Critical role of carbon support in metal nanoaggregate facilitating Fe-N-C catalyst for PEM fuel cell application

Metal nanoaggregates can simultaneously enhance the activity and stability of Fe-N-C catalysts in proton-exchange-membrane fuel cells(PEMFC).Previous studies on the relevant mechanism have focused on the direct interaction between FeN_(4)active sites and metal nanoaggregates.However,the role of carbon support that hosts metal nanoaggregates and active sites has been overlooked.Here,a Fe-N-C catalyst encapsulating inactive gold nanoparticles is prepared as a model catalyst to investigate the electronic tuning of Au nanoparticles(NPs)towards the carbon support.Au NPs donate electrons to carbon support,making it rich inπelectrons,which reduces the work function and regulates the electronic configuration of the FeN_(4)sites for an enhanced ORR activity.Meanwhile,the electron-rich carbon support can mitigate the electron depletion of FeN_(4)sites caused by carbon support oxidation,thereby preserving its high activity.The yield and accumulation of H_(2)O_(2)are thus alleviated,which delays the oxidation of the catalyst and benefits the stability.Due to the electron-rich carbon support,the composite catalyst achieves a top-level peak power density of 0.74 W/cm^(2) in a 1.5 bar H_(2)-air PEMFC,as well as the improved stability.This work elucidates the key role of carbon support in the performance enhancement of the FeN-C/metal nanoaggregate composite catalysts for fuel cell application.

A post-modification strategy to precisely construct dual-atom sites for oxygen reduction electrocatalysis

Dual-atom catalysts(DACs) afford promising potential for oxygen reduction electrocatalysis due to their high atomic efficiency and high intrinsic activity.However,precise construction of dual-atom sites remains a challenge.In this work,a post-modification strategy is proposed to precisely fabricate DACs for oxygen reduction electrocatalysis.Concretely,a secondary metal precursor is introduced to the primary single-atom sites to introduce direct metal-metal interaction,which ensures the formation of desired atom pair structure during the subsequent pyrolysis process and allows for successful construction of DACs.The as-prepared FeCo-NC DAC exhibits superior oxygen reduction electrocatalytic activity with a half-wave potential of 0,91 V vs.reversible hydrogen electrode.Zn-air batteries equipped with the FeCo-NC DAC demonstrate higher peak power density than those with the Pt/C benchmark.More importantly,this post-modification strategy is demonstrated universal to achieve a variety of dual-atom sites.This work presents an effective synthesis methodology for precise construction of catalytic materials and propels their applications in energy-related devices.

Boosting the Oxygen Reduction Performance of Fe-N-C Catalyst Using Zeolite as an Oxygen Reservoir

Non-precious metal electrocatalysts(such as Fe-N-C materials) for the oxygen(O_(2)) reduction reaction demand a high catalyst loading in fuel cell devices to achieve workable performance. However, the extremely low solubility of O_(2) in water creates severe mass transport resistance in the thick catalyst layer of Fe-N-C catalysts. Here, we introduce silicalite-1 nanocrystals with hydrophobic cavities as sustainable O_(2) reservoirs to overcome the mass transport issue of Fe-N-C catalysts. The extra O_(2) supply to the adjacent catalysts significantly alleviated the negative effects of the severe mass transport resistance. The hybrid catalyst(Fe-N-C@silicalite-1) achieved a higher limiting current density than Fe-N-C in the half-cell test. In the H_(2)-O_(2) and H_2-air proton exchange membrane fuel cells, Fe-N-C@silicalite-1 exhibited a 16.3% and 20.2% increase in peak power density compared with Fe-N-C, respectively. The O_(2)-concentrating additive provides an effective approach for improving the mass transport imposed by the low solubility of O_(2) in water.

