Methanol oxidation reaction(MOR)is a key process in direct methanol fuel cells(DMFCs),determining both energy efficiency and stability.Despite efforts,the impact of dynamic structural changes of Pt-based catalysts on ...Methanol oxidation reaction(MOR)is a key process in direct methanol fuel cells(DMFCs),determining both energy efficiency and stability.Despite efforts,the impact of dynamic structural changes of Pt-based catalysts on MOR performance remains poorly understood.Here,we report on the impact mechanism of dynamic changes on MOR performance in the Pd-Pt concave nanocubes(CNCs)system.Pt with high-index facets exposed abundant active sites for methanol oxidation,resulting in an exceptional mass activity of 0.89 A·mg_(Pt)^(-1).Pd underwent an oxidationredeposition process during MOR,dynamically restructuring the catalyst and producing a volcano-type activity.Pd^(δ+)species generated during oxidative etching promoted OH*formation,accelerating CO oxidation on Pt sites,thus mitigating poisoning.With continued cycling,redeposited Pd partially blocked Pt sites,counteracting the positive effect of the generated Pd^(δ+).The dynamic balance of Pd oxidation and redeposition governed the activity evolution while sustaining the exceptional durability of Pd-Pt CNCs during prolonged cycling.展开更多
The sluggish reaction kinetics of the oxygen evolution reaction(OER)and methanol oxidation reaction(MOR)remain obstacles to the commercial promotion of water splitting and direct methanol fuel cells.Considering the vi...The sluggish reaction kinetics of the oxygen evolution reaction(OER)and methanol oxidation reaction(MOR)remain obstacles to the commercial promotion of water splitting and direct methanol fuel cells.Considering the vital role of noble metals in electrocatalytic activity,this work focuses on the rational synthesis of Ni-noble metal composite nanocatalysts for overcoming the drawbacks of high cost and susceptible oxidized surfaces of noble metals.The inherent catalytic activity is improved by the altered electronic structure and effective active sites of the catalyst induced by the size effect of noble metal clusters.In particular,a series of Ni-noble metal nanocomposites are successfully synthesized by partially introducing noble metal into Ni with porous interfacial defects derived from Ni-Al layered double hydroxide(LDH).The Ni_(10)Pd_(1)nanocomposite exhibits high OER catalytic activity with an overpotential of 0.279 V at 10 m A/cm^(2),surpassing Ni_(10)Ag_(1)and Ni_(10)Au_(1)counterparts.Furthermore,the average diameter of Pd clusters gradually increases from 5.57 nm to 44.44 nm with the increased proportion of doped Pd,leading to the passivation of catalytic activity due to the exacerbated surface oxidation of Pd in the form of Pd^(2+).After optimization,Ni_(10)Pd_(1)delivers significantly enhanced OER and MOR electroactivities and long-term stability compared to that of Ni_(2)Pd_(1),Ni_(1)Pd_(1)and Ni_(1)Pd_(2),which is conducive to the effective utilization of Pd and alleviation of surface oxidation.展开更多
Pt-based methanol oxidation reaction(MOR)electrocatalysts with high activity,stability,and carbon monoxide(CO)tolerance are critical for advancing direct methanol fuel cells(DMFC).Herein,a low-Pt-content electrocataly...Pt-based methanol oxidation reaction(MOR)electrocatalysts with high activity,stability,and carbon monoxide(CO)tolerance are critical for advancing direct methanol fuel cells(DMFC).Herein,a low-Pt-content electrocatalyst(Pt/CeO_(2)-carbon nanofiber(CNF))is developed through electrospinning,high-temperature calcination,and sodium borohydride(NaBH4)reduction,featuring highly dispersed Pt nanoparticles anchored on oxygen vacancy(Ov)-rich CeO_(2) embedded within CNF.The strong metal–support interaction(SMSI)induces Pt–O–Ce interfacial bonding,facilitating electron transfer and enhancing MOR performance.Pt/CeO_(2)-CNF achieves a mass activity of 5.29 A·mgPt^(-1),3.5 times higher than commercial Pt/C,alongside exceptional stability(92%retention after 1000 cycles)and CO tolerance.When deployed as a DMFC anode,it delivers a peak power density of 34.72 mW·cm^(-2),outperforming Pt/C by 31%.Characterization results indicate that SMSI induces charge redistribution between Pt and CeO_(2),which synergistically enhances the reaction kinetics of MOR with the hydroxyl groups produced by CeO_(2) hydrolysis.In addition,the uniform dispersion of in-situ grown CeO_(2) is ensured on CNF,and Ov acts as an anchoring point to stabilize Pt nanoparticles,improving the stability of the catalyst.This work establishes a design framework for synthesizing high-performance Pt-based DMFC electrocatalysts through controlled structural and electronic modulation strategies.展开更多
Highly active and robust electrocatalysts for methanol oxidation reaction(MOR)are of great significance to the commercial availability of alkaline direct methanol fuel cells(ADMFC).Pd-based nanostructures have receive...Highly active and robust electrocatalysts for methanol oxidation reaction(MOR)are of great significance to the commercial availability of alkaline direct methanol fuel cells(ADMFC).Pd-based nanostructures have received considerable attention in ADMFCs among non-platinum catalysts due to their high activity and tolerance against CO poisoning,which is strongly determined by their composition and structure.Herein,a one-spot hydrothermal method to synthesize Cu-doped Pd_(7)Te_(3)ultrathin nanowires was proposed.The density functional theory calculations show that the Cu doping simultaneously facilitates the desorption of CO^(*)and adsorption of OH,which refreshes the active sites quickly and thus enhances the electroactivity for MOR.Benefiting from their ultrathin architecture and the modified bonding and anti-bonding d states of Pd,Cu-doped Pd_(7)Te_(3)nanowires show about twofold and threefold mass activity promotion and enhanced durability for MOR when compared to the pure Pd_(7)Te_(3)nanowires and commercial Pd/C catalysts.This work not only provides a simple one-step synthesis strategy for Pd-based nanowire catalysts,but also helps to inspire the catalyst design in ADMFC.展开更多
Highly dispersed tungsten carbide（WC） nanoparticles（NPs） sandwiched between few-layer reduced graphene oxide（RGO） have been successfully synthesized by using thiourea as an anchoring and inducing reagent.The met...Highly dispersed tungsten carbide（WC） nanoparticles（NPs） sandwiched between few-layer reduced graphene oxide（RGO） have been successfully synthesized by using thiourea as an anchoring and inducing reagent.The metatungstate ion,[H2W（12）O（40）]^6-,is assembled on thiourea-modified graphene oxide（GO） by an impregnation method.The WC NPs,with a mean diameter of 1.5 nm,are obtained through a process whereby ammonium metatungstate first turns to WS2,which then forms an intercalation compound with RGO before growing,in situ,to WC NPs.The Pt/WC-RGO electrocatalysts are fabricated by a microwave-assisted method.The intimate contacts between Pt,WC,and RGO are confirmed by X-ray diffraction,scanning electron microscope,transmission electron microscope,and Raman spectroscopy.For methanol oxidation,the Pt/WC-RGO electrocatalyst exhibited an electrochemical surface area value of 246.1 m^2/g Pt and a peak current density of1364.7 mA/mg Pt,which are,respectively,3.66 and 4.77 times greater than those of commercial Pt/C electrocatalyst（67.2 m^2/g Pt,286.0 mA/mg Pt）.The excellent CO-poisoning resistance and long-term stability of the electrocatalyst are also evidenced by CO stripping,chronoamperometry,and accelerated durability testing.Because Pt/WC-RGO has higher catalytic activity compared with that of commercial Pt/C,as a result of its intercalated structure and synergistic effect,less Pt will be required for the same performance,which in turn will reduce the cost of the fuel cell.The present method is facile,efficient,and scalable for mass production of the nanomaterials.展开更多
