Catalytic performance enhancement by alloying Pd with Pt on ordered mesoporous manganese oxide for methane combustion

Ordered mesoporous Mn2O3 (meso‐Mn2O3) and meso‐Mn2O3‐supported Pd, Pt, and Pd‐Pt alloy x(PdyPt)/meso‐Mn2O3; x = (0.10?1.50) wt%; Pd/Pt molar ratio (y) = 4.9?5.1 nanocatalysts were prepared using KIT‐6‐templated and poly(vinyl alcohol)‐protected reduction methods, respectively.The meso‐Mn2O3 had a high surface area, i.e., 106 m2/g, and a cubic crystal structure. Noble‐metalnanoparticles (NPs) of size 2.1?2.8 nm were uniformly dispersed on the meso‐Mn2O3 surfaces. AlloyingPd with Pt enhanced the catalytic activity in methane combustion; 1.41(Pd5.1Pt)/meso‐Mn2O3gave the best performance; T10%, T50%, and T90% (the temperatures required for achieving methaneconversions of 10%, 50%, and 90%) were 265, 345, and 425 °C, respectively, at a space velocity of20000 mL/(g?h). The effects of SO2, CO2, H2O, and NO on methane combustion over1.41(Pd5.1Pt)/meso‐Mn2O3 were also examined. We conclude that the good catalytic performance of1.41(Pd5.1Pt)/meso‐Mn2O3 is associated with its high‐quality porous structure, high adsorbed oxygen species concentration, good low‐temperature reducibility, and strong interactions between Pd‐Pt alloy NPs and the meso‐Mn2O3 support.

High-loading Pt-alloy catalysts for boosted oxygen reduction reaction performance

To improve performance of membrane electrode assembly(MEA)at large current density region,efficient mass transfer at the cathode is desired,for which a feasible strategy is to lower catalyst layer thickness by constructing high loading Pt-alloy catalysts on carbon.But the high loading may induce unwanted par-ticle aggregation.In this work,H-PtNi/C with 33%(mass)Pt loading on carbon and monodisperse distri-bution of 3.55 nm PtNi nanoparticles,was prepared by a bimodal-pore route.In electrocatalytic oxygen reduction reaction(ORR),H-PtNi/C displays an activity inferior to the low Pt loading catalyst L-PtNi/C(13.3%(mass))in the half-cell.While in H_(2)-0_(2) MEA,H-PtNi/C delivers the peak power density of 1.51 W·cm^(-2) and the mass transfer limiting current density of 4.4 A·cm^(-2),being 21%and 16%higher than those of L-PtNi/C(1.25 W·cm^(-2),3.8 A·cm^(-2))respectively,which can be ascribed to enhanced mass trans-fer brought by the thinner catalyst layer in the former.In addition,the same method can be used to pre-pare PtFe alloy catalyst with a high-Pt loading of 36%(mass).This work may lead to a range of catalyst materials for the large current density applications,such as fuel cell vehicles.

Possible Martensitic Transformation in Heusler Alloy Pt_2MnSn from First Principles

Using density functional theory calculations, we investigate the tetragonal distortion, electronic structure and magnetic property of Pt2MnSn. The results indicate that, when the volume-conserving tetragonal distortion occurs, the energy minimum appears at c/a = 0.84, and the energy difference between the minimum and cubic phase is as high as 107 me V/f. u. Thus from the point of view of thermodynamics, martensitie transformation may occur in Pt2MnSn with decreasing the temperature. The electronic structure of its cubic and martensitic phases also approves this. Moreover, both the cubic and tetragonal phases of Pt2MnSn are ferromagnetic structures and their total magnetic moments are 4.26 μB and 4.12 μB, respectively.