Environmentally Tough and Stretchable MXene Organohydrogel with Exceptionally Enhanced Electromagnetic Interference Shielding Performances

Conductive hydrogels have potential applications in shielding electromagnetic(EM)radiation interference in deformable and wearable electronic devices,but usually suffer from poor environmental stability and stretching-induced shielding performance degradation.Although organohydrogels can improve the environmental stability of materials,their development is at the expense of reducing electrical conductivity and thus weakening EM interference shielding ability.Here,a MXene organohydrogel is prepared which is composed of MXene network for electron conduction,binary solvent channels for ion conduction,and abundant solvent-polymer-MXene interfaces for EM wave scattering.This organohydrogel possesses excellent anti-drying ability,low-temperature tolerance,stretchability,shape adaptability,adhesion and rapid self-healing ability.Two effective strategies have been proposed to solve the problems of current organohydrogel shielding materials.By reasonably controlling the MXene content and the glycerol-water ratio in the gel,MXene organohydrogel can exhibit exceptionally enhanced EM interference shielding performances compared to MXene hydrogel due to the increased physical cross-linking density of the gel.Moreover,MXene organohydrogel shows attractive stretching-enhanced interference effectiveness,caused by the connection and parallel arrangement of MXene nanosheets.This well-designed MXene organohydrogel has potential applications in shielding EM interference in deformable and wearable electronic devices.

Fe-N-C catalysts for PEMFC: Progress towards the commercial application under DOE reference

Proton exchange membrane fuel cells(PEMFC)have attracted much attention because of their high energy conversion efficiency,high power density and zero emission of pollutants.However,the high cost of the cathode platinum group metal(PGM)catalysts creates a barrier for the large-scale application of PEMFC.Tremendous efforts have been devoted to the development of low-cost PGM-free catalysts,especially the Fe-N-C catalysts,to replace the expensive PGM catalysts.However,the characterization methods and evaluation standards of the catalysts varies,which is not conducive to the comparison of PGM-free catalysts.U.S.Department of energy(DOE)is the only authority that specifies the testing standards and activity targets for PGM-free catalysts.In this review,the major breakthroughs of Fe-N-C catalysts are outlined with the reference of DOE standards and targets.The preparation and characteristics of these highly active Fe-N-C catalysts are briefly introduced.Moreover,the efforts on improving the mass transfer and the durability issue of Fe-N-C fuel cell are discussed.Finally,the prospective directions concerning the comprehensive evaluation of the Fe-N-C catalysts are proposed.

Performance improvement of lithium-ion battery by pulse current

Periodically changed current is called pulse current.It has been found that using the pulse current to charge/discharge lithium-ion batteries can improve the safety and cycle stability of the battery.In this short review,the mechanisms of pulse current improving the performance of lithium-ion batteries are summarized from four aspects:activation,warming up,fast charging and inhibition of lithium dendrites.Related content may help us use the pulse current to improve the performance of lithium-ion batteries and further optimize pulse current technology.

Identification of the optimal doping position of hetero-atoms in chalcogen-doped Fe-N-C catalysts for oxygen reduction reaction

The excellent oxygen reduction reaction(ORR)activity of Fe–N–C catalysts in acidic media makes them potential for low-cost proton exchange membrane fuel cells.In recent years,it has been shown that heteroatoms(B,O,S,P,Cl,F,etc.)can be used as electron-withdrawing groups to modulate the planar structure and electron distribution of the Fe–Nx active sites to achieve simultaneous improvement of catalytic activity and stability.However,the optimal location of the heteroatoms remains unclear.Here,taking chalcogen heteroatoms(S and Se)as an example,we control the doping positions and investigate their effect on the ORR performance of the Fe–N–C catalysts.The first coordination shell of the iron single atom is identified as the optimal doping position.The optimized catalysts Fe–N_(3)Se_(1)/NC and Fe–N_(3)Se_(1)/NC demonstrate improved activity and stability in both half cells and fuel cells.This work provides insights into the enhancement mechanism of heteroatom doping in single-atom catalysts.

A simple path to ambient temperature ionic H^(-)superconductors

Hydride ion(H^(-))has high polarizability(α_(H^(-))=10.17A^(3))and high redox potential(H^(-)/H_(2):-2.3 V),and therefore is an attractive energy carrier[1,2].The H^(-)superconductors play a crucial role in the development of high-density energy storage and chemical conversion technologies[3].

Precious trimetallic single-cluster catalysts for oxygen and hydrogen electrocatalytic reactions:Theoretical considerations

Single cluster catalysts(SCCs),which exhibit remarkable catalytic performance due to their high metal loading and synergy effect between metal atoms,have attracted great attention in research.Herein,by means of density functional theory calculations,the oxygen reduction reaction(ORR),oxygen evolution reaction(OER),hydrogen evolution reaction(HER)performances of precious metal(Pt,Pd,Rh,Ir)trimetallic single-cluster electrocatalyst(U_(x)V_(y)W_(z)-NG)are investigated.The calculation results show that Pt,Pd,Ir have significant effect on ORR,OER,HER,respectively,all the calculated U_(x)V_(y)W_(z)-NG structures are thermodynamically stable due to the negative formation energies and binding energies.The Pt_(3)-NG,Pd_(3)-NG,Ir_(3)-NG show the lowest ORR,OER,HER overpotentials of 0.63,0.77,−0.02 V,respectively,among all combinations of U_(x)V_(y)W_(z)-NG.These overpotentials are lower than that of precious metal single atom catalysts(SACs),which indicate better activities of precious trimetallic SCCs than those of SACs.The electronic structure reveals that the O-2p orbital shows strong hybridization strength with Pt-3d orbitals in the system of OH adsorbed Pt_(3)-NG and thus facilitates the electrocatalytic reactions.The results are helpful for the rational design of high-performance triatomic catalysts.

Synergy between metallic components of MoNi alloy for catalyzing highly efficient hydrogen storage of MgH2

Catalysts play a critical role in improving the hydrogen storage kinetics in Mg/MgH2 system.Exploring highly efficient catalysts and catalyst design principles are hot topics but challenging.The catalytic activity of metallic elements on dehydrogenation kinetics generally follows a sequence of Ti>Nb>Ni>V>Co>Mo.Herein,we report a highly efficient alloy catalyst composed of low-active elements of Mo and Ni(i.e.MoNi alloy)for MgH2 particles.MoNi alloy nanoparticles show excellent catalytic effect,even outperforming most advanced Ti-based catalysts.The synergy between Mo and Ni elements can promote the break of Mg-H bonds and the dissociation of hydrogen molecules,thus significantly improves the kinetics of Mg/MgH2 system.The MoNi-catalyzed Mg/MgH2 system can absorb and release 6.7 wt.%hydrogen within 60 s and 10 min at 300℃,respectively,and exhibits excellent cycling stability and low-temperature hydrogen storage performance.This study provides a strategy for designing efficient catalysts for hydrogen storage materials using the synergy of metal elements.

Catalysis stability enhancement of Fe/Co dual-atom site via phosphorus coordination for proton exchange membrane fuel cell

Non-precious metal catalysts(NPMCs)are promising low-cost alternatives of Pt/C for oxygen reduction reaction(ORR),which however suffer from serious stability challenge in the devices of proton-exchange-membrane fuel cells(PEMFC).Different from the traditional strategies of increasing the degree of graphitization of carbon substrates and using less Fenton-reactive metals,we prove here that proper regulation of coordination anions is also an effective way to improve the stability of NPMC.N/P cocoordinated Fe-Co dual-atomic-sites are constructed on ZIF-8 derived carbon support using a molecular precursor of C_(34)H_(28)Cl_(2)CoFeP_(2)and a“precursor-preselected”method.A composition of FeCoN_(5)P1 is infered for the dual-atom active site by microscopy and spectroscopy analysis.By comparing with N-coordinated references,we investigate the effect of P-coodination on the ORR catalysis of Fe-Co dual-atom catalysts in PEMFC.The metals in FeCoN_(5)P1 have the lower formation energy than those in the solo N-coordinated active sites of FeCoN6 and FeN_(4),and exhibits a much better fuel cell stability.This anion approach provides a new way to improve the stability of dual-atom catalysts.