Methanol oxidation reaction （MOR） at Pt and Pt electrode surface deposited with various amounts of Ru （denoted as PtxRuy, nominal coverage y is 0.17, 0.27, and 0.44 ML） in 0.1 mol/L HClO4＋0.5 mol/L MeOH has been ...Methanol oxidation reaction （MOR） at Pt and Pt electrode surface deposited with various amounts of Ru （denoted as PtxRuy, nominal coverage y is 0.17, 0.27, and 0.44 ML） in 0.1 mol/L HClO4＋0.5 mol/L MeOH has been studied under potentiostatic conditions by in situ FTIR spectroscopy in attenuated-total-reflection con guration and di erential electro-chemical mass spectrometry under controlled flow conditions. Results reveal that （i） CO is the only methanol-related adsorbate observed by IR spectroscopy at all the Pt and PtRu electrodes examined at potentials from 0.3 V to 0.6 V （vs. RHE）; （ii） at Pt0.56Ru0.44, two IR bands, one from CO adsorbed at Ru islands and the other from COL at Pt substrate are detected, while at other electrodes, only a single band for COL adsorbed at Pt is observed; （iii） MOR activity decreases in the order of Pt0.73Ru0.27〉Pt0.56Ru0.44〉Pt0.83Ru0.17〉Pt; （iv） at 0.5 V, MOR at Pt0.73Ru0.27 reaches a current e ciency of 50% for CO2 production, the turn-over frequency from CH3OH to CO2 is ca. 0.1 molecule/（site sec）. Suggestions for further improving of PtRu catalysts for MOR are provided.展开更多
Although one-dimensional Pt nanocrystals have long been regarded as ideal electrode catalysts for fuel cells,the synthetic techniques commonly involve the use of various complicated templates or surfactants,which have...Although one-dimensional Pt nanocrystals have long been regarded as ideal electrode catalysts for fuel cells,the synthetic techniques commonly involve the use of various complicated templates or surfactants,which have largely hampered their large-scale industrial application.Herein,we present a convenient and cost-effective approach to the stereoassembly of quasi-one-dimensional grain boundary-enriched Pt nanoworms on nitrogen-doped low-defect graphitic carbon nanosheets(Pt NWs/NL-CNS).Benefiting from its numerous catalytically active grain boundaries as well as optimized electronic structure,the as-derived Pt NWs/NL-CNS catalyst possesses exceptionally good electrocatalytic properties for methanol oxidation,including an ultrahigh mass activity of 1949.5 mA mg^(-1), reliable long-term durability,and strong poison tolerance,affording one of the most active Pt-based electrocatalysts for methanol oxidation reaction.Density functional theory calculation further reveals that the formation of worm-shape Pt morphology is attributed to the modified electronic structure as well as controllable defect density of the carbon matrix,which could also weaken the adsorption ability of Pt towards CO molecule and meanwhile synergistically promotes the catalytic reaction kinetics.展开更多
Direct methanol fuel cells are one of the most promising alternative energy technologies in the foreseeable future, but its successful commercialization in large scale is still heavily hindered by several technical sh...Direct methanol fuel cells are one of the most promising alternative energy technologies in the foreseeable future, but its successful commercialization in large scale is still heavily hindered by several technical shortfalls, especially the undesirable activity and durability issues of electrocatalysts toward methanol oxidation reaction. In light of these challenges, the inherent advantages of unsupported Pt based nanostructures demonstrate their great potentials as durable and efficient electrocatalysts for direct methanol fuel cells. This review will summarize recent achievements of unsupported Pt-based electrocatalysts toward methanol oxidation, with highlighting the interactions between the performance and structure tailoring and composition modulating. At last, a perspective is proposed for the upcoming challenges and possible opportunities to further prompt the practical application of unsupported Pt-based electrocatalysts for direct methanol fuel cells.展开更多
Reasonable design and controllable synthesis of non-Pt catalysts with high methanol oxidation activity are regarded as a valid way to promote the large-scale com-mercial applications of direct methanol fuel cells(DMFC...Reasonable design and controllable synthesis of non-Pt catalysts with high methanol oxidation activity are regarded as a valid way to promote the large-scale com-mercial applications of direct methanol fuel cells(DMFCs).Herein,we develop a convenient and cost-ef-fective approach to the successful fabrication of nanosized Rh grown on single-walled carbon nanohorns(Rh/SWCNH)as anode catalysts for DMFCs.The unique architectural configuration endows the as-obtained hybrids with a series of intriguing structural merits,including large specific surface areas,abundant opened holes,optimized electronic structures,homogeneous Rh dispersion,and good electrical conductivity.As a consequence,the resulting Rh/SWCNH catalysts exhibit exceptional elec-trocatalytic properties in terms of a large electrochemically active surface area of 102.5 m^(2)·g^(-1),a high mass activity of 784.0 mA·mg^(-1),as well as reliable long-term durability towards the methanol oxidation reaction in alkaline media,thereby holding great potential as alternatives for com-mercial Pt/carbon black and Pd/carbon black catalysts.展开更多
Searching for non-noble metal catalysts with high activities and low price is critical to the commercialization of methanol oxidation in the process of fuel cells.Herein,two new pseudo-isomeric Ni metal-organic framew...Searching for non-noble metal catalysts with high activities and low price is critical to the commercialization of methanol oxidation in the process of fuel cells.Herein,two new pseudo-isomeric Ni metal-organic frameworks(Ni-MOFs)(CTGU-17/CTGU-18)have been prepared with 1,4-naphthalenedi-carboxylate(H_(2)NDC),4,4’-dipyridyl amine(DPA)and Ni(ClO_(4))_(2)under hydrothermal condition.Each phase contains one water molecule,but differs dramatically in its bonding to the framework,resulting in different topological networks with fourfold interpenetrating 4-connected dia net(CTGU-17)and(3,7)-connected net(CTGU-18)and diverse electrocatalytic performance for methanol oxidation reaction(MOR).Remarkably,by combining each MOF with the conductive additive,acetylene black(AB),a composite material,AB&CTGU-18(2:4)was confirmed to have an excellent performance for MOR with a high mass specific peak current of 442.3 mA·mg^(-1).The enhanced electrocatalytic activities and robustness might be attributed to the synergetic effect of acetylene black and the active metal centers of MOFs particles for methanol oxidation.The present work would provide a new insight for the rational design of MOFs-based composites with enhanced methanol oxidation reaction performance.展开更多
Pt based materials are the most efficient electrocatalysts for the oxygen reduction reaction(ORR)and methanol oxidation reaction(MOR)in fuel cells.Maximizing the utilization of Pt based materials by modulating their m...Pt based materials are the most efficient electrocatalysts for the oxygen reduction reaction(ORR)and methanol oxidation reaction(MOR)in fuel cells.Maximizing the utilization of Pt based materials by modulating their morphologies to expose more active sites is a fundamental objective for the practical application of fuel cells.Herein,we report a new class of hierarchically skeletal Pt-Ni nanocrystals(HSNs)with a multi-layered structure,prepared by an inorganic acid-induced solvothermal method.The addition of H_(2)SO_(4)to the synthetic protocol provides a critical trigger for the successful growth of Pt-Ni nanocrystals with the desired structure.The Pt-Ni HSNs synthesized by this method exhibit enhanced mass activity of 1.25 A mgpt−1 at 0.9 V(versus the reversible hydrogen electrode)towards ORR in 0.1-M HClO_(4),which is superior to that of Pt-Ni multi-branched nanocrystals obtained by the same method in the absence of inorganic acid;it is additionally 8.9-fold higher than that of the commercial Pt/C catalyst.Meanwhile,it displays enhanced stability,with only 21.6%mass activity loss after 10,000 cycles(0.6–1.0 V)for ORR.Furthermore,the Pt-Ni HSNs show enhanced activity and anti-toxic ability in CO for MOR.The superb activity of the Pt-Ni HSNs for ORR and MOR is fully attributed to an extensively exposed electrochemical surface area and high intrinsic activity,induced by strain effects,provided by the unique hierarchically skeletal alloy structure.The novel open and hierarchical structure of Pt-Ni alloy provides a promising approach for significant improvements of the activity of Pt based alloy electrocatalysts.展开更多
Pt/CeO_(2)-C catalysts with CeO_(2)pre-calcined at 300-600℃were synthesized by combining hydrothermal calcination and wet im-pregnation.The effects of the pre-calcined CeO_(2)on the performance of Pt/CeO_(2)-C cataly...Pt/CeO_(2)-C catalysts with CeO_(2)pre-calcined at 300-600℃were synthesized by combining hydrothermal calcination and wet im-pregnation.The effects of the pre-calcined CeO_(2)on the performance of Pt/CeO_(2)-C catalysts in methanol oxidation were investigated.The Pt/CeO_(2)-C catalysts with pre-calcined CeO_(2)at 300-600℃showed an average particle size of 2.6-2.9 nm and exhibited better methanol elec-tro-oxidation catalytic activity than the commercial Pt/C catalyst.In specific,the Pt/CeO_(2)-C catalysts with pre-calcined CeO_(2)at 400℃dis-played the highest electrochemical surface area value of 68.14 m2·g−1 and If/Ib ratio(the ratio of the forward scanning peak current density(If)and the backward scanning peak current density(Ib))of 1.26,which are considerably larger than those(53.23 m2·g−1 and 0.79,respectively)of the commercial Pt/C catalyst,implying greatly enhanced CO tolerance.展开更多
Exploring effective, durable, and affordable electrocatalysts of methanol oxidation reaction(MOR) is of vital significance for the industrial application of direct methanol fuel cells. Herein, an efficient, general,an...Exploring effective, durable, and affordable electrocatalysts of methanol oxidation reaction(MOR) is of vital significance for the industrial application of direct methanol fuel cells. Herein, an efficient, general,and expandable method is developed to synthesis two-dimensional(2D) ternary Pt Bi M nanoplates(NPLs), in which various M(Co, Ni, Cu, Zn, Sn) is severed as the third component to the binary Pt Bi system. The MOR performance of Pt Bi M NPLs is entirely investigated, demonstrating that both the MOR activity and durability is enhanced with the introduction of the additional composition. Pt3Bi3Zn NPLs shows much higher MOR activity and stability than that of the Pt Bi counterparts, not to mention the current advanced Pt Ru/C and Pt/C catalysts. The prominent performances are attributed to the modulated electronic structure of the surface Pt in Pt Bi NPLs by the addition of Zn, resulting in a weakened affination between Pt and the adsorbed poisoning species(mainly CO) compared with Pt Bi NPLs, verified by density functional theory(DFT) calculations. In addition, the absorbed OH can be generated on the surface of Zn atom due to its favorable water activation properties, thus the CO removal on the adjacent Pt atoms is accelerated, further leading to a high activity and anti-poisoning performance of the resulting Pt_(3)Bi_(3)Zn catalyst. This work provides new insights and robust strategy for highly efficient MOR electrocatalyst with extraordinary anti-poisoning performance and stability.展开更多
In this paper,a new two-dimensional(2 D)/2 D composite of Bi2 WO6/MoS2 was facile synthesized,and then was used as supporting material for depositing Pt nanoparticles.The as-synthesized Pt-Bi2 WO6/MoS2 was extended in...In this paper,a new two-dimensional(2 D)/2 D composite of Bi2 WO6/MoS2 was facile synthesized,and then was used as supporting material for depositing Pt nanoparticles.The as-synthesized Pt-Bi2 WO6/MoS2 was extended into photo-assisted electrocatalytic oxidation of methanol,which is a model anode reaction for direct methanol fuel cell.Compare with traditional electrocatalytic process,PtBi2 WO6/MoS2 displays 1.5 times enhanced electrocatalytic performance on methanol oxidation with assistance of visible light irradiation and 2.2 times for commercial Pt/C.Besides,from the results of chronoamperometric and chronopotentiometry experiments,the stability of Pt-Bi2 WO6/MoS2 electrode is clearly improved under visible light irradiation.The synergistic effects of photo-and electro-catalytic in the heterojunction of Pt-Bi2 WO6/MoS2 in favor of the above enhancement.This research gives more insights in the fields of photo-assisted traditional electrocatalytic application by constructing of semiconductor heterojunction carrier.展开更多
Catalyst support is extremely important for future fuel cell devices.In this work,we developed doubleshelled C/TiO2(DSCT)hollow spheres as an excellent catalyst support via a template-directed method.The combination o...Catalyst support is extremely important for future fuel cell devices.In this work,we developed doubleshelled C/TiO2(DSCT)hollow spheres as an excellent catalyst support via a template-directed method.The combination of hollow structure,TiO2 shell and carbon layer results in excellent electron conductivity,electrocatalytic activity,and chemical stability.These uniformed DSCT hollow spheres are used as catalyst support to synthesize Pt/DSCT hollow spheres electrocatalyst.The resulting Pt/DSCT hollow spheres exhibited high catalytic performance with a current density of 462 mA mg^-1 for methanol oxidation reaction,which is 2.52 times higher than that of the commercial Pt/C.Furthermore,the increased tolerance to carbonaceous poisoning with a higher If/Ibratio and a better long-term stability in acid media suggests that the DSCT hollow sphere is a promising C/TiO2-based catalyst support for direct methanol fuel cells applications.展开更多
The polyaniline/polysulfone（PAN/PSF） composite films were prepared by electropolymerization,and then CeO2-Pt particles were codeposited into this composite film to obtain the CeO2-Pt-modified polyaniline/polysulfone...The polyaniline/polysulfone（PAN/PSF） composite films were prepared by electropolymerization,and then CeO2-Pt particles were codeposited into this composite film to obtain the CeO2-Pt-modified polyaniline/polysulfone（CeO2-Pt/PAN/PSF） electrodes.Their morphol-ogy and chemical component were characterized by field emission scanning electron microscopy（FESEM） and energy dispersive X-ray spectroscopy（EDS）,respectively.The results showed that the composite film had bi-layer structure with asymmetrical pores,and platinum and cerium oxide particles were homogeneously dispersed in the modified film electrodes.The cyclic voltammetry（CV） and electrochemical impedance spectroscopy（EIS） techniques were applied to investigate the electrocatalytic activity of the Pt-CeO2/PAN/PSF electrodes.It was indicated that appropriate amount of CeO2 could enhance the catalytic activity of Pt for methanol electro-oxidation.Chronoamperometry（i-t） measurements revealed that the Pt-CeO2/PAN/PSF electrode was relatively endurable for intermediate production.In addition,different mix-ing amounts of Pt and CeO2 nanoparticles were also investigated in detail.展开更多
Platinum and palladium(PtPd)alloy nanoparticles(NPs)are excellent catalysts for direct methanol fuel cells.In this study,we developed PtPd alloy NPs through the co‐reduction of K2PtCl4and Na2PdCl4in a polyol synthesi...Platinum and palladium(PtPd)alloy nanoparticles(NPs)are excellent catalysts for direct methanol fuel cells.In this study,we developed PtPd alloy NPs through the co‐reduction of K2PtCl4and Na2PdCl4in a polyol synthesis environment.During the reaction,the feed molar ratio of the two precursors was carried over to the final products,which have a narrow size distribution with a mean size of approximately4nm.The catalytic activity for methanol oxidation reactions possible depends closely on the composition of as‐prepared PtPd alloy NPs,and the NPs with a Pt atomic percentage of approximately75%result in higher activity and stability with a mass specific activity that is7times greater than that of commercial Pt/C catalysts.The results indicate that through composition control,PtPd alloy NPs can improve the effectiveness of catalytic performance.展开更多
To simultaneously reduce noble metal Pd usage and enhance electrocatalytic performance for methanol oxidation,Pd/Co2O3 composites with ultrafine three-dimensional(3D)nanoporous structures were designed and synthesized...To simultaneously reduce noble metal Pd usage and enhance electrocatalytic performance for methanol oxidation,Pd/Co2O3 composites with ultrafine three-dimensional(3D)nanoporous structures were designed and synthesized by simple one-step dealloying of a melt-spun Al-Pd-Co alloy with an alkaline solution.Their electrocatalytic activity in alkaline media was determined by a Versa-STAT MC workstation.The results indicate that the typical sizes of the ligaments and pores of the composites were approximately 8-9 nm.The Co2O3 was uniformly distributed on the Pd ligament surface.Among the as-prepared samples,the nanoporous Pd/Co2O3 composite generated from dealloying of the Al84.5Pd15Co0.5 alloy had the best electrocatalytic activity,and its activity was enhanced by approximately 230%compared with the nanoporous Pd from dealloying of Al85Pd15.The improvement of the electrocatalytic performance was mainly attributed to the electronic modification effect between Pd and Co as well as the bifunctional mechanism between Pd and Co2O3.展开更多
A successful approach to assemble Au core Pd shell （Au@Pd） nanoparticles on the surface of multi-walled carbon nanotubes functionalized by methylene blue （MB） （Au@Pd/fuv-MWCNTs） was reported. In this method, MWC...A successful approach to assemble Au core Pd shell （Au@Pd） nanoparticles on the surface of multi-walled carbon nanotubes functionalized by methylene blue （MB） （Au@Pd/fuv-MWCNTs） was reported. In this method, MWCNTs were functionalized under ultraviolet irradiation. UV-Vis analysis and high-angle annular dark-field trans- mission electron microscope （HAADF-TEM） image prove that core-shell structure of Au@Pd nanoparticles forms. TEM results indicate that Au@Pd nanoparticles （ - 5.2 nm） are well-dispersed on the surface of fuv-MWCNTs. X-ray photoelectron spectroscopy （XPS） reveals that ultraviolet irradiation can promote the interaction between Au@Pd nanoparticles and the functional groups on the surface of MWCNTs. Cyclic voltammograms （CV）, chronoampero- grams （CA）, and electrochemical impedance spectroscopy （EIS） results demonstrate that the Au@Pd/fuv-MWCNTs catalysts show excellent electrocatalytic performance for methanol oxidation in alkaline media. The catalytic activity of the Au@Pd/fuv-MWCNTs is ~ 2 times higher than that of the commercial Pd/C catalysts. This is mostly attributed to that ultraviolet irradiation can make the moieties of MB provide a uniform surface with active and anchoring sites, and improves the functional effect of MB on the surface of MWCNTs. Especially, ultraviolet irradiation modifies electronic structure of Pd and is beneficial for the enhance- ment of catalytic activity.展开更多
Bimetallic Pt-based catalysts have been extensively investigated to enhance the performance of direct methanol fuel cells(DMFCs) because CO, a by-product, reduces the activity of the pure Pt catalysts. Herein, we synt...Bimetallic Pt-based catalysts have been extensively investigated to enhance the performance of direct methanol fuel cells(DMFCs) because CO, a by-product, reduces the activity of the pure Pt catalysts. Herein, we synthesized Pt-Pb hexagonal nanoplates as a model catalyst for the methanol oxidation reaction(MOR) and further controlled the Pt and Pb distributions on the surface of the nanoplates through acetic acid(HAc) treatment. As a result, we obtained Pt-Pb nanoplates and HAc-treated Pt-Pb nanoplates with homogeneous and heterogeneous distributions of the Pt-Pb alloy surfaces, respectively. We showed that the MOR activity and stability of the Pt-Pb nanoplates improved compared to those of the HAc-treated Pt-Pb nanoplates, mainly due to the enhanced CO tolerance and the modified electronic structure of Pt under the influence of the oxophilic Pb.展开更多
基金supported by the National Natural Science Foundation of China(Nos.12222508 and 12475325)the National Key Research and Development Program of China(Nos.2024YFA1509201 and 2023YFA1506304)the beamlines BL10B(No.31131.02.HLS.PES)and BL01B(No.31131.02.HLS.IRSM)in NSRL,and BL11B(No.31124.02.SSRF.BL11B)in SSRF for synchrotron radiation measurements.
文摘Methanol oxidation reaction(MOR)is a key process in direct methanol fuel cells(DMFCs),determining both energy efficiency and stability.Despite efforts,the impact of dynamic structural changes of Pt-based catalysts on MOR performance remains poorly understood.Here,we report on the impact mechanism of dynamic changes on MOR performance in the Pd-Pt concave nanocubes(CNCs)system.Pt with high-index facets exposed abundant active sites for methanol oxidation,resulting in an exceptional mass activity of 0.89 A·mg_(Pt)^(-1).Pd underwent an oxidationredeposition process during MOR,dynamically restructuring the catalyst and producing a volcano-type activity.Pd^(δ+)species generated during oxidative etching promoted OH*formation,accelerating CO oxidation on Pt sites,thus mitigating poisoning.With continued cycling,redeposited Pd partially blocked Pt sites,counteracting the positive effect of the generated Pd^(δ+).The dynamic balance of Pd oxidation and redeposition governed the activity evolution while sustaining the exceptional durability of Pd-Pt CNCs during prolonged cycling.
基金support by the National Natural Science Foundation of China(Nos.U20A20123,51874357,22379166)Natural Science Foundation for Distinguished Young Scholars of Hunan Province(No.2022JJ10089)。
文摘The sluggish reaction kinetics of the oxygen evolution reaction(OER)and methanol oxidation reaction(MOR)remain obstacles to the commercial promotion of water splitting and direct methanol fuel cells.Considering the vital role of noble metals in electrocatalytic activity,this work focuses on the rational synthesis of Ni-noble metal composite nanocatalysts for overcoming the drawbacks of high cost and susceptible oxidized surfaces of noble metals.The inherent catalytic activity is improved by the altered electronic structure and effective active sites of the catalyst induced by the size effect of noble metal clusters.In particular,a series of Ni-noble metal nanocomposites are successfully synthesized by partially introducing noble metal into Ni with porous interfacial defects derived from Ni-Al layered double hydroxide(LDH).The Ni_(10)Pd_(1)nanocomposite exhibits high OER catalytic activity with an overpotential of 0.279 V at 10 m A/cm^(2),surpassing Ni_(10)Ag_(1)and Ni_(10)Au_(1)counterparts.Furthermore,the average diameter of Pd clusters gradually increases from 5.57 nm to 44.44 nm with the increased proportion of doped Pd,leading to the passivation of catalytic activity due to the exacerbated surface oxidation of Pd in the form of Pd^(2+).After optimization,Ni_(10)Pd_(1)delivers significantly enhanced OER and MOR electroactivities and long-term stability compared to that of Ni_(2)Pd_(1),Ni_(1)Pd_(1)and Ni_(1)Pd_(2),which is conducive to the effective utilization of Pd and alleviation of surface oxidation.
基金supported by the Natural Science Foundation of Beijing Municipal(No.2252043)the National Natural Science Foundation of China(No.52170019),the Fundamental Research Funds for the Central Universities(No.06500100)the“Ten Thousand Plan”-National High-level personnel of special support program.
文摘Pt-based methanol oxidation reaction(MOR)electrocatalysts with high activity,stability,and carbon monoxide(CO)tolerance are critical for advancing direct methanol fuel cells(DMFC).Herein,a low-Pt-content electrocatalyst(Pt/CeO_(2)-carbon nanofiber(CNF))is developed through electrospinning,high-temperature calcination,and sodium borohydride(NaBH4)reduction,featuring highly dispersed Pt nanoparticles anchored on oxygen vacancy(Ov)-rich CeO_(2) embedded within CNF.The strong metal–support interaction(SMSI)induces Pt–O–Ce interfacial bonding,facilitating electron transfer and enhancing MOR performance.Pt/CeO_(2)-CNF achieves a mass activity of 5.29 A·mgPt^(-1),3.5 times higher than commercial Pt/C,alongside exceptional stability(92%retention after 1000 cycles)and CO tolerance.When deployed as a DMFC anode,it delivers a peak power density of 34.72 mW·cm^(-2),outperforming Pt/C by 31%.Characterization results indicate that SMSI induces charge redistribution between Pt and CeO_(2),which synergistically enhances the reaction kinetics of MOR with the hydroxyl groups produced by CeO_(2) hydrolysis.In addition,the uniform dispersion of in-situ grown CeO_(2) is ensured on CNF,and Ov acts as an anchoring point to stabilize Pt nanoparticles,improving the stability of the catalyst.This work establishes a design framework for synthesizing high-performance Pt-based DMFC electrocatalysts through controlled structural and electronic modulation strategies.
基金supported by the National Natural Science Foundation of China(Nos.22275178 and 22005285)the Fundamental Research Funds for the Central Universities(Nos.JUSRP123013 and JUSRP123015)+1 种基金performed on Hefei advanced computing centerSupercomputing USTC and National Supercomputing Center in Shenzhen are acknowledged for computational support.
文摘Highly active and robust electrocatalysts for methanol oxidation reaction(MOR)are of great significance to the commercial availability of alkaline direct methanol fuel cells(ADMFC).Pd-based nanostructures have received considerable attention in ADMFCs among non-platinum catalysts due to their high activity and tolerance against CO poisoning,which is strongly determined by their composition and structure.Herein,a one-spot hydrothermal method to synthesize Cu-doped Pd_(7)Te_(3)ultrathin nanowires was proposed.The density functional theory calculations show that the Cu doping simultaneously facilitates the desorption of CO^(*)and adsorption of OH,which refreshes the active sites quickly and thus enhances the electroactivity for MOR.Benefiting from their ultrathin architecture and the modified bonding and anti-bonding d states of Pd,Cu-doped Pd_(7)Te_(3)nanowires show about twofold and threefold mass activity promotion and enhanced durability for MOR when compared to the pure Pd_(7)Te_(3)nanowires and commercial Pd/C catalysts.This work not only provides a simple one-step synthesis strategy for Pd-based nanowire catalysts,but also helps to inspire the catalyst design in ADMFC.
基金supported by the International Science & Technology Cooperation Program of China(2010DFB63680)the National Natural Science Foundation of China(21376220)Zhejiang Provincial Natural Science Foundation of China(LY16B060009,LY12B03008)~~
文摘Highly dispersed tungsten carbide（WC） nanoparticles（NPs） sandwiched between few-layer reduced graphene oxide（RGO） have been successfully synthesized by using thiourea as an anchoring and inducing reagent.The metatungstate ion,[H2W（12）O（40）]^6-,is assembled on thiourea-modified graphene oxide（GO） by an impregnation method.The WC NPs,with a mean diameter of 1.5 nm,are obtained through a process whereby ammonium metatungstate first turns to WS2,which then forms an intercalation compound with RGO before growing,in situ,to WC NPs.The Pt/WC-RGO electrocatalysts are fabricated by a microwave-assisted method.The intimate contacts between Pt,WC,and RGO are confirmed by X-ray diffraction,scanning electron microscope,transmission electron microscope,and Raman spectroscopy.For methanol oxidation,the Pt/WC-RGO electrocatalyst exhibited an electrochemical surface area value of 246.1 m^2/g Pt and a peak current density of1364.7 mA/mg Pt,which are,respectively,3.66 and 4.77 times greater than those of commercial Pt/C electrocatalyst（67.2 m^2/g Pt,286.0 mA/mg Pt）.The excellent CO-poisoning resistance and long-term stability of the electrocatalyst are also evidenced by CO stripping,chronoamperometry,and accelerated durability testing.Because Pt/WC-RGO has higher catalytic activity compared with that of commercial Pt/C,as a result of its intercalated structure and synergistic effect,less Pt will be required for the same performance,which in turn will reduce the cost of the fuel cell.The present method is facile,efficient,and scalable for mass production of the nanomaterials.
文摘Methanol oxidation reaction （MOR） at Pt and Pt electrode surface deposited with various amounts of Ru （denoted as PtxRuy, nominal coverage y is 0.17, 0.27, and 0.44 ML） in 0.1 mol/L HClO4＋0.5 mol/L MeOH has been studied under potentiostatic conditions by in situ FTIR spectroscopy in attenuated-total-reflection con guration and di erential electro-chemical mass spectrometry under controlled flow conditions. Results reveal that （i） CO is the only methanol-related adsorbate observed by IR spectroscopy at all the Pt and PtRu electrodes examined at potentials from 0.3 V to 0.6 V （vs. RHE）; （ii） at Pt0.56Ru0.44, two IR bands, one from CO adsorbed at Ru islands and the other from COL at Pt substrate are detected, while at other electrodes, only a single band for COL adsorbed at Pt is observed; （iii） MOR activity decreases in the order of Pt0.73Ru0.27〉Pt0.56Ru0.44〉Pt0.83Ru0.17〉Pt; （iv） at 0.5 V, MOR at Pt0.73Ru0.27 reaches a current e ciency of 50% for CO2 production, the turn-over frequency from CH3OH to CO2 is ca. 0.1 molecule/（site sec）. Suggestions for further improving of PtRu catalysts for MOR are provided.
基金financially supported by the National Natural Science Foundation of China(51802077,21975129)the Fundamental Research Funds for the Central Universities(2019B16214)+1 种基金China Postdoctoral Science Foundation(2016 T90414)Jiangsu Planned Projects for Postdoctoral Research Funds(1601026A)。
文摘Although one-dimensional Pt nanocrystals have long been regarded as ideal electrode catalysts for fuel cells,the synthetic techniques commonly involve the use of various complicated templates or surfactants,which have largely hampered their large-scale industrial application.Herein,we present a convenient and cost-effective approach to the stereoassembly of quasi-one-dimensional grain boundary-enriched Pt nanoworms on nitrogen-doped low-defect graphitic carbon nanosheets(Pt NWs/NL-CNS).Benefiting from its numerous catalytically active grain boundaries as well as optimized electronic structure,the as-derived Pt NWs/NL-CNS catalyst possesses exceptionally good electrocatalytic properties for methanol oxidation,including an ultrahigh mass activity of 1949.5 mA mg^(-1), reliable long-term durability,and strong poison tolerance,affording one of the most active Pt-based electrocatalysts for methanol oxidation reaction.Density functional theory calculation further reveals that the formation of worm-shape Pt morphology is attributed to the modified electronic structure as well as controllable defect density of the carbon matrix,which could also weaken the adsorption ability of Pt towards CO molecule and meanwhile synergistically promotes the catalytic reaction kinetics.
基金financial supported by National 1000 Young Talents Program of ChinaNation Natural Science Foundation of China(21473111)+2 种基金The Innovation Foundation of Shenzhen Government(JCYJ20160408173202143)the Joint Fund of Energy Storage of Qingdao(20160012)the Innovation Research Funds of HUST(3004013109,0118013089,and 2017KFYXJJ164)
文摘Direct methanol fuel cells are one of the most promising alternative energy technologies in the foreseeable future, but its successful commercialization in large scale is still heavily hindered by several technical shortfalls, especially the undesirable activity and durability issues of electrocatalysts toward methanol oxidation reaction. In light of these challenges, the inherent advantages of unsupported Pt based nanostructures demonstrate their great potentials as durable and efficient electrocatalysts for direct methanol fuel cells. This review will summarize recent achievements of unsupported Pt-based electrocatalysts toward methanol oxidation, with highlighting the interactions between the performance and structure tailoring and composition modulating. At last, a perspective is proposed for the upcoming challenges and possible opportunities to further prompt the practical application of unsupported Pt-based electrocatalysts for direct methanol fuel cells.
基金financially supported by the National Natural Science Foundation of China (No.51802077)the Fundamental Research Funds for the Central Universities (No. B210202093)
文摘Reasonable design and controllable synthesis of non-Pt catalysts with high methanol oxidation activity are regarded as a valid way to promote the large-scale com-mercial applications of direct methanol fuel cells(DMFCs).Herein,we develop a convenient and cost-ef-fective approach to the successful fabrication of nanosized Rh grown on single-walled carbon nanohorns(Rh/SWCNH)as anode catalysts for DMFCs.The unique architectural configuration endows the as-obtained hybrids with a series of intriguing structural merits,including large specific surface areas,abundant opened holes,optimized electronic structures,homogeneous Rh dispersion,and good electrical conductivity.As a consequence,the resulting Rh/SWCNH catalysts exhibit exceptional elec-trocatalytic properties in terms of a large electrochemically active surface area of 102.5 m^(2)·g^(-1),a high mass activity of 784.0 mA·mg^(-1),as well as reliable long-term durability towards the methanol oxidation reaction in alkaline media,thereby holding great potential as alternatives for com-mercial Pt/carbon black and Pd/carbon black catalysts.
基金the National Natural Science Foundation of China(Nos.21971143,21673127,21671119,51572152 and 21805165)the Program of the Ministry of Education of China for Introducing Talents of Discipline to Universities(No.DT20015)Innovation Team of Young and Middle-aged Research(ITOYMR)in the Higher Education Institutions of Hubei Province(No.T201904)。
文摘Searching for non-noble metal catalysts with high activities and low price is critical to the commercialization of methanol oxidation in the process of fuel cells.Herein,two new pseudo-isomeric Ni metal-organic frameworks(Ni-MOFs)(CTGU-17/CTGU-18)have been prepared with 1,4-naphthalenedi-carboxylate(H_(2)NDC),4,4’-dipyridyl amine(DPA)and Ni(ClO_(4))_(2)under hydrothermal condition.Each phase contains one water molecule,but differs dramatically in its bonding to the framework,resulting in different topological networks with fourfold interpenetrating 4-connected dia net(CTGU-17)and(3,7)-connected net(CTGU-18)and diverse electrocatalytic performance for methanol oxidation reaction(MOR).Remarkably,by combining each MOF with the conductive additive,acetylene black(AB),a composite material,AB&CTGU-18(2:4)was confirmed to have an excellent performance for MOR with a high mass specific peak current of 442.3 mA·mg^(-1).The enhanced electrocatalytic activities and robustness might be attributed to the synergetic effect of acetylene black and the active metal centers of MOFs particles for methanol oxidation.The present work would provide a new insight for the rational design of MOFs-based composites with enhanced methanol oxidation reaction performance.
文摘Pt based materials are the most efficient electrocatalysts for the oxygen reduction reaction(ORR)and methanol oxidation reaction(MOR)in fuel cells.Maximizing the utilization of Pt based materials by modulating their morphologies to expose more active sites is a fundamental objective for the practical application of fuel cells.Herein,we report a new class of hierarchically skeletal Pt-Ni nanocrystals(HSNs)with a multi-layered structure,prepared by an inorganic acid-induced solvothermal method.The addition of H_(2)SO_(4)to the synthetic protocol provides a critical trigger for the successful growth of Pt-Ni nanocrystals with the desired structure.The Pt-Ni HSNs synthesized by this method exhibit enhanced mass activity of 1.25 A mgpt−1 at 0.9 V(versus the reversible hydrogen electrode)towards ORR in 0.1-M HClO_(4),which is superior to that of Pt-Ni multi-branched nanocrystals obtained by the same method in the absence of inorganic acid;it is additionally 8.9-fold higher than that of the commercial Pt/C catalyst.Meanwhile,it displays enhanced stability,with only 21.6%mass activity loss after 10,000 cycles(0.6–1.0 V)for ORR.Furthermore,the Pt-Ni HSNs show enhanced activity and anti-toxic ability in CO for MOR.The superb activity of the Pt-Ni HSNs for ORR and MOR is fully attributed to an extensively exposed electrochemical surface area and high intrinsic activity,induced by strain effects,provided by the unique hierarchically skeletal alloy structure.The novel open and hierarchical structure of Pt-Ni alloy provides a promising approach for significant improvements of the activity of Pt based alloy electrocatalysts.
基金financially supported by the National Nat-ural Science Foundation of China(No.51774145).
文摘Pt/CeO_(2)-C catalysts with CeO_(2)pre-calcined at 300-600℃were synthesized by combining hydrothermal calcination and wet im-pregnation.The effects of the pre-calcined CeO_(2)on the performance of Pt/CeO_(2)-C catalysts in methanol oxidation were investigated.The Pt/CeO_(2)-C catalysts with pre-calcined CeO_(2)at 300-600℃showed an average particle size of 2.6-2.9 nm and exhibited better methanol elec-tro-oxidation catalytic activity than the commercial Pt/C catalyst.In specific,the Pt/CeO_(2)-C catalysts with pre-calcined CeO_(2)at 400℃dis-played the highest electrochemical surface area value of 68.14 m2·g−1 and If/Ib ratio(the ratio of the forward scanning peak current density(If)and the backward scanning peak current density(Ib))of 1.26,which are considerably larger than those(53.23 m2·g−1 and 0.79,respectively)of the commercial Pt/C catalyst,implying greatly enhanced CO tolerance.
基金supported by the Hainan Province Science and Technology Special Fund(ZDYF2020037,2020207)the National Natural Science Foundation of China(21805104,22109034,22109035,52164028,62105083)+3 种基金the Basic and Applied Basic Research Foundation of Guangdong Province(2019A1515110558)the Research Fund Program of Key Laboratory of Fuel Cell Technology of Guangdong Province(202021)the Innovative Research Projects for Graduate Students of Hainan Province(Qhys2021-134)the Start-up Research Foundation of Hainan University(KYQD(ZR)-20008,20082,20083,20084,21065,21124,21125)。
文摘Exploring effective, durable, and affordable electrocatalysts of methanol oxidation reaction(MOR) is of vital significance for the industrial application of direct methanol fuel cells. Herein, an efficient, general,and expandable method is developed to synthesis two-dimensional(2D) ternary Pt Bi M nanoplates(NPLs), in which various M(Co, Ni, Cu, Zn, Sn) is severed as the third component to the binary Pt Bi system. The MOR performance of Pt Bi M NPLs is entirely investigated, demonstrating that both the MOR activity and durability is enhanced with the introduction of the additional composition. Pt3Bi3Zn NPLs shows much higher MOR activity and stability than that of the Pt Bi counterparts, not to mention the current advanced Pt Ru/C and Pt/C catalysts. The prominent performances are attributed to the modulated electronic structure of the surface Pt in Pt Bi NPLs by the addition of Zn, resulting in a weakened affination between Pt and the adsorbed poisoning species(mainly CO) compared with Pt Bi NPLs, verified by density functional theory(DFT) calculations. In addition, the absorbed OH can be generated on the surface of Zn atom due to its favorable water activation properties, thus the CO removal on the adjacent Pt atoms is accelerated, further leading to a high activity and anti-poisoning performance of the resulting Pt_(3)Bi_(3)Zn catalyst. This work provides new insights and robust strategy for highly efficient MOR electrocatalyst with extraordinary anti-poisoning performance and stability.
基金support of the National Natural Science Foundation of China (No.21603111)
文摘In this paper,a new two-dimensional(2 D)/2 D composite of Bi2 WO6/MoS2 was facile synthesized,and then was used as supporting material for depositing Pt nanoparticles.The as-synthesized Pt-Bi2 WO6/MoS2 was extended into photo-assisted electrocatalytic oxidation of methanol,which is a model anode reaction for direct methanol fuel cell.Compare with traditional electrocatalytic process,PtBi2 WO6/MoS2 displays 1.5 times enhanced electrocatalytic performance on methanol oxidation with assistance of visible light irradiation and 2.2 times for commercial Pt/C.Besides,from the results of chronoamperometric and chronopotentiometry experiments,the stability of Pt-Bi2 WO6/MoS2 electrode is clearly improved under visible light irradiation.The synergistic effects of photo-and electro-catalytic in the heterojunction of Pt-Bi2 WO6/MoS2 in favor of the above enhancement.This research gives more insights in the fields of photo-assisted traditional electrocatalytic application by constructing of semiconductor heterojunction carrier.
基金supported by the Scholarship from China Scholarship Council(CSC)(Grant no.201604910621)。
文摘Catalyst support is extremely important for future fuel cell devices.In this work,we developed doubleshelled C/TiO2(DSCT)hollow spheres as an excellent catalyst support via a template-directed method.The combination of hollow structure,TiO2 shell and carbon layer results in excellent electron conductivity,electrocatalytic activity,and chemical stability.These uniformed DSCT hollow spheres are used as catalyst support to synthesize Pt/DSCT hollow spheres electrocatalyst.The resulting Pt/DSCT hollow spheres exhibited high catalytic performance with a current density of 462 mA mg^-1 for methanol oxidation reaction,which is 2.52 times higher than that of the commercial Pt/C.Furthermore,the increased tolerance to carbonaceous poisoning with a higher If/Ibratio and a better long-term stability in acid media suggests that the DSCT hollow sphere is a promising C/TiO2-based catalyst support for direct methanol fuel cells applications.
基金Project supported by the National Natural Science Foundation of China (20475077)
文摘The polyaniline/polysulfone（PAN/PSF） composite films were prepared by electropolymerization,and then CeO2-Pt particles were codeposited into this composite film to obtain the CeO2-Pt-modified polyaniline/polysulfone（CeO2-Pt/PAN/PSF） electrodes.Their morphol-ogy and chemical component were characterized by field emission scanning electron microscopy（FESEM） and energy dispersive X-ray spectroscopy（EDS）,respectively.The results showed that the composite film had bi-layer structure with asymmetrical pores,and platinum and cerium oxide particles were homogeneously dispersed in the modified film electrodes.The cyclic voltammetry（CV） and electrochemical impedance spectroscopy（EIS） techniques were applied to investigate the electrocatalytic activity of the Pt-CeO2/PAN/PSF electrodes.It was indicated that appropriate amount of CeO2 could enhance the catalytic activity of Pt for methanol electro-oxidation.Chronoamperometry（i-t） measurements revealed that the Pt-CeO2/PAN/PSF electrode was relatively endurable for intermediate production.In addition,different mix-ing amounts of Pt and CeO2 nanoparticles were also investigated in detail.
基金supported by the National Natural Science Foundation of China (21373272)~~
文摘Platinum and palladium(PtPd)alloy nanoparticles(NPs)are excellent catalysts for direct methanol fuel cells.In this study,we developed PtPd alloy NPs through the co‐reduction of K2PtCl4and Na2PdCl4in a polyol synthesis environment.During the reaction,the feed molar ratio of the two precursors was carried over to the final products,which have a narrow size distribution with a mean size of approximately4nm.The catalytic activity for methanol oxidation reactions possible depends closely on the composition of as‐prepared PtPd alloy NPs,and the NPs with a Pt atomic percentage of approximately75%result in higher activity and stability with a mass specific activity that is7times greater than that of commercial Pt/C catalysts.The results indicate that through composition control,PtPd alloy NPs can improve the effectiveness of catalytic performance.
基金Project(51371135)supported by the National Natural Science Foundation of China
文摘To simultaneously reduce noble metal Pd usage and enhance electrocatalytic performance for methanol oxidation,Pd/Co2O3 composites with ultrafine three-dimensional(3D)nanoporous structures were designed and synthesized by simple one-step dealloying of a melt-spun Al-Pd-Co alloy with an alkaline solution.Their electrocatalytic activity in alkaline media was determined by a Versa-STAT MC workstation.The results indicate that the typical sizes of the ligaments and pores of the composites were approximately 8-9 nm.The Co2O3 was uniformly distributed on the Pd ligament surface.Among the as-prepared samples,the nanoporous Pd/Co2O3 composite generated from dealloying of the Al84.5Pd15Co0.5 alloy had the best electrocatalytic activity,and its activity was enhanced by approximately 230%compared with the nanoporous Pd from dealloying of Al85Pd15.The improvement of the electrocatalytic performance was mainly attributed to the electronic modification effect between Pd and Co as well as the bifunctional mechanism between Pd and Co2O3.
基金financially supported by the National Natural Science Foundation of China (Nos. 51164017, 51374117, and 21363012)
文摘A successful approach to assemble Au core Pd shell （Au@Pd） nanoparticles on the surface of multi-walled carbon nanotubes functionalized by methylene blue （MB） （Au@Pd/fuv-MWCNTs） was reported. In this method, MWCNTs were functionalized under ultraviolet irradiation. UV-Vis analysis and high-angle annular dark-field trans- mission electron microscope （HAADF-TEM） image prove that core-shell structure of Au@Pd nanoparticles forms. TEM results indicate that Au@Pd nanoparticles （ - 5.2 nm） are well-dispersed on the surface of fuv-MWCNTs. X-ray photoelectron spectroscopy （XPS） reveals that ultraviolet irradiation can promote the interaction between Au@Pd nanoparticles and the functional groups on the surface of MWCNTs. Cyclic voltammograms （CV）, chronoampero- grams （CA）, and electrochemical impedance spectroscopy （EIS） results demonstrate that the Au@Pd/fuv-MWCNTs catalysts show excellent electrocatalytic performance for methanol oxidation in alkaline media. The catalytic activity of the Au@Pd/fuv-MWCNTs is ~ 2 times higher than that of the commercial Pd/C catalysts. This is mostly attributed to that ultraviolet irradiation can make the moieties of MB provide a uniform surface with active and anchoring sites, and improves the functional effect of MB on the surface of MWCNTs. Especially, ultraviolet irradiation modifies electronic structure of Pd and is beneficial for the enhance- ment of catalytic activity.
文摘Bimetallic Pt-based catalysts have been extensively investigated to enhance the performance of direct methanol fuel cells(DMFCs) because CO, a by-product, reduces the activity of the pure Pt catalysts. Herein, we synthesized Pt-Pb hexagonal nanoplates as a model catalyst for the methanol oxidation reaction(MOR) and further controlled the Pt and Pb distributions on the surface of the nanoplates through acetic acid(HAc) treatment. As a result, we obtained Pt-Pb nanoplates and HAc-treated Pt-Pb nanoplates with homogeneous and heterogeneous distributions of the Pt-Pb alloy surfaces, respectively. We showed that the MOR activity and stability of the Pt-Pb nanoplates improved compared to those of the HAc-treated Pt-Pb nanoplates, mainly due to the enhanced CO tolerance and the modified electronic structure of Pt under the influence of the oxophilic Pb.
