active phase in electrocatalysis has hampered...Active-phase engineering is regularly utilized to tune the selectivity of metal nanoparticles （NPs） in heterogeneous catalysis. However, the lack of understanding of the active phase in electrocatalysis has hampered the development of efficient catalysts for CO2 electroreduction. Herein, we report the systematic engineering of active phases of Pd NPs, which are exploited to select reaction pathways for CO2 electroreduction. In situ X-ray absorption spectroscopy, in situ attenuated total reflection-infrared spectroscopy, and density functional theory calculations suggest that the formation of a hydrogen-adsorbed Pd surface on a mixture of the α- and β-phases of a palladium-hydride core （α＋β PdHx@PdHx） above -0.2 V （vs. a reversible hydrogen electrode） facilitates formate production via the HCOO intermediate, whereas the formation of a metallic Pd surface on the β-phase Pd hydride core （β PdHx@Pd） below -0.5 V promotes CO production via the COOH＂ intermediate. The main product, which is either formate or CO, can be selectively produced with high Faradaic efficiencies （〉90%） and mass activities in the potential window of 0.05 to -0.9 V with scalable application demonstration.展开更多
In this work,a novel in situ auto-reduction strategy was developed to encapsulate uniformly dispersed Pd clusters/nanoparticles in MIL-125-NH_(2).It is demonstrated that the amino groups in MIL-125-NH_(2)can react wit...In this work,a novel in situ auto-reduction strategy was developed to encapsulate uniformly dispersed Pd clusters/nanoparticles in MIL-125-NH_(2).It is demonstrated that the amino groups in MIL-125-NH_(2)can react with formaldehyde to form novel reducing groups(-NH-CH_(2)OH),which can in situ auto-reduce the encapsulated Pd^(2+)ions to metallic Pd clusters/nanoparticles.As no additional reductants are required,the strategy limits the aggregation and migration of Pd clusters and the formation of large Pd nanoparticles via controlling the amount of Pd^(2+)precursor.When applied as catalysts in the hydrogenation of phenol in the aqueous phase,the obtained Pd(1.5)/MIL-125-NH-CH_(2)OH catalyst with highly dispersed Pd clusters/nanoparticles with the size of around 2 nm exhibited 100%of phenol conversion and 100%of cyclohexanone selectivity at 70℃ after 5 h,as well as remarkable reusability for at least five cycles due to the large MOF surface area,the highly dispersed Pd clusters/nanoparticles and their excellent stability within the MIL-125-NH-CH_(2)OH framework.展开更多
Product selectivity adjustment is a much-studied topic in mesoscience that is critical for industrial processes and strongly related to reaction intermediates formed by interactions between catalytic active sites and ...Product selectivity adjustment is a much-studied topic in mesoscience that is critical for industrial processes and strongly related to reaction intermediates formed by interactions between catalytic active sites and reactants.Herein,we report efficient adjustment of the product selectivity in the hydrogenation of substituted nitroarenes via rational reaction intermediates achieved using controllable Pd nanoparticles.Pd nanoparticles fixed within zeolite Beta crystals(Pd@Beta)afforded rational Pd-NO2 interactions,in which the Pd nanoparticle-adsorbed substituted nitroarenes,such as nitrobenzaldehyde,were reasonably hydrogenated into the corresponding aminobenzaldehyde.However,for Pd nanoparticles supported on the external surfaces of zeolite beta crystals,various side products were obtained owing to the coexistence of Pd-NO2 and Pd-C=O interactions.When Pd nanoparticles were artificially controlled in various positions in a fixed-bed reactor,the product selectivity was significantly affected.These results demonstrate the importance of molecular adsorption and diffusion processes in adjusting product selectivity in catalytic reactions.展开更多
Pd nanoparticles less than 8 nm were photoinduced by a near-IR femtosecond laser. The sign of the refraction nonlinearity is negative for the Pd nanoparticles with TiO2, while it is positive for those without TiO2.