High index surface‐exposed and composition‐graded PtCu_(3)@Pt_(3)Cu@Pt nanodendrites for high‐performance oxygen reduction

Alloying and nanostructuring are two strategies used to facilitate the efficient electrocatalysis of the oxygen reduction reaction(ORR)by Pt,where the high index surfaces(HISs)of Pt exhibit superior activity for ORR.Here,we report the fabrication of PtCu3 nanodendrites possessing rich spiny branches exposing n(111)×(110)HISs.The dendrites were formed through an etching‐modulated seeding and growing strategy.Specifically,an oxidative atmosphere was initially applied to form the concaved nanocubes of the Pt‐Cu seeds,which was then switched to an inert atmosphere to promote an explosive growth of dendrites.Separately,the oxidative or inert atmosphere failed to produce this hyperbranched structure.Electrochemical dealloying of the PtCu3 nanodendrites produced Pt3Cu shells with Pt‐rich surfaces where HIS‐exposed dendrite structures were maintained.The resulting PtCu_(3)@Pt_(3)Cu@Pt nanodendrites in 0.1 M HClO4 exhibited excellent mass and area specific activities for ORR,which were 14 and 24 times higher than that of commercial Pt/C,respectively.DFT calculations revealed that Cu alloying and HISs both contributed to the significantly enhanced activity of Pt,and that the oxygen binding energy on the step sites of HISs on the PtCu_(3)@Pt_(3)Cu@Pt nanodendrites approached the optimal value to achieve a near peak‐top ORR activity.

An alternate aqueous phase synthesis of the Pt3Co/C catalyst towards efficient oxygen reduction reaction

Carbon supported Pt-Co alloys are among the most promising electrocatalysts towards oxygen reduction reaction(ORR)for the application in low temperature fuel cells and beyond,thus their facile and green synthesis is highly demanded.Herein we initially report an alternate aqueous phase one-pot synthesis of such catalysts(containing nominally ca.20 wt.%Pt)based on dimethylamine borane(DMAB)reduction.The as-obtained electrocatalyst(denoted as Pt3Co/C-DMAB)is compared with the ones obtained by NaBH4 and N2H4·H2O reduction(denoted as Pt3Co/C-NaBH4 and Pt3Co/C-N2H4·H2O,respectively)as well as a commercial Pt/C,in terms of the structure and electrocatalytic property.It turns out that Pt3Co/C-DMAB exhibits the highest ORR performance among all the tested samples in an O2-saturated 0.1 mol/L HClO4,with the mass activity(specific activity)ca.4(6)times as large as that for Pt/C.After 10000 cycles of the accelerated degradation test,the half-wave potential for ORR on Pt3Co/C-DMAB decreases only by 4 mV,in contrast to 24 mV for that on Pt/C.Pt3Co/C-NaBH4 or Pt3Co/C-N2H4·H2O shows a specific activity comparable to that for Pt3Co/C-DMAB,but a mass activity similar to that for Pt/C.ICP-AES,TEM,XRD and XPS characterizations indicate that Pt3Co nanoparticles are well-dispersed and alloyed with a mean particle size of ca.3.4±0.4 nm,contributing to the prominent electrocatalytic performance of Pt3Co/C-DMAB.This simple aqueous synthetic route may provide an alternate opportunity for developing efficient practical electrocatalysts for ORR.

Rational design and synthesis of one‐dimensional platinum‐based nanostructures for oxygen‐reduction electrocatalysis

Fuel cells have attracted extensive attention due to their high conversion efficiency and environmental friendliness.However,their wider application is limited by the poor activity and high cost of platinum(Pt),which is widely used as the cathode catalyst to overcome the slow kinetics associated with oxygen reduction reaction(ORR).Pt‐based composites with one‐dimensional(1D)nanoarchitectures demonstrate great advantages towards efficient ORR catalysis.This review focuses on the recent advancements in the design and synthesis of 1D Pt‐based ORR catalysts.After introducing the fundamental ORR mechanism and the advanced 1D architectures,their synthesis strategies(template‐based and template‐free methods)are discoursed.Subsequently,their morphology and structure optimization are highlighted,followed by the superstructure assembly using 1D Pt‐based blocks.Finally,the challenges and perspectives on the synthesis innovation,structure design,physical characterization,and theoretical investigations are proposed for 1D Pt‐based ORR nanocatalysts.We anticipate this study will inspire more research endeavors on efficient ORR nanocatalysts in fuel cell application.

Dendrite‐free lithium and sodium metal anodes with deep plating/stripping properties for lithium and sodium batteries

Although lithium(Li)and sodium(Na)metals can be selected as the promising anode materials for next‐generation rechargeable batteries of high energy density,their practical applications are greatly restricted by the uncontrollable dendrite growth.Herein,a platinum(Pt)–copper(Cu)alloycoated Cu foam(Pt–Cu foam)is prepared and then used as the substrate for Li and Na metal anodes.Owing to the ultrarough morphology with a threedimensional porous structure and the quite large surface area as well as lithiophilicity and sodiophilicity,both Li and Na dendrite growths are significantly suppressed on the substrate.Moreover,during Li plating,the lithiated Pt atoms can dissolve into Li phase,leaving a lot of microsized holes on the substrate.During Na plating,although the sodiated Pt atoms cannot dissolve into Na phase,the sodiation of Pt atoms elevates many microsized blocks above the current collector.Either the holes or the voids on the surface of Pt–Cu foam what can be extra place for deposited alkali metal,what effectively relaxes the internal stress caused by the volume exchange during Li and Na plating/stripping.Therefore,the symmetric batteries of Li@Pt–Cu foam and Na@Pt–Cu foam have both achieved long‐term cycling stability even at ultrahigh areal capacity at 20 mAh cm−2.

Suppressing the surface passivation of Pt-Mo nanowires via constructing Mo-Se coordination for boosting HER performance

Modulating the surface coordination environment of Pt based nanocrystals at the atomic level is of great importance to obtain good electrocatalytic performance.Given the fundamental understandings of surface structure degeneration of Pt based nanocrystals,introducing a weak electronegative element to the surface of Pt-based catalysts is beneficial for suppressing surface passivation and improving hydrogen evolution reaction performance of Pt.Density functional theory results reveal that the energy barrier of water dissociation process can be greatly reduced by using Se element as the surface modifier to replace the O.This hypothesis is further validated by experiments that ultralong Pt_(85)Mo_(15)-Se nanowires were fabricated to suppress the excessive passivation behavior of transition metals of Pt based alloy.The Pt_(85)Mo_(15)-Se nanowires exhibit higher activity with 4.98 times the specific activity and 4.87 times the mass activity of commercial Pt/C,as well as a better stability towards alkaline hydrogen evolution reaction.The deep exploration of X-ray photoelectron spectroscopy and theoretical calculations disclose that Se element could maintain the electron-rich state around the electronic orbit of Pt.This study provides a new insight to advance the fundamental understanding on electrocatalytic materials,which exhibits a promising approach to protect the surface chemical environment of Pt based nanocrystals.

Promoting the methanol oxidation catalytic activity by introducing surface nickel on platinum nanoparticles

High performance methanol oxidation reaction （MOR） catalysts are critical to the performance of attractive, direct methanol fuel cells. Here, we use surface controlled PtNi alloy nanoparticles as model catalysts to study the MOR mechanism and give further guidance to the design of new high performance MOR catalysts. The enhanced MOR activity of PtNi alloy was mainly attributed to the enhanced OH adsorption owing to surface Ni sites. This suggests that the MOR undergoes the Langmuir-Hinshelwood mechanism, whereby adsorbed CO is removed with the assistance of adsorbed OH. Within the PtNi catalyst, Pt provides methanol adsorption sites （in which methanol is converted to adsorbed CO） and Ni provides OH adsorption sites. The optimized Pt-Ni ratio for MOR was found to be 1：1. This suggests that bifunctional catalysts with both CO and OH adsorption sites can lead to highly active MOR catalysts.

Identification of the hydrogen utilization pathway for the electrocatalytic hydrogenation of phenol

Electrochemical hydrogenation(ECH)of biomass-derived platform molecules is a burgeoning route for the sustainable utilization of hydrogen.However,the noble-metal-catalyzed ECH of phenolic compounds suffers from intense competition with hydrogen evolution reaction.We prepared Pt Rh bimetallic nanoparticles dispersed on highly ordered mesoporous carbon nanospheres,which improves the utilization efficiency of adsorbed hydrogen(H_(ad))to ECH in H-UPD region(>0 V vs.RHE).Further analysis reveals(i)the strong overlapping between the d-orbitals of Pt and Rh enhances specific adsorption of phenol;(ii)incorporation of Rh devotes an electronic effect on weakening the alloy-H_(ad)interaction to increase the FE of ECH.DFT calculations confirm the selectivity difference and the ECH parallel pathways:cyclohexanol and cyclohexanone are formed via hydrogenation/dehydrogenation of the intermediate ^(*)C_(6)H_(10) OH.These findings deepen our fundamental understanding of the ECH process,and cast new light on exploration of highly efficient electrocatalysts for biomass upgrading.