Boosting electrocatalytic water splitting via metal-metalloid combined modulation in quaternary Ni-Fe-P-B amorphous compound

Design and synthesis of highly efficient and cost-effective bifunctional catalysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)remain a big challenge.Herein,a quaternary amorphous nanocompound Ni-Fe-P-B has been synthesized by a facile,scalable co-reduction method.The Ni-Fe-P-B exhibits high electrocatalytic activity and outstanding durability for both HER and OER,delivering a current density of 10 mA·cm^-2 at overpotentials of 220 and 269 mV,respectively.When loaded on carbon fiber paper(CFP)as a bifunctional catalyst,the Ni-Fe-P-B@CFP electrode requires a low cell voltage of 1.58 V to obtain 10 mA·cm^-2 for overall water splitting with negligible recession over 60 h.The excellent catalytic performances of Ni-Fe-P-B mainly benefit from the metal-metalloid combined composition modulation and the unique amorphous structure.This work provides new insights into the design of robust bifunctional catalysts for water splitting,and may promote the development of multicomponent amorphous catalysts.

High-throughput screening of carbon-supported single metal atom catalysts for oxygen reduction reaction

Carbon-supported transition metal single atoms are promising oxygen reduction reaction(ORR)electrocatalyst.Since there are many types of carbon supports and transition metals,the accurate prediction of the components with high activity through theoretical calculations can greatly save experimental time and costs.In this work,the ORR catalytic properties of 180 types single-atom catalysts(SACs)composed of the eight representative carbon-based substrates(graphdiyne,C_(2)N,C_(3)N_(4),phthalocyanine,C-coordination graphene,N-coordination graphene,covalent organic frameworks and metal-organic frameworks)and 3d,4d,and 5d transition metal elements are investigated by density functional theory(DFT).The adsorption free energy of OH^(*) is proved a universal descriptor capable of accurately prediction of the ORR catalytic activity.It is found that the oxygen reduction reaction overpotentials of all the researched SACs follow one volcano shape very well with the adsorption free energy of OH^(*).Phthalocyanine,N-coordination graphene and metal-organic frameworks stand out as the promising supports for single metal atom due to the relatively lower overpotentials.Notably,the Co-doped metal-organic frameworks,Ir-doped phthalocyanine,Co-doped N-coordination graphene,Co-doped graphdiyne and Rh-doped phthalocyanine show extremely low overpotentials comparable to that of Pt(111).The study provides a guideline for design and selection of carbon-supported SACs toward oxygen reduction reaction.

Effect of Zn atom in Fe-N-C catalysts for electro-catalytic reactions: theoretical considerations

Due to the high specific surface area,abundant nitrogen and micropores,ZIF-8 is a commonly used precursor for preparing high performance Fe-N-C catalysts.However,the Zn element is inevitably remained in the prepared Fe-N-C catalyst.Whether the residual Zn element affects the catalytic activity and active site center of the Fe-N-C catalyst caused widespread curiosity,but has not been studied yet.Herein,we built several Fe,Zn,and N co-doped graphene models to investigate the effect of Zn atoms on the electrocatalytic performance of Fe-N-C catalysts by using density functional theory method.The calculation results show that all the calculated Fe-Zn-N_(x) structures are thermodynamically stable due to the negative formation energies and relative stabilities.The active sites around Fe and Zn atoms in the structure of Fe-Zn-N_(6)(III)show the lowest oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)overpotentials of 0.38 and 0.43 V,respectively.The bridge site of Fe-Zn in Fe-Zn-N_(5) shows the lowest η^(HER) of−0.26 V.A few structures with a better activity than that of FeN_(4) or ZnN_(4) are attributed to the synergistic effects between Fe and Zn atoms.The calculated ORR reaction pathways on Fe-Zn-N6(III)show that H_(2)O is the final product and the ORR mechanism on the catalyst would be a four-electron process,and the existence of Zn element in the Fe-N-C catalysts plays a key role in reducing the ORR activation energy barrier.The results are helpful for the deep understand of high-performance Fe-N-C catalysts.

Phosphated IrMo bimetallic cluster for efficient hydrogen evolution reaction

Developing low-cost,high-performance electrocatalