The electrochemical methanol oxidation is a crucial reaction in the conversion of renewable energy.To enable the widespread adoption of direct methanol fuel cells(DMFCs),it is essential to create and engineer catalyst...The electrochemical methanol oxidation is a crucial reaction in the conversion of renewable energy.To enable the widespread adoption of direct methanol fuel cells(DMFCs),it is essential to create and engineer catalysts that are both highly effective and robust for conducting the methanol oxidation reaction(MOR).In this work,trimetallic PtCoRu electrocatalysts on nitrogen-doped carbon and multi-wall carbon nanotubes(PtCoRu@NC/MWCNTs)were prepared through a two-pot synthetic strategy.The acceleration of CO oxidation to CO_(2) and the blocking of CO reduction on adjacent Pt active sites were attributed to the crucial role played by cobalt atoms in the as-prepared electrocatalysts.The precise control of Co atoms loading was achieved through precursor stoichiometry.Various physicochemical techniques were employed to analyze the morphology,element composition,and electronic state of the catalyst.Electrochemical investigations and theoretical calculations confirmed that the Pt_(1)Co_(3)Ru_(1)@NC/MWCNTs exhibit excellent electrocatalytic performance and durability for the process of MOR.The enhanced MOR activity can be attributed to the synergistic effect between the multiple elements resulting from precisely controlled Co loading content on surface of the electrocatalyst,which facilitates efficient charge transfer.This interaction between the multiple components also modifies the electronic structures of active sites,thereby promoting the conversion of intermediates and accelerating the MOR process.Thus,achieving precise control over Co loading in PtCoRu@NC/MWCNTs would enable the development of high-performance catalysts for DMFCs.展开更多
Constructing the efficacious and applicable bifunctional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction(OER) are critical to the develop...Constructing the efficacious and applicable bifunctional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction(OER) are critical to the development of electrochemicallydriven technologies for efficient hydrogen production and avoid CO_(2) emission. Herein, the hetero-nanocrystals between monodispersed Pt(~ 2 nm) and Ni_(3)S_(2)(~ 9.6 nm) are constructed as active electrocatalysts through interfacial electronic modulation, which exhibit superior bi-functional activities for methanol selective oxidation and H_(2) generation. The experimental and theoretical studies reveal that the asymmetrical charge distribution at Pt–Ni_(3)S_(2) could be modulated by the electronic interaction at the interface of dual-monodispersed heterojunctions, which thus promote the adsorption/desorption of the chemical intermediates at the interface. As a result, the selective conversion from CH_(3)OH to formate is accomplished at very low potentials(1.45 V) to attain 100 m A cm^(-2) with high electronic utilization rate(~ 98%) and without CO_(2) emission. Meanwhile, the Pt–Ni_(3)S_(2) can simultaneously exhibit a broad potential window with outstanding stability and large current densities for hydrogen evolution reaction(HER) at the cathode. Further, the excellent bi-functional performance is also indicated in the coupled methanol oxidation reaction(MOR)//HER reactor by only requiring a cell voltage of 1.60 V to achieve a current density of 50 m A cm^(-2) with good reusability.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
Noble metal-based electrocatalysts present high activities for methanol oxidation reaction(MOR),but are limited by their high cost,low stability and poor resistance to carbon monoxide(CO) poisoning.The development of ...Noble metal-based electrocatalysts present high activities for methanol oxidation reaction(MOR),but are limited by their high cost,low stability and poor resistance to carbon monoxide(CO) poisoning.The development of active and stable non-noble metal electrocatalysts for MOR is desired,but remains a challenge.Herein,we report a simple strategy to make copper nanocrystal/nitrogen-doped carbon(Cu/N-C)monoliths,which can serve as active and robust electrodes for MOR.Copper nanocrystals were electrochemically deposited onto a conductive polyaniline hydrogel and calcined to form Cu/N-C monolith,where the active copper nanocrystals are protected by nitrogen-doped carbon.Owing to their extremely high electrical conductivity(1.25 × 10^(5) S cm^(-1)) and mechanical robustness,these Cu/N-C monoliths can be directly used as electrodes for MOR,without using substrates or additives.The optimal Cu/N-C(FT)@500 monolith shows a high MOR activity of 189 mA cm^(-2) at 0.6 V vs.SCE in alkaline methanol solution,superior to most of reported Cu-based MOR catalysts.Cu/N-C(FT)@500 also presents a better stability than Pt/C catalyst in the long-term MOR test at high current densities.Upon carbon monoxide(CO) poisoning,Cu/N-C(FT)@500 retains 96% of its MOR activity,far exceeding the performance of Pt/C catalyst(61% retention).Owing to its facile synthesis,outstanding activity,high stability and mechanical robustness,Cu/N-C(FT)@500 monolith is promising as a low-cost,efficient and CO-resistant electrocatalyst for MOR.展开更多
Methanol fuel cells have been intensively developed as clean and high-efficiency energy conversion system due to their high efficiency and low emission of pollutants.Here,we developed a simple aqueous synthetic method...Methanol fuel cells have been intensively developed as clean and high-efficiency energy conversion system due to their high efficiency and low emission of pollutants.Here,we developed a simple aqueous synthetic method to prepare bimetallic PdAu nanoflowers catalysts for methanol oxidation reaction(MOR)in alkaline environment.Their composition can be directly tuned by changing the ratio between Pd and Au precursors.Compared with commercial Pd/C catalyst,all of the PdAu nanoflowers catalysts show the enhanced catalytic activity and durability.In particular,the PdAu nanoflowers specific activity reached 0.72 mA/cm^(2),which is 14 times that of commercial Pd/C catalyst.The superior MOR activity could be attributed to the unique porous structure and the shift of the d-band center of Pd.展开更多
Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,...Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,we fabricated self-supported ultrathin NiCo layered double hydroxides(LDHs)electrodes as anode for methanol electrooxidation to achieve a high formate production rate(5.89 mmol h^(-1)cm^(-2))coupled with CO_(2)electro-reduction at the cathode.A total formate faradic efficiency of both anode for methanol oxidation and cathode for CO_(2)reduction can reach up to 188%driven by a low cell potential of only 2.06 V at 100 mA cm^(-2)in membrane-electrode assembly(MEA).Physical characterizations demonstrated that Ni^(3+)species,formed on the electrochemical oxidation of Ni-containing hydroxide,acted as catalytically active species for the oxidation of methanol to formate.Furthermore,DFT calculations revealed that ultrathin LDHs were beneficial for the formation of Ni^(3+)in hydroxides and introducing oxygen vacancy in NiCo-LDH could decrease the energy barrier of the rate-determining step for methanol oxidation.This work presents a promising approach for fabricating advanced electrodes towards electrocatalytic reactions.展开更多
Heterostructures have emerged as elaborate structures to improve catalytic activity owing to their combined surface and distinct inverse interface.However,fabricating advanced nanocatalysts with facetdependent interfa...Heterostructures have emerged as elaborate structures to improve catalytic activity owing to their combined surface and distinct inverse interface.However,fabricating advanced nanocatalysts with facetdependent interface remains an unexploited and promising area.Herein,we render the controlled growth of Pt nanoparticles(NPs)on Pd nanosheets(NSs)by regulating the reduction kinetics of Pt^(2+)with solvents.Specifically,the fast reduction kinetic makes the Pt NPs uniformly deposited on the Pd NSs(U-Pd@Pt HS),while the slow reduction kinetic leads to the preferential growth of Pt NPs on the edge of the Pd NSs(E-Pd@Pt HS).Density functional theory calculations demonstrate that Pd(111)-Pt interface in U-Pd@Pt HS induces the electron-deficient status of Pd substrates,triggering the d-band center downshift and amplifying the Pd-Pt intermetallic interaction.The synergy between the electronic effect and interfacial effect facilitates the removal of poisonous intermediates on U-Pd@Pt HS.By virtue of the Pd NSs@Pt NPs interface,the heterostructure achieves exceptional methanol oxidation reaction activity as well as improved durability.This study innovatively proposes heterostructure engineering with facetdependent interfacial modulation,offering instructive guidelines for the rational design of versatile heterocatalysts.展开更多
Sluggish kinetics of methanol oxidation reaction(MOR)and alkaline hydrogen evolution reaction(HER)even on precious Pt catalyst impede the large-scale commercialization of direct methanol fuel cell(DMFC)and water elect...Sluggish kinetics of methanol oxidation reaction(MOR)and alkaline hydrogen evolution reaction(HER)even on precious Pt catalyst impede the large-scale commercialization of direct methanol fuel cell(DMFC)and water electrolysis technologies.Since both of MOR and alkaline HER are related to water dissociation reaction(WDR),it is reasonable to invite secondary active sites toward WDR to pair with Pt for boosted MOR and alkaline HER activity on Pt.Mo_(2)C and Ni species are therefore employed to engineer NiPt-Mo_(2)C active site pairs,which can be encapsulated in carbon cages,via an in-situ self-confinement strategy.Mass activity of Pt in NiPt-Mo_(2)C@C toward HER is boosted to11.3 A mg_(pt)^(-1),33 times higher than that of Pt/C.Similarly,MOR catalytic activity of Pt in NiPt-Mo_(2)C@C is also improved by 10.5 times and the DMFC maximum power density is hence improved by 9-fold.By considering the great stability,NiPt-Mo_(2)C@C exhibits great practical application potential in DMFCs and water electrolysers.展开更多
With the rapid development of society and economy, the excessive consumption of fossil energy has led to the global energy and environment crisis. In order to explore the sustainable development of new energy, researc...With the rapid development of society and economy, the excessive consumption of fossil energy has led to the global energy and environment crisis. In order to explore the sustainable development of new energy, research based on electrocatalysis has attracted extensive attention in the academic circle. The main challenge in this field is to develop nano-catalysts with excellent electrocatalytic activity and selectivity for target products. The state of the active site in catalyst plays a decisive role in the activity and selectivity of the reaction. In order to design efficient and excellent catalysts, it is an effective means to adjust the electronic structure of catalysts. Electronic effects are also called ligand effects. By alloying with rare earth(RE) elements, electrons can be redistributed between RE elements and transition metal elements, achieving accurate design of the electronic structure of the active site in the alloy. Because of the unique electronic structure of RE, it has been paid attention in the field of catalysis. The outermost shell structure of RE elements is basically the same as that of the lower shell, except that the number of electrons in the 4f orbital is different, but the energy level is similar, so their properties are very similar. When RE elements form compounds, both the f electrons in the outermost shell and the d electrons in the lower outer shell can participate in bonding. In addition, part of the 4f electrons in the third outer shell can also participate in bonding.In order to improve the performance of metal catalysts, alloying provides an effective method to design advanced functional materials. RE alloys can integrate the unique electronic structure and catalytic behavior of RE elements into metal materials, which not only provides an opportunity to adjust the electronic structure and catalytic activity of the active component, but also enhances the structural stability of the alloy and is expected to significantly improve the catalytic performance of the catalyst. From the perspective of electronic and catalytic activity, RE elements have unique electronic configuration and lanthanide shrinkage effect. Alloying with RE elements will make the alloy have more abundant electronic structure, activity, and spatial arrangement, effectively adjusting the reaction kinetics of the electrochemical process of the catalyst. In this paper, the composition,structure, synthesis of RE alloys and their applications in the field of electrocatalysis are summarized, including the hydrogen evolution reaction, the oxygen evolution reaction, the oxygen reduction reaction, the methanol oxidation reaction, the ethanol oxidation reaction, and other catalytic reactions. At the same time, the present challenges of RE alloy electrocatalytic materials are summarized and their future development direction is pointed out. In the field of electrocatalysis, the cost of catalyst is too high and the stability is not strong. Therefore, the testing process should be related to the actual application, and the test method should be standardized, so as to carry forward the field of electrocatalysis.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