Solar-driven CO_(2)conversion to prepare value-added products is highly desirable but challenging.Central to the achievement of multi-carbon products via CO_(2)photoconversion is to break the bottlenecks of C-C coupli...Solar-driven CO_(2)conversion to prepare value-added products is highly desirable but challenging.Central to the achievement of multi-carbon products via CO_(2)photoconversion is to break the bottlenecks of C-C coupling and multi-electron transfer.Herein,a charge relay system consisting of Pd-decorated BiOCl-wrapped CuBi_(2)O_(4)is reported by taking advantage of the synergy of Pd nanoparticles(PdNPs)and heterojunction for efficient CO_(2)-to-C_(2)H_(6)photoconversion.The C_(2)H_(6)production rate reached 167.1µmol g^(-1)h^(-1)with the electron selectivity of 81.1%in the absence of any sacrificial agents.The spectroscopic characterizations indicated that BiOCl nanosheets,acting as the charge relay,directionally transferred the photogenerated electrons from itself and CuBi2O4 nanorods to PdNPs for C-C coupling.The coordinated ensemble of PdNPs and heterojunction significantly elevated the charge separation and transfer efficiency.Moreover,the in-situ spectroscopic analysis supported by theoretical simulations demonstrated that the electron-rich PdNPs generated by the charge relay of PdNPs and heterojunction optimized the CO_(2)-to-C_(2)H_(6)reaction pathway and reduced the energy barrier of the key*CHOCO intermediates.This work develops an innovative strategy to design the multifunctional catalysts for the photoconversion of CO_(2)to value-added carbon products.展开更多
An indium tin oxide(ITO)electrode coated with monolayer TiO2/[Ru(phen)2(dC18bpy)] 2+ (phen=1,10-phenanthroline, dC18bpy=4,4′-dioctadecyl-2,2′-bipyridyl)hybrid film(denoted as ITO/TiO2-Ru)has been prepared using the ...An indium tin oxide(ITO)electrode coated with monolayer TiO2/[Ru(phen)2(dC18bpy)] 2+ (phen=1,10-phenanthroline, dC18bpy=4,4′-dioctadecyl-2,2′-bipyridyl)hybrid film(denoted as ITO/TiO2-Ru)has been prepared using the modified Langmuir-Blodgett(LB)method,and the electrocatalytic oxidation of mononucleotide of guanosine 5′-monophosphate(GMP)on an ITO/TiO2-Ru electrode after Pd-photodeposition(denoted as ITO/TiO2-Ru/Pd)has been studied.Atomic force microscopy reveals that the single-layered hybrid film of TiO2 nanosheets/[Ru(phen)2(dC18bpy)] 2+is closely packed at a surface pressure of 25 mN m 1and has a thickness of(3.20±0.5)nm.X-ray photoelectron spectra show the formation of Pd nanoparticles on the surface of hybrid film with radii of 20–200 nm by the reduction of[Pd(NH3)4] 2+ under light irradiation.When it is applied to oxidize GMP,a larger catalytic oxidative current is achieved on the ITO/TiO2-Ru/Pd electrode at the external potential above 700 mV(vs.Ag|AgCl|KCl)in comparison with the naked ITO electrode and ITO/TiO2-Ru electrode.Such a result indicates that the Pd nanoparticles are able to hamper the combination of electron hole pairs and reduce the counterwork of insulating long alkyl chains of amphiphilic Ru(II)complexes,and thus develops the electron transfer efficiency and produces the enhanced redox current.展开更多
Hybrid materials with synergistic properties have been used for various applications.Herein,we report a green biosynthesis strategy for the fabrication of a novel Pd/bacteria@ZIF-8 composite,featuring a sandwiched str...Hybrid materials with synergistic properties have been used for various applications.Herein,we report a green biosynthesis strategy for the fabrication of a novel Pd/bacteria@ZIF-8 composite,featuring a sandwiched structure and size-selective capabilities.The Shewanella oneidensis(S.oneidensis)MR-1 was selected as the biological reductant to reduce Pd ions and synthesize Pd nanoparticles anchored on the surface of bacteria without the need for additional chemical reductants,bonding agents and toxic surfactants.This innovative sandwiched Pd/bacteria@ZIF-8 catalyst was further coated by the ZIF-8 to enhance its structural integrity.The as-prepared composite exhibits significant catalytic activity and excellent size-selective performance in the hydrogenation of olefins.This methodology opens up a horizon to designing size-selective catalysts through constructing the sandwiched structure.展开更多