We present a straightforward physical approach for synthesizing multiwalled carbon nanotubes(CNTs)-Pd Au/Pt trimetallic nanoparticles(NPs), which allows predesign and control of the metal compositional ratio by simply...We present a straightforward physical approach for synthesizing multiwalled carbon nanotubes(CNTs)-Pd Au/Pt trimetallic nanoparticles(NPs), which allows predesign and control of the metal compositional ratio by simply adjusting the sputtering targets and conditions. The small-sized CNTs-Pd Au/Pt NPs(~3 nm, Pd/Au/Pt ratio of 3:1:2) act as nanocatalysts for the methanol oxidationreaction(MOR), showing excellent performance with electrocatalytic peak current of 4.4 A mg^(-1) Pt and high stability over 7000 s. The electrocatalytic activity and stability of the Pd Au/Pt trimetallic NPs are much superior to those of the corresponding Pd/Pt and Au/Pt bimetallic NPs,as well as a commercial Pt/C catalyst. Systematic investigation of the microscopic, crystalline, and electronic structure of the Pd Au/Pt NPs reveals alloying and charge redistribution in the Pd Au/Pt NPs, which are responsible for the promotion of the electrocatalytic performance.展开更多
Morphology engineering has been developed as one of the most widely used strategies for improving the performance of electrocatalysts.However,the harsh reaction conditions and cumbersome reaction steps during the nano...Morphology engineering has been developed as one of the most widely used strategies for improving the performance of electrocatalysts.However,the harsh reaction conditions and cumbersome reaction steps during the nanomaterials synthesis still limit their industrial applications.Herein,one-dimensional(1D)novel-segmented PtTe porous nanochains(PNCs)were successfully synthesized by the template methods assisted by Pt autocatalytic reduction.The PtTe PNCs consist of consecutive mesoporous architectures that provide a large electrochemical surface area(ECSA)and abundant active sites to enhance methanol oxidation reaction(MOR).Furthermore,1D nanostructure as a robust sustaining frame can maintain a high mass/charge transfer rate in a long-term durability test.After 2,000 cyclic voltammetry(CV)cycles,the ECSA value of PtTe PNCs remained as high as 44.47 m^(2)·gPt^(-1),which was much larger than that of commercial Pt/C(3.95 m^(2)·gPt^(-1)).The high catalytic activity and durability of PtTe PNCs are also supported by CO stripping test and density functional theory calculation.This autocatalytic reduction-assisted synthesis provides new insights for designing efficient low-dimensional nanocatalysts.展开更多
Hierarchical zeolites and single-crystalline zeolite nanosheets(NSs)have been recognized as two separate types of targeting porous materials to overcome the diffusion limitations of traditional bulk zeolites.The synth...Hierarchical zeolites and single-crystalline zeolite nanosheets(NSs)have been recognized as two separate types of targeting porous materials to overcome the diffusion limitations of traditional bulk zeolites.The synthesis of uniform single-crystalline hierarchical zeolite NSs featured with NS morphology and interconnected mesoporosity,remains rarely reported.In this work,we prepared ZSM-5 zeolites with the above microstructural features via simple alkaline etching.Moreover,both their microstructure and acid strength could be accurately tuned with this approach,resulting in not only higher conversion rate and BTX selectivity but also superior anti-coking performance in the subsequent methanol aromatization reaction.展开更多
Two acidic carbon materials (H-PRC and HS-C) were used as catalysts for the condensation reaction of methanol with formaldehyde to produce dimethoxymethane (DMM) in aqueous solution (hydrophilic system) and for ...Two acidic carbon materials (H-PRC and HS-C) were used as catalysts for the condensation reaction of methanol with formaldehyde to produce dimethoxymethane (DMM) in aqueous solution (hydrophilic system) and for the etherification of isopentene with methanol to produce tert amyl methyl ether (TAME) in toluene solution (lipophilic system). Microcalorimetric adsorptions of water and benzene showed that the HS-C was highly hydrophilic without the lipophilicity, while the H-PRC exhibited both the hydrophilicity and lipophilicity. Thus, the HS-C was well dispersed in aqueous solution and difficult to separate from it. On the other hand, the H-PRC was highly active, more active than the acidic resin (D008) and sulfuric acid, for the synthesis of DMM in aqueous solution. The H-PRC was also highly active, more active than the HS-C, for the etherification of isopentene with methanol to produce TAME in toluene solution, probably owing to its amphiphilic surface property as well as its strong surface acidity as measured by the microcalorirnetric adsorption of NH3.展开更多
Methanol-assisted water-splitting reaction for green hydrogen generation is more competitive to the traditional water electrolysis driven by sustainable energies due to the largely reduced energy costs.Increasing atte...Methanol-assisted water-splitting reaction for green hydrogen generation is more competitive to the traditional water electrolysis driven by sustainable energies due to the largely reduced energy costs.Increasing attention currently is directed to the highly efficient methanol electrooxidation catalysts that determine the catalysis efficiency,and some advanced catalysts have been developed.Given the significant advances,this review proposed a summary of the recent progress in catalysts for methanol-assisted water electrolysis.The mechanism of methanol-assisted water-splitting reaction classified by noble and non-noble metals was first presented by taking into account their distinct redox reactions.Then,the research progress of these catalysts for methanol-assisted water-splitting reactions is summarized and discussed,and the challenges and problems associated with catalyst design and optimization as well as their practical application were finally commented on.This review would be a valuable reference for catalyst development and mechanism understanding in methanol-assisted water-splitting reactions for hydrogen generation.展开更多
The sluggish kinetics of oxygen evolution reaction(OER)is the key tailback for hydrogen production from the water electrolysis.Masking OER with thermodynamically auspicious methanol oxidation reaction(MOR)can signific...The sluggish kinetics of oxygen evolution reaction(OER)is the key tailback for hydrogen production from the water electrolysis.Masking OER with thermodynamically auspicious methanol oxidation reaction(MOR)can significantly boost the H_(2) and value-added products production.However,it is currently challenging to achieve a synergistic manipulation of product selectivity and performance for MOR electrocatalyst.Herein,we report NiSnPH@OOH/CC(CC=carbon cloth)perovskite hydroxide nanosphere as an efficient MOR electrocatalyst with high activity,stability,and selectivity towards methanol oxidation to formate.A surface amorphous layer of defect rich NiOOH was generated in operando by selective Sn leaching with stable perovskite hydroxide bulk structure,which mitigates the oxidative power and optimizes the local coordination environment of the active NiOOH sites.In situ Raman combined with electrochemical studies further confirm the key active species,NiOOH,generated in operando enhance the MOR and blocking the over oxidation of methanol to CO_(2).As a result,NiSnPH@OOH/CC effectively masks the OER and attains>99%selectivity with 100%Faradic efficiency for methanol-to-formate.The results of this study show the advances of NiSnPH@OOH/CC as an efficient electrocatalyst for MOR and also suggest its potential applications for various small organic molecules oxidation.展开更多
The recent development of Aurum(Au)introduced Platinum(Pt)based nanomaterials is of great significance to direct methanol fuel cell as electrocatalysts for anode reactions,due to its stability and anti-poisoning featu...The recent development of Aurum(Au)introduced Platinum(Pt)based nanomaterials is of great significance to direct methanol fuel cell as electrocatalysts for anode reactions,due to its stability and anti-poisoning features.Therefore,the performance of PtAu based catalysts with different elements,atomic ratio,and morphology was studied in methanol solution to further improve its electrocatalytic activity.Furthermore,the effects of Au have aroused the researchers'attention in Pt-based nanocatalysts.In this review,we summarize the controllable synthesis,mechanism,and catalytic performance of Au introduced Pt-based electrocatalysts such as PtAu core-shell nanostructures,PtAu dendrite,PtAu nanowires,self-supporting Au@Pt NPs,and Au@Pt star-like nanocrystals for the methanol oxidation reaction.Finally,the challenges and research directions for the future development of PtAu based catalysts are provided.展开更多
Surface engineering has been found to be an efficient strategy to boost the catalytic performance of noble-metal-based nanocatalysts.In this work,a small amount of P was doped to the surface of PtNi concave cube(P-PtN...Surface engineering has been found to be an efficient strategy to boost the catalytic performance of noble-metal-based nanocatalysts.In this work,a small amount of P was doped to the surface of PtNi concave cube(P-PtNi CNC).Interestingly,the P-PtNi CNC nanocatalyst shows an enhanced methanol oxidation reaction(MOR)performance with achieving 8.19 times of specific activity than that of comercial Pt/C.The electrochemical in situ Fourier transform infrared spectroscopy(FTIR)results reveal that the surface P doping promotes the adsorption energy of OH,enhancing the resistance against CO poisoning.Therefore,the intermediate adsorbed CO(COads)reacted with adsorbed OH(OHads)through the Langmuir–Hinshelwood(LH)mechanism to generate CO_(2)and release surface active sites for further adsorption.This work provides a promising strategy via the incorporation of non-metallic elements into the PtNi alloys bounded with high-index facets(HIFs)as efficient fuel cell catalysts.展开更多
The application of direct methanol fuel cells (DMFC) is hampered by high cost, low activity, and poor CO tolerance by the Pt catalyst. Herein, we designed a fancy 3D hybrid by anchoring tungsten nitride (WN) nanop...The application of direct methanol fuel cells (DMFC) is hampered by high cost, low activity, and poor CO tolerance by the Pt catalyst. Herein, we designed a fancy 3D hybrid by anchoring tungsten nitride (WN) nanoparticles (NPs), of about 3 nm in size, into a 3D carbon nanotube-reduced graphene oxide framework (CNT-rGO) using an assembly route. After depositing Pt, the contacted and strongly coupled Pt-WN NPs were formed, resulting in electron transfer from Pt to WN. The 3D Pt-WN/CNT-rGO hybrid can be used as a bifunctional electrocatalyst for both methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR). In MOR, the catalysts showed excellent CO tolerance and a high mass activity of 702.4 mA.mgpt-1, 2.44 and 3.81 times higher than those of Pt/CNT-rGO and Pt/C(JM) catalysts, respectively. The catalyst also exhibited a more positive onset potential (1.03 V), higher mass activity (151.3 mA.mgpt-1), and better cyclic stability and tolerance in MOR than ORR. The catalyst mainly exhibited a 4e-transfer mechanism with a low peroxide yield. The high activity was closely related to hybrid structure. That is, the 3D framework provided a favorable path for mass-transfer, the CNT-rGO support was favorable for charge transfer, and strongly coupled Pt-WN can enhance the catalytic activity and CO-tolerance of Pt. Pt-WN/CNT-rGO represents a new 3D catalytic platform that is promising as an electrocatalyst for DMFC because it can catalyze both ORR and MOR in an acidic medium with good stability and highly efficient Pt utilization.展开更多
基金financially supported by the National Natural Science Foundation of China (52200076,22169005,52370057)the Growth Project of Young Scientific and Technological Talents in General Colleges and Universities in Guizhou Province ([2022]143)+4 种基金the Science and Technology Foundation of Guizhou Province ([2022]109)the Natural Science Special Foundation of Guizhou University (202017,702775203301)the Natural Science Foundation of Chongqing (CSTB2022NSCQ-BHX0035)the Special Research Assistant Program of Chinese Academy of Sciencethe Research Foundation of Chongqing University of Science and Technology (ckrc2022026)。
文摘The electrochemical methanol oxidation is a crucial reaction in the conversion of renewable energy.To enable the widespread adoption of direct methanol fuel cells(DMFCs),it is essential to create and engineer catalysts that are both highly effective and robust for conducting the methanol oxidation reaction(MOR).In this work,trimetallic PtCoRu electrocatalysts on nitrogen-doped carbon and multi-wall carbon nanotubes(PtCoRu@NC/MWCNTs)were prepared through a two-pot synthetic strategy.The acceleration of CO oxidation to CO_(2) and the blocking of CO reduction on adjacent Pt active sites were attributed to the crucial role played by cobalt atoms in the as-prepared electrocatalysts.The precise control of Co atoms loading was achieved through precursor stoichiometry.Various physicochemical techniques were employed to analyze the morphology,element composition,and electronic state of the catalyst.Electrochemical investigations and theoretical calculations confirmed that the Pt_(1)Co_(3)Ru_(1)@NC/MWCNTs exhibit excellent electrocatalytic performance and durability for the process of MOR.The enhanced MOR activity can be attributed to the synergistic effect between the multiple elements resulting from precisely controlled Co loading content on surface of the electrocatalyst,which facilitates efficient charge transfer.This interaction between the multiple components also modifies the electronic structures of active sites,thereby promoting the conversion of intermediates and accelerating the MOR process.Thus,achieving precise control over Co loading in PtCoRu@NC/MWCNTs would enable the development of high-performance catalysts for DMFCs.
基金the financial support of Guangdong Basic and Applied Basic Research Foundation (No. 2023A1515010940)Shenzhen Natural Science Fund (the Stable Support Plan Program No. 20220809160022001)the Shenzhen Science and Technology Programs (No. ZDSYS20220527171401003, KQTD20190929173914967)。
文摘Constructing the efficacious and applicable bifunctional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction(OER) are critical to the development of electrochemicallydriven technologies for efficient hydrogen production and avoid CO_(2) emission. Herein, the hetero-nanocrystals between monodispersed Pt(~ 2 nm) and Ni_(3)S_(2)(~ 9.6 nm) are constructed as active electrocatalysts through interfacial electronic modulation, which exhibit superior bi-functional activities for methanol selective oxidation and H_(2) generation. The experimental and theoretical studies reveal that the asymmetrical charge distribution at Pt–Ni_(3)S_(2) could be modulated by the electronic interaction at the interface of dual-monodispersed heterojunctions, which thus promote the adsorption/desorption of the chemical intermediates at the interface. As a result, the selective conversion from CH_(3)OH to formate is accomplished at very low potentials(1.45 V) to attain 100 m A cm^(-2) with high electronic utilization rate(~ 98%) and without CO_(2) emission. Meanwhile, the Pt–Ni_(3)S_(2) can simultaneously exhibit a broad potential window with outstanding stability and large current densities for hydrogen evolution reaction(HER) at the cathode. Further, the excellent bi-functional performance is also indicated in the coupled methanol oxidation reaction(MOR)//HER reactor by only requiring a cell voltage of 1.60 V to achieve a current density of 50 m A cm^(-2) with good reusability.
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supported by the National Natural Science Foundation of China(21722406,21975240,21676258)by the Fundamental Research Funds for the Central Universities(WK2060190102)+1 种基金by the Central Leading Local Science and Technology Development Special Fund Project(YDZX20191400002636)by the Scientific and Technologial Innovation Programs of Higher Education Institutions in Shanxi(STIP 2020L0695)。
文摘Noble metal-based electrocatalysts present high activities for methanol oxidation reaction(MOR),but are limited by their high cost,low stability and poor resistance to carbon monoxide(CO) poisoning.The development of active and stable non-noble metal electrocatalysts for MOR is desired,but remains a challenge.Herein,we report a simple strategy to make copper nanocrystal/nitrogen-doped carbon(Cu/N-C)monoliths,which can serve as active and robust electrodes for MOR.Copper nanocrystals were electrochemically deposited onto a conductive polyaniline hydrogel and calcined to form Cu/N-C monolith,where the active copper nanocrystals are protected by nitrogen-doped carbon.Owing to their extremely high electrical conductivity(1.25 × 10^(5) S cm^(-1)) and mechanical robustness,these Cu/N-C monoliths can be directly used as electrodes for MOR,without using substrates or additives.The optimal Cu/N-C(FT)@500 monolith shows a high MOR activity of 189 mA cm^(-2) at 0.6 V vs.SCE in alkaline methanol solution,superior to most of reported Cu-based MOR catalysts.Cu/N-C(FT)@500 also presents a better stability than Pt/C catalyst in the long-term MOR test at high current densities.Upon carbon monoxide(CO) poisoning,Cu/N-C(FT)@500 retains 96% of its MOR activity,far exceeding the performance of Pt/C catalyst(61% retention).Owing to its facile synthesis,outstanding activity,high stability and mechanical robustness,Cu/N-C(FT)@500 monolith is promising as a low-cost,efficient and CO-resistant electrocatalyst for MOR.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.118740271 and 1774124)Technology Development Program of Jilin Province,China(Grant No.20180101285JC)the China Postdoctoral Science Foundation(Grant Nos.2019T120233 and 2017M621198)
文摘Methanol fuel cells have been intensively developed as clean and high-efficiency energy conversion system due to their high efficiency and low emission of pollutants.Here,we developed a simple aqueous synthetic method to prepare bimetallic PdAu nanoflowers catalysts for methanol oxidation reaction(MOR)in alkaline environment.Their composition can be directly tuned by changing the ratio between Pd and Au precursors.Compared with commercial Pd/C catalyst,all of the PdAu nanoflowers catalysts show the enhanced catalytic activity and durability.In particular,the PdAu nanoflowers specific activity reached 0.72 mA/cm^(2),which is 14 times that of commercial Pd/C catalyst.The superior MOR activity could be attributed to the unique porous structure and the shift of the d-band center of Pd.
基金the financial support from the National Nature Science Foundation of China(22078232 and 21938008)the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,we fabricated self-supported ultrathin NiCo layered double hydroxides(LDHs)electrodes as anode for methanol electrooxidation to achieve a high formate production rate(5.89 mmol h^(-1)cm^(-2))coupled with CO_(2)electro-reduction at the cathode.A total formate faradic efficiency of both anode for methanol oxidation and cathode for CO_(2)reduction can reach up to 188%driven by a low cell potential of only 2.06 V at 100 mA cm^(-2)in membrane-electrode assembly(MEA).Physical characterizations demonstrated that Ni^(3+)species,formed on the electrochemical oxidation of Ni-containing hydroxide,acted as catalytically active species for the oxidation of methanol to formate.Furthermore,DFT calculations revealed that ultrathin LDHs were beneficial for the formation of Ni^(3+)in hydroxides and introducing oxygen vacancy in NiCo-LDH could decrease the energy barrier of the rate-determining step for methanol oxidation.This work presents a promising approach for fabricating advanced electrodes towards electrocatalytic reactions.
基金supported by the National Natural Science Foundation of China(Grant numbers 52274304,52073199)。
文摘Heterostructures have emerged as elaborate structures to improve catalytic activity owing to their combined surface and distinct inverse interface.However,fabricating advanced nanocatalysts with facetdependent interface remains an unexploited and promising area.Herein,we render the controlled growth of Pt nanoparticles(NPs)on Pd nanosheets(NSs)by regulating the reduction kinetics of Pt^(2+)with solvents.Specifically,the fast reduction kinetic makes the Pt NPs uniformly deposited on the Pd NSs(U-Pd@Pt HS),while the slow reduction kinetic leads to the preferential growth of Pt NPs on the edge of the Pd NSs(E-Pd@Pt HS).Density functional theory calculations demonstrate that Pd(111)-Pt interface in U-Pd@Pt HS induces the electron-deficient status of Pd substrates,triggering the d-band center downshift and amplifying the Pd-Pt intermetallic interaction.The synergy between the electronic effect and interfacial effect facilitates the removal of poisonous intermediates on U-Pd@Pt HS.By virtue of the Pd NSs@Pt NPs interface,the heterostructure achieves exceptional methanol oxidation reaction activity as well as improved durability.This study innovatively proposes heterostructure engineering with facetdependent interfacial modulation,offering instructive guidelines for the rational design of versatile heterocatalysts.
基金financial support from the National Natural Science Foundation of China(Nos.21875224,22179121)the Fundamental Research Founds for National University,China University of Geosciences(Wuhan)。
文摘Sluggish kinetics of methanol oxidation reaction(MOR)and alkaline hydrogen evolution reaction(HER)even on precious Pt catalyst impede the large-scale commercialization of direct methanol fuel cell(DMFC)and water electrolysis technologies.Since both of MOR and alkaline HER are related to water dissociation reaction(WDR),it is reasonable to invite secondary active sites toward WDR to pair with Pt for boosted MOR and alkaline HER activity on Pt.Mo_(2)C and Ni species are therefore employed to engineer NiPt-Mo_(2)C active site pairs,which can be encapsulated in carbon cages,via an in-situ self-confinement strategy.Mass activity of Pt in NiPt-Mo_(2)C@C toward HER is boosted to11.3 A mg_(pt)^(-1),33 times higher than that of Pt/C.Similarly,MOR catalytic activity of Pt in NiPt-Mo_(2)C@C is also improved by 10.5 times and the DMFC maximum power density is hence improved by 9-fold.By considering the great stability,NiPt-Mo_(2)C@C exhibits great practical application potential in DMFCs and water electrolysers.
基金financial support from the National Key R&D Program of China (2022YFB3506200)the National Nature Science Foundation of China (22122113)。
文摘With the rapid development of society and economy, the excessive consumption of fossil energy has led to the global energy and environment crisis. In order to explore the sustainable development of new energy, research based on electrocatalysis has attracted extensive attention in the academic circle. The main challenge in this field is to develop nano-catalysts with excellent electrocatalytic activity and selectivity for target products. The state of the active site in catalyst plays a decisive role in the activity and selectivity of the reaction. In order to design efficient and excellent catalysts, it is an effective means to adjust the electronic structure of catalysts. Electronic effects are also called ligand effects. By alloying with rare earth(RE) elements, electrons can be redistributed between RE elements and transition metal elements, achieving accurate design of the electronic structure of the active site in the alloy. Because of the unique electronic structure of RE, it has been paid attention in the field of catalysis. The outermost shell structure of RE elements is basically the same as that of the lower shell, except that the number of electrons in the 4f orbital is different, but the energy level is similar, so their properties are very similar. When RE elements form compounds, both the f electrons in the outermost shell and the d electrons in the lower outer shell can participate in bonding. In addition, part of the 4f electrons in the third outer shell can also participate in bonding.In order to improve the performance of metal catalysts, alloying provides an effective method to design advanced functional materials. RE alloys can integrate the unique electronic structure and catalytic behavior of RE elements into metal materials, which not only provides an opportunity to adjust the electronic structure and catalytic activity of the active component, but also enhances the structural stability of the alloy and is expected to significantly improve the catalytic performance of the catalyst. From the perspective of electronic and catalytic activity, RE elements have unique electronic configuration and lanthanide shrinkage effect. Alloying with RE elements will make the alloy have more abundant electronic structure, activity, and spatial arrangement, effectively adjusting the reaction kinetics of the electrochemical process of the catalyst. In this paper, the composition,structure, synthesis of RE alloys and their applications in the field of electrocatalysis are summarized, including the hydrogen evolution reaction, the oxygen evolution reaction, the oxygen reduction reaction, the methanol oxidation reaction, the ethanol oxidation reaction, and other catalytic reactions. At the same time, the present challenges of RE alloy electrocatalytic materials are summarized and their future development direction is pointed out. In the field of electrocatalysis, the cost of catalyst is too high and the stability is not strong. Therefore, the testing process should be related to the actual application, and the test method should be standardized, so as to carry forward the field of electrocatalysis.
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supported by the National Natural Science Foundation of China (Nos. 61675143, 11661131002)the Natural Science Foundation of Jiangsu Province (No. BK20160277)+2 种基金the Soochow University-Western University Joint Centre for Synchrotron Radiation Researchthe Collaborative Innovation Center of Suzhou Nano Science & Technologythe Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)
文摘We present a straightforward physical approach for synthesizing multiwalled carbon nanotubes(CNTs)-Pd Au/Pt trimetallic nanoparticles(NPs), which allows predesign and control of the metal compositional ratio by simply adjusting the sputtering targets and conditions. The small-sized CNTs-Pd Au/Pt NPs(~3 nm, Pd/Au/Pt ratio of 3:1:2) act as nanocatalysts for the methanol oxidationreaction(MOR), showing excellent performance with electrocatalytic peak current of 4.4 A mg^(-1) Pt and high stability over 7000 s. The electrocatalytic activity and stability of the Pd Au/Pt trimetallic NPs are much superior to those of the corresponding Pd/Pt and Au/Pt bimetallic NPs,as well as a commercial Pt/C catalyst. Systematic investigation of the microscopic, crystalline, and electronic structure of the Pd Au/Pt NPs reveals alloying and charge redistribution in the Pd Au/Pt NPs, which are responsible for the promotion of the electrocatalytic performance.
基金This work was supported by the National Natural Science Foundation of China(Nos.52171051,52130103,52271237,52271163,51971026,12034002,and 11904025)the Natural Science Foundation of Henan province(No.222300420086).We thank Dr.Song Hong from the Electron Microscopy Laboratory at Beijing University of Chemical Technology for the help with the aberration-corrected transmission electron microscope.
文摘Morphology engineering has been developed as one of the most widely used strategies for improving the performance of electrocatalysts.However,the harsh reaction conditions and cumbersome reaction steps during the nanomaterials synthesis still limit their industrial applications.Herein,one-dimensional(1D)novel-segmented PtTe porous nanochains(PNCs)were successfully synthesized by the template methods assisted by Pt autocatalytic reduction.The PtTe PNCs consist of consecutive mesoporous architectures that provide a large electrochemical surface area(ECSA)and abundant active sites to enhance methanol oxidation reaction(MOR).Furthermore,1D nanostructure as a robust sustaining frame can maintain a high mass/charge transfer rate in a long-term durability test.After 2,000 cyclic voltammetry(CV)cycles,the ECSA value of PtTe PNCs remained as high as 44.47 m^(2)·gPt^(-1),which was much larger than that of commercial Pt/C(3.95 m^(2)·gPt^(-1)).The high catalytic activity and durability of PtTe PNCs are also supported by CO stripping test and density functional theory calculation.This autocatalytic reduction-assisted synthesis provides new insights for designing efficient low-dimensional nanocatalysts.
基金financially supported by the Dalian Bureau of Science and Technology(No.2020JJ25CY007)the National Natural Science Foundation of China(21978282,22078039,21176231)+3 种基金the Science Fund for Creative Research Groups of the National Natural Science Foundation of China(22021005)the Fok Ying-Tong Education Foundation of China(171063)the Science and Technology Innovation Fund of Dalian(2020JJ26GX026)the National Key Research and Development Program of China(2019YFE0119200)。
文摘Hierarchical zeolites and single-crystalline zeolite nanosheets(NSs)have been recognized as two separate types of targeting porous materials to overcome the diffusion limitations of traditional bulk zeolites.The synthesis of uniform single-crystalline hierarchical zeolite NSs featured with NS morphology and interconnected mesoporosity,remains rarely reported.In this work,we prepared ZSM-5 zeolites with the above microstructural features via simple alkaline etching.Moreover,both their microstructure and acid strength could be accurately tuned with this approach,resulting in not only higher conversion rate and BTX selectivity but also superior anti-coking performance in the subsequent methanol aromatization reaction.
文摘Two acidic carbon materials (H-PRC and HS-C) were used as catalysts for the condensation reaction of methanol with formaldehyde to produce dimethoxymethane (DMM) in aqueous solution (hydrophilic system) and for the etherification of isopentene with methanol to produce tert amyl methyl ether (TAME) in toluene solution (lipophilic system). Microcalorimetric adsorptions of water and benzene showed that the HS-C was highly hydrophilic without the lipophilicity, while the H-PRC exhibited both the hydrophilicity and lipophilicity. Thus, the HS-C was well dispersed in aqueous solution and difficult to separate from it. On the other hand, the H-PRC was highly active, more active than the acidic resin (D008) and sulfuric acid, for the synthesis of DMM in aqueous solution. The H-PRC was also highly active, more active than the HS-C, for the etherification of isopentene with methanol to produce TAME in toluene solution, probably owing to its amphiphilic surface property as well as its strong surface acidity as measured by the microcalorirnetric adsorption of NH3.
基金support from the National Natural Science Foundation of China(21972124 and 22272148).
文摘Methanol-assisted water-splitting reaction for green hydrogen generation is more competitive to the traditional water electrolysis driven by sustainable energies due to the largely reduced energy costs.Increasing attention currently is directed to the highly efficient methanol electrooxidation catalysts that determine the catalysis efficiency,and some advanced catalysts have been developed.Given the significant advances,this review proposed a summary of the recent progress in catalysts for methanol-assisted water electrolysis.The mechanism of methanol-assisted water-splitting reaction classified by noble and non-noble metals was first presented by taking into account their distinct redox reactions.Then,the research progress of these catalysts for methanol-assisted water-splitting reactions is summarized and discussed,and the challenges and problems associated with catalyst design and optimization as well as their practical application were finally commented on.This review would be a valuable reference for catalyst development and mechanism understanding in methanol-assisted water-splitting reactions for hydrogen generation.
基金supported by the Shenzhen Government’s Plan of Science and Technology(Nos.20220804193203001 and GXWD20220811164046002)Guangdong Basic and Applied Basic Research Foundation(No.2021A1515010735)+2 种基金Featured Innovation Project of Colleges and Universities of Guangdong Province(No.2021KTSCX365)Innovation Team Project of Guangdong Colleges and Universities(No.2021KCXTD006)the National Natural Science Foundation of China(No.52072247).
文摘The sluggish kinetics of oxygen evolution reaction(OER)is the key tailback for hydrogen production from the water electrolysis.Masking OER with thermodynamically auspicious methanol oxidation reaction(MOR)can significantly boost the H_(2) and value-added products production.However,it is currently challenging to achieve a synergistic manipulation of product selectivity and performance for MOR electrocatalyst.Herein,we report NiSnPH@OOH/CC(CC=carbon cloth)perovskite hydroxide nanosphere as an efficient MOR electrocatalyst with high activity,stability,and selectivity towards methanol oxidation to formate.A surface amorphous layer of defect rich NiOOH was generated in operando by selective Sn leaching with stable perovskite hydroxide bulk structure,which mitigates the oxidative power and optimizes the local coordination environment of the active NiOOH sites.In situ Raman combined with electrochemical studies further confirm the key active species,NiOOH,generated in operando enhance the MOR and blocking the over oxidation of methanol to CO_(2).As a result,NiSnPH@OOH/CC effectively masks the OER and attains>99%selectivity with 100%Faradic efficiency for methanol-to-formate.The results of this study show the advances of NiSnPH@OOH/CC as an efficient electrocatalyst for MOR and also suggest its potential applications for various small organic molecules oxidation.
基金supported by the Guangxi Science and Technology Project(Nos.AA17204083 and AB16380030)the link project of the National Natural Science Foundation of China and Fujian Province(No.U1705252)the Natural Science Foundation of Guangdong Province(No.2015A030312007).
文摘The recent development of Aurum(Au)introduced Platinum(Pt)based nanomaterials is of great significance to direct methanol fuel cell as electrocatalysts for anode reactions,due to its stability and anti-poisoning features.Therefore,the performance of PtAu based catalysts with different elements,atomic ratio,and morphology was studied in methanol solution to further improve its electrocatalytic activity.Furthermore,the effects of Au have aroused the researchers'attention in Pt-based nanocatalysts.In this review,we summarize the controllable synthesis,mechanism,and catalytic performance of Au introduced Pt-based electrocatalysts such as PtAu core-shell nanostructures,PtAu dendrite,PtAu nanowires,self-supporting Au@Pt NPs,and Au@Pt star-like nanocrystals for the methanol oxidation reaction.Finally,the challenges and research directions for the future development of PtAu based catalysts are provided.
基金the National Natural Science Foundation of China(No.21573286)the Natural Science Foundation of Hebei Province of China(No.E2020408004)the Funded by Science and Technology Project of Hebei Education Department(No.QN2021124).
文摘Surface engineering has been found to be an efficient strategy to boost the catalytic performance of noble-metal-based nanocatalysts.In this work,a small amount of P was doped to the surface of PtNi concave cube(P-PtNi CNC).Interestingly,the P-PtNi CNC nanocatalyst shows an enhanced methanol oxidation reaction(MOR)performance with achieving 8.19 times of specific activity than that of comercial Pt/C.The electrochemical in situ Fourier transform infrared spectroscopy(FTIR)results reveal that the surface P doping promotes the adsorption energy of OH,enhancing the resistance against CO poisoning.Therefore,the intermediate adsorbed CO(COads)reacted with adsorbed OH(OHads)through the Langmuir–Hinshelwood(LH)mechanism to generate CO_(2)and release surface active sites for further adsorption.This work provides a promising strategy via the incorporation of non-metallic elements into the PtNi alloys bounded with high-index facets(HIFs)as efficient fuel cell catalysts.
基金We gratefully acknowledge the support of this research by the Key Program of the National Natural Science Foundation of China (No. 21031001), the National Natural Science Foundation of China (Nos. 21371053, 21571054, and 21401048), Program for Innovative Research Team in University (No. IRT-1237), Special Research Fund for the Doctoral Program of Higher Education of China (No. 20112301110002), the Natural Science Foundation of Heilongjiang Province (No. QC2014C007), China Postdoctoral Science Foundation funded project (No. 2015T80374), and Excellent Youth Foundation of Heilongjiang University.
文摘The application of direct methanol fuel cells (DMFC) is hampered by high cost, low activity, and poor CO tolerance by the Pt catalyst. Herein, we designed a fancy 3D hybrid by anchoring tungsten nitride (WN) nanoparticles (NPs), of about 3 nm in size, into a 3D carbon nanotube-reduced graphene oxide framework (CNT-rGO) using an assembly route. After depositing Pt, the contacted and strongly coupled Pt-WN NPs were formed, resulting in electron transfer from Pt to WN. The 3D Pt-WN/CNT-rGO hybrid can be used as a bifunctional electrocatalyst for both methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR). In MOR, the catalysts showed excellent CO tolerance and a high mass activity of 702.4 mA.mgpt-1, 2.44 and 3.81 times higher than those of Pt/CNT-rGO and Pt/C(JM) catalysts, respectively. The catalyst also exhibited a more positive onset potential (1.03 V), higher mass activity (151.3 mA.mgpt-1), and better cyclic stability and tolerance in MOR than ORR. The catalyst mainly exhibited a 4e-transfer mechanism with a low peroxide yield. The high activity was closely related to hybrid structure. That is, the 3D framework provided a favorable path for mass-transfer, the CNT-rGO support was favorable for charge transfer, and strongly coupled Pt-WN can enhance the catalytic activity and CO-tolerance of Pt. Pt-WN/CNT-rGO represents a new 3D catalytic platform that is promising as an electrocatalyst for DMFC because it can catalyze both ORR and MOR in an acidic medium with good stability and highly efficient Pt utilization.