基金financially supported by the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning(No.A30B191410)the Sailing Project from Science and Technology Commission of Shanghai Municipality(No.17YF1406600)+6 种基金Chenguang Project Supported by Shanghai Municipal Education Commission(No.18CG68)Gaoyuan Discipline of Shanghai-Materials Science and Engineering(No.A30NH221903)the Open Project of Jiangsu Key Laboratory for Carbon-Based Functional Materials&Devices(Soochow University)(No.KS2022)Collaborative Innovation Center of Suzhou Nano Science&Technologythe 111 ProjectJoint International Research Laboratory of Carbon-Based Functional Materials and Devicesthe Project of Guangdong Provincial Education(No.2020KTSCX131)。
文摘Fabrication of superior catalytic performance palladium-based catalysts with affordable cost is the key to develop direct ethanol fuel cell.Herein,Pd-decorated three-dimensional(3D)porous constructed from graphene oxide(GO)and MXene combining with polystyrene(PS)particles as sacrificial templates(Pd/GO-MXene-PS)to elevate the catalytic performance for ethanol oxidation was proposed.The 3D porous interconnected structure of Pd/GO-MXene-PS was characterized by scanning electron microscope(SEM),transmission electron microscope(TEM)and Brunner−Emmet−Teller(BET).By optimizing the doping ratio of MXene to GO,the mass activity of Pd/GO_(5)-MXene_(5)-PS(2944.0 mA·mg^(−1))was 3.0 times higher than that of commercial Pd/C(950.4 mA·mg^(−1))toward ethanol oxidation in base solution.Meanwhile,the rotating disk electrode(RDE)results demonstrated that Pd/GO5-MXene5-PS had a faster kinetics of ethanol oxidation.The enhanced ethanol oxidation over Pd/GO5-MXene5-PS could attribute to the excellent 3D interconnected porous structure,large surface area,good conductivity and homogeneous Pd distribution.This work provided a new idea for creating 3D porous MXene composite materials in electrocatalysis.
基金supported by the National Natural Science Foudation of China(21473232,21673271,U1710112)
文摘Hierarchical Si C nanowire-supported Pd nanoparticles showed high photocatalytic activity for the C–X(X = Br, I) borylation of aryl halides at 30 °C. The Si C/Pd Mott-Schottky contact enhances the rapid transfer of the photogenerated electrons from Si C to the Pd nanoparticles. As a result, the concentrated energetic electrons in the Pd nanoparticles can facilitate the cleavage of C–I or C–Br bonds, which normally requires high-temperature thermal processes. We show that the present Pd/Si C photocatalyst is capable of catalyzing the transformation of a large variety of aryl halides to their corresponding boronate esters under visible light irradiation, with excellent yields.
基金Supported by SINOPEC Beijing Research Institute of Chemical Industry(01-09ZS0440,11-08ZS0442)
文摘Size-controlled Pd nanoparticles （PdNPs） were synthesized in aqueous solution, using sodium car-boxymethyl cellulose as the stabilizer. Size-controlled PdNPs were supported onα-Al2O3 by the incipient wetness impregnation method. The PdNPs onα-Al2O3 support were in a narrow particle size distribution in the range of 1-6 nm. A series of PdNPs/α-Al2O3 catalysts were used for the selective hydrogenation of acetylene in ethylene-rich stream. The results show that PdNPs/α-Al2O3 catalyst with 0.03%（by mass） Pd loading is a very effective and sta-ble catalyst. With promoter Ag added, ethylene selectivity is increased from 41.0%to 63.8%at 100 ＆#176;C. Comparing with conventional Pd-Ag/α-Al2O3 catalyst, PdNPs-Ag/α-Al2O3 catalyst has better catalytic performance in acety-lene hydrogenation and shows good prospects for industrial application.
基金supported by the National Basic Research Program of China(Grant No.2007CB209700)the Graduate Student Innovation Foundation of Jiangsu Province,China(Grant No.CX09B_075Z)the Research Funding of Nanjing University of Aeronautics and Astronautics,China(Grant No.NS2010165)
文摘A novel electrode material based on chemically modified graphene （CMG） with aminophenyl groups is covalently functionalized by a nucleophilic ring-opening reaction between the epoxy groups of graphene oxide and the aminophenyl groups of p-phenylenediamine. Palladium nanoparticles with an average diameter of 4.2 nm are deposited on the CMG by a liquid-phase borohydride reduction. The electrocatalytic activity and stability of the Pd/CMG composite towards formic acid oxidation are found to be higher than those of reduced graphene oxide and commercial carbon materials such as Vulcan XC-72 supported Pd electrocatalysts.
基金the Nanomaterials and Micro-devices Research Center(NMRC)of OIT for financial and instrumental supportssupported by the Joint Studies Program(2010)of the Institute for Mo-lecular Science.
文摘Palladium nanoparticles generated in situ for Suzuki coupling reactions and aerobic alcohol oxidation in water were recovered completely using linear polystyrene. The resultant polystyrene-stabilized palladium nanoparticles were shown to be reusable without any loss of activity.
基金We appreciate the financial support from the National Natural Science Foundation of China(22272150,22102145)the Major Program of Zhejiang Provincial Natural Science Foundation(LD22B030002)+3 种基金Zhejiang Provincial Ten Thousand Talent Program(2021R51009)Zhejiang Provincial Natural Science Foundation of China(LQ23B030006,LY22B030012)Shandong Provincial Natural Science Foundation of China(2020MB053)the Fundamental Research Funds for the Central Universities(DUT22RC(3)084).
文摘Modulating electronic structures of single-atom metal cocatalysts is vital for highly active photoreduction of CO_(2),and it's especially challenging to develop a facile method to modify the dispersion of atomical photocatalytic sites.We herein report an ion-loading pyrolysis route to in-situ anchor Pd single atoms as well as twinned Pd nanoparticles on ultra-thin graphitic carbon nitride nanosheets(PdTP/Pd_(SA)-CN)for high-efficiency photoreduction of CO_(2).The anchored Pd twinned nanoparticles donate electrons to adjacent single Pd–N_(4) sites through the carbon nitride networks,and the optimized PdTP/Pd_(SA)-CN photocatalyst exhibits a CO evolution rate up to 46.5μmol g^(-1) h^(-1) with nearly 100%selectivity.As revealed by spectroscopic and theoretical analyses,the superior photocatalytic activity is attributed to the lowered desorption barrier of carbonyl species at electron-enriched Pd single atoms,together with the improved efficiencies of light-harvesting and charge separation/transport.This work has demonstrated the engineering of the electron density of single active sites with twinned metal nanoparticles assisted by strong electronic interaction with the support of the atomic metal,and unveiled the underlying mechanism for expedited photocatalytic efficiency.
基金supported by National Basic Research Program of China(2013CB934102)National Natural Science Foundation of China(21331004,21301116)SJTU-MPI partner group,SJTU-UM joint grant,Shanghai Eastern Scholar Program and Shanghai Rising-Star Program(16QA1402100).
文摘A highly active heterogeneous catalyst,Pd nanoparticles@g-C_(3)N_(4)/SiO_(2) with tunable band structure,was successfully fabricated by a sol–gel method.The nanocomposite catalyst exhibits an extraordinary hydrogen production rate from formic acid which leads to a high turnover frequency(TOF)of around 306 mol H_(2) per mole Pd per h after 10 min.The characterization analysis shows that the bandgap of the g-C_(3)N_(4)/SiO_(2) support widens with decreasing synthesis temperature,which in turn allows tuning of the band structure by simply controlling the synthesis temperature.After Pd nanoparticles were embedded,the nanocomposite Pd@g-C_(3)N_(4)/SiO_(2) showed excellent catalytic performance in the dehydrogenation of formic acid at 303.15 K,and the lower the synthesis temperature of the catalyst,the higher its performance.
基金supported by the National Natural Science Foundation of China(21872109 and 22002115)the Fundamental Research Funds for the Central Universities(D5000210283,D5000210601 and D5000210829)+2 种基金S.Zhang is also supported by the Guangdong Basic and Applied Basic Research Foundation(2022B1515020092)the Young Elite Scientists Sponsorship Program by CAST(2019QNRC001)Technology and the support of the National Natural Science Foundation of China(Grant No:22038011).
文摘Nitrile hydrogenation represents an atom-economical and green approach to yield the highly valueadded primary amines,which suffers from harsh conditions and serious selectivity challenges.Herein,we demonstrated Pd nanoparticles anchored on ultrathin plate-like porous magnesium hydrate(Mg(OH)_(2))supports for the highly selective synthesis of benzylamine from benzonitrile hydrogenation in the absence of additives at 30℃.
基金support from the National Key R&D Program of China(2023YFA507101,2022YFA1503900,and 2018YFA0704502)the NSFC(22033008 and 22220102005).
文摘The electrochemical CO_(2) reduction reaction(CO_(2)RR)offers a promising pathway to convert CO_(2) into value-added chemicals,with CO production being a primary target.While the conversion of CO_(2) to CO hinges on the delicate balance of*COOH and*CO binding energies,this study introduces a series of Pdbased hybrid catalysts,Me_(10)CB[5]-M/Pd(M=Sr,Ca,and Cd),to address this challenge.The catalysts were synthesized via thermal treatment of supramolecular precursors formed by Me_(10)CB[5],M^(2+),and[PdCl_(4)]^(2-)ions.Notably,Me_(10)CB[5]-Sr/Pd exhibited exceptional CO selectivity(91.3%FECO at-0.7 V vs.RHE)and long-term stability.The incorporation of Me_(10)CB[5]-Sr into the Pd catalyst system enhanced CO_(2) adsorption,modulated the electronic structure of Pd,and optimized the adsorption/desorption energies of critical intermediates,ultimately leading to superior CO_(2)RR performance.This work underscores the potential of supramolecular engineering in designing high-performance electrocatalysts for CO_(2) conversion.
基金support from UKRI/EPSRC(ActionSpec,Grant Ref:EP/X030822/1)Imperial College London for a Dean’s PhD Scholarship.B.T.and A.K.thank the EPSRC for a Programme Grant(EP/W017075/1)funding by the Imperial College London President’s PhD Scholarships.
文摘This study demonstrates that the integration of plasmonic palladium(Pd)nanoparticles between a bismuth vanadate(BVO)coating and an electrode interface can significantly improve solar-driven glycerol oxidation.Pd nanoparticles of controllable shape,size and coverage were produced using a novel aerosol-assisted chemical vapour deposition(AACVD)synthetic route and then coated with BVO using the same technique.The nanoparticles enhanced visible light absorption and crystallinity.At 1.23 VRHE,the photocurrent density of bare BVO increased from 0.62 mA cm^(-2) in the absence of glycerol to 1.20 mA cm^(-2) with 0.5 M glycerol.When Pd nanoparticles were incorporated beneath BVO,the photocurrent further increased from 0.86 mA cm^(-2) without glycerol to 1.58 mA cm^(-2) with 0.5 M glycerol,and the incident photon-to-current conversion efficiency(IPCE)boosted from~15%to~40%at 400 nm.Ultra-fast transient absorption spectroscopy suggests that the addition of Pd nanoparticles introduces additional charge transfer pathways,including hot electron injection and plasmon-coupled states,which prolong carrier lifetimes and suppress recombination.These combined effects provide a promising strategy to improve the efficiency and durability of photoelectrochemical devices for sustainable fuel generation and selective organic oxidation reactions.
基金supported by the National Natural Science Foundation of China(No.52071001)the Key Research and Development Program of Anhui Province of China(No.2022l07020011)+1 种基金the Scientific Research Foundation of the Education Department of Anhui Province of China(No.2022AH050341 and 2022AH010025)the Anhui Postdoctoral Scientific Research Project(2024C933).
文摘In recent years,there has been growing interest in direct formic acid fuel cells and direct methanol fuel cells due to the diminishing energy resources and escalating environmental concerns,which stimulates the rapid development of advanced anode catalysts towards formic acid and methanol oxidation reactions.This study outlines an efficient bottom-up approach for the controllable fabrication of threedimensional(3D)crosslinked CeO_(2)nanosheet/graphene architectures anchored with Pd nanoparticles(Pd/CeO_(2)–G)via a solvothermal co-building process.The existence of 3D graphene skeletons introduces numerous pore channels for the fast transportation of reactants and electrons,while the incorporation of CeO_(2)nanosheets provides abundant oxygen vacancies to stabilize Pd species as well as reduce CO adsorption on active surfaces.As a result,the as-synthesized Pd/CeO_(2)–G architectures exhibit impressive electrocatalytic formic acid and methanol oxidation properties including mass activities of 681.0 and 2143.5 mA mg^(−1)and ECSA values of 107.9 and 115.8 m^(−2)g^(−1)in acidic and alkaline electrolytes,respectively.This makes them more competitive than traditional Pd catalysts supported by carbon black,carbon nanotubes,and graphene matrices.
基金the China Scholarship Council of the People’s Republic of China(PhD grant to W.W.),the National Science Center of Poland under the program OPUS(E.C.and S.M.:2019/33/B/ST5/01495)the University of Bordeaux,the Centre National de la Recherche Scientifique(CNRS)and CIC biomaGUNE is gratefully acknowledged.
文摘The Ullmann coupling reaction of aromatic halides is the most challenging C–C coupling reaction.Both MOF-based and MOF-deriffed types of catalysts haffe recently proffided useful nanocatalysts for a ffariety of reactions,but they haffe rarely been compared.Herein,the Ullmann-type aryl iodide homocoupling is effciently catalyzed by gold and palladium nanoparticles(NPs)loaded on ZIF-8 before(ZIF-8-based nanocatalyst:M@ZIF-8)and after calcination(ZIF-8-deriffed catalyst:M@CN).The nanocatalysts M@ZIF-8(M=Pd,Au)are found to be more effcient than the catalysts M@CN.Pd@ZIF-8 exhibits better perform ances than those of Au@ZIF-8 for a series of aryl iodides,but in the case of 4-nitro-iodobenzene,deshy droiodination was obserffed besides the coupling product.Mechanisms are proposed and discussed for both Au(0)and Pd(0)nanocatalysts.
基金IIT Indore and CSIR New Delhi for financial support.
文摘Efficient catalytic aerial oxidation of biomass-derived 5-hydroxymethyl-2-furfural(5-HMF)to the industrially important furan-2,5-dicarboxylic acid(FDCA)was achieved over bimetallic M0.90-Pd0.10(M=Ni,Co or Cu)alloy nanoparticles supported on in situ prepared Mg(OH)_(2)nanoflakes.In comparison to Co-and Cu-based bimetallic nanoparticles,Ni_(0.90)Pd_(0.10)/Mg(OH)_(2)exhibited superior catalytic performance.Catalytic reactions performed using Ni_(1-x)Pd_(x)/Mg(OH)_(2)(x=0.10 to 1)and a physical mixture of Ni/Mg(OH)_(2)and Pd/Mg(OH)_(2)revealed that the significant synergistic cooperation between Ni and Pd plays a crucial role in the observed high catalytic activity of Ni_(0.90)Pd_(0.10)/Mg(OH)_(2)for the oxidation of 5-HMF to FDCA.Experiments performed with Ni_(0.90)Pd_(0.10)on different supports(SiO_(2),Al_(2)O_(3),ZnO and Mg(OH)_(2))revealed that the basicity of the support is advantageous for efficient oxidation of 5-HMF,and it avoids the use of an external base additive.Moreover,the Ni_(0.90)Pd_(0.10)/Mg(OH)_(2)catalytic system can be scaled to gram-level oxidation of 5-HMF to FDCA.Subsequently,the synthesized FDCA was employed for the synthesis of various furan diesters(bis(2-hydroxyethyl),dimethyl,diethyl,dipropyl and dibutyl furan-2,5-dicarboxylate)as precursors for biomass-derived plastics.Moreover,structural and chemical identification of the highly active Ni_(0.90)Pd_(0.10)/Mg(OH)_(2)was established by P-XRD,SEM,TEM,EDS,elemental mapping and ICP-AES analysis.
文摘Active-phase engineering is regularly utilized to tune the selectivity of metal nanoparticles （NPs） in heterogeneous catalysis. However, the lack of understanding of the active phase in electrocatalysis has hampered the development of efficient catalysts for CO2 electroreduction. Herein, we report the systematic engineering of active phases of Pd NPs, which are exploited to select reaction pathways for CO2 electroreduction. In situ X-ray absorption spectroscopy, in situ attenuated total reflection-infrared spectroscopy, and density functional theory calculations suggest that the formation of a hydrogen-adsorbed Pd surface on a mixture of the α- and β-phases of a palladium-hydride core （α＋β PdHx@PdHx） above -0.2 V （vs. a reversible hydrogen electrode） facilitates formate production via the HCOO intermediate, whereas the formation of a metallic Pd surface on the β-phase Pd hydride core （β PdHx@Pd） below -0.5 V promotes CO production via the COOH＂ intermediate. The main product, which is either formate or CO, can be selectively produced with high Faradaic efficiencies （〉90%） and mass activities in the potential window of 0.05 to -0.9 V with scalable application demonstration.
基金financial support from the National Natural Science Foundation of China(Grant No.51802015)the Research Department Closed Carbon Cycle Economy(CCCE)at the Ruhr-University Bochum,Fundamental Research Funds for the Central Universities(No.FRF-TP-20-005A3)the Fundamental Research Funds for the Central Universities and the Youth Teacher International Exchange&Growth Program(Grant No.QNXM20210016)。
文摘In this work,a novel in situ auto-reduction strategy was developed to encapsulate uniformly dispersed Pd clusters/nanoparticles in MIL-125-NH_(2).It is demonstrated that the amino groups in MIL-125-NH_(2)can react with formaldehyde to form novel reducing groups(-NH-CH_(2)OH),which can in situ auto-reduce the encapsulated Pd^(2+)ions to metallic Pd clusters/nanoparticles.As no additional reductants are required,the strategy limits the aggregation and migration of Pd clusters and the formation of large Pd nanoparticles via controlling the amount of Pd^(2+)precursor.When applied as catalysts in the hydrogenation of phenol in the aqueous phase,the obtained Pd(1.5)/MIL-125-NH-CH_(2)OH catalyst with highly dispersed Pd clusters/nanoparticles with the size of around 2 nm exhibited 100%of phenol conversion and 100%of cyclohexanone selectivity at 70℃ after 5 h,as well as remarkable reusability for at least five cycles due to the large MOF surface area,the highly dispersed Pd clusters/nanoparticles and their excellent stability within the MIL-125-NH-CH_(2)OH framework.
基金This work is supported by the National Natural Science Foundation of China(91634201,21403192 and 91645105)the China Postdoctoral Science Foundation(2018M630662)。
文摘Product selectivity adjustment is a much-studied topic in mesoscience that is critical for industrial processes and strongly related to reaction intermediates formed by interactions between catalytic active sites and reactants.Herein,we report efficient adjustment of the product selectivity in the hydrogenation of substituted nitroarenes via rational reaction intermediates achieved using controllable Pd nanoparticles.Pd nanoparticles fixed within zeolite Beta crystals(Pd@Beta)afforded rational Pd-NO2 interactions,in which the Pd nanoparticle-adsorbed substituted nitroarenes,such as nitrobenzaldehyde,were reasonably hydrogenated into the corresponding aminobenzaldehyde.However,for Pd nanoparticles supported on the external surfaces of zeolite beta crystals,various side products were obtained owing to the coexistence of Pd-NO2 and Pd-C=O interactions.When Pd nanoparticles were artificially controlled in various positions in a fixed-bed reactor,the product selectivity was significantly affected.These results demonstrate the importance of molecular adsorption and diffusion processes in adjusting product selectivity in catalytic reactions.
文摘Pd nanoparticles less than 8 nm were photoinduced by a near-IR femtosecond laser. The sign of the refraction nonlinearity is negative for the Pd nanoparticles with TiO2, while it is positive for those without TiO2.
基金supported by the National Natural Science Foundation of China(22302002,22375006)the University Science Research Project of Anhui Province(2022AH050182,2022AH020020)。
文摘Solar-driven CO_(2)conversion to prepare value-added products is highly desirable but challenging.Central to the achievement of multi-carbon products via CO_(2)photoconversion is to break the bottlenecks of C-C coupling and multi-electron transfer.Herein,a charge relay system consisting of Pd-decorated BiOCl-wrapped CuBi_(2)O_(4)is reported by taking advantage of the synergy of Pd nanoparticles(PdNPs)and heterojunction for efficient CO_(2)-to-C_(2)H_(6)photoconversion.The C_(2)H_(6)production rate reached 167.1µmol g^(-1)h^(-1)with the electron selectivity of 81.1%in the absence of any sacrificial agents.The spectroscopic characterizations indicated that BiOCl nanosheets,acting as the charge relay,directionally transferred the photogenerated electrons from itself and CuBi2O4 nanorods to PdNPs for C-C coupling.The coordinated ensemble of PdNPs and heterojunction significantly elevated the charge separation and transfer efficiency.Moreover,the in-situ spectroscopic analysis supported by theoretical simulations demonstrated that the electron-rich PdNPs generated by the charge relay of PdNPs and heterojunction optimized the CO_(2)-to-C_(2)H_(6)reaction pathway and reduced the energy barrier of the key*CHOCO intermediates.This work develops an innovative strategy to design the multifunctional catalysts for the photoconversion of CO_(2)to value-added carbon products.
基金supported by the National Natural Science Foundation of China(21073133,20843007,20471043)Zhejiang Provincial Natural Science Foundation of China(Y5100283,Y4090248,Y4080177)Wenzhou University Foundation(2007L019)
文摘An indium tin oxide(ITO)electrode coated with monolayer TiO2/[Ru(phen)2(dC18bpy)] 2+ (phen=1,10-phenanthroline, dC18bpy=4,4′-dioctadecyl-2,2′-bipyridyl)hybrid film(denoted as ITO/TiO2-Ru)has been prepared using the modified Langmuir-Blodgett(LB)method,and the electrocatalytic oxidation of mononucleotide of guanosine 5′-monophosphate(GMP)on an ITO/TiO2-Ru electrode after Pd-photodeposition(denoted as ITO/TiO2-Ru/Pd)has been studied.Atomic force microscopy reveals that the single-layered hybrid film of TiO2 nanosheets/[Ru(phen)2(dC18bpy)] 2+is closely packed at a surface pressure of 25 mN m 1and has a thickness of(3.20±0.5)nm.X-ray photoelectron spectra show the formation of Pd nanoparticles on the surface of hybrid film with radii of 20–200 nm by the reduction of[Pd(NH3)4] 2+ under light irradiation.When it is applied to oxidize GMP,a larger catalytic oxidative current is achieved on the ITO/TiO2-Ru/Pd electrode at the external potential above 700 mV(vs.Ag|AgCl|KCl)in comparison with the naked ITO electrode and ITO/TiO2-Ru electrode.Such a result indicates that the Pd nanoparticles are able to hamper the combination of electron hole pairs and reduce the counterwork of insulating long alkyl chains of amphiphilic Ru(II)complexes,and thus develops the electron transfer efficiency and produces the enhanced redox current.
基金supported by the Young Talent Support Fund from Jiangsu University(No.5501310013)Jiangsu Provincial Founds for Young Scholars(Nos.BK20210782 and BK20210744)+2 种基金the Fellowship of China Postdoctoral Science Foundation(No.2022M720057)Wenzhou Science&Technology Program(No.ZG2021025)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515111017).
文摘Hybrid materials with synergistic properties have been used for various applications.Herein,we report a green biosynthesis strategy for the fabrication of a novel Pd/bacteria@ZIF-8 composite,featuring a sandwiched structure and size-selective capabilities.The Shewanella oneidensis(S.oneidensis)MR-1 was selected as the biological reductant to reduce Pd ions and synthesize Pd nanoparticles anchored on the surface of bacteria without the need for additional chemical reductants,bonding agents and toxic surfactants.This innovative sandwiched Pd/bacteria@ZIF-8 catalyst was further coated by the ZIF-8 to enhance its structural integrity.The as-prepared composite exhibits significant catalytic activity and excellent size-selective performance in the hydrogenation of olefins.This methodology opens up a horizon to designing size-selective catalysts through constructing the sandwiched structure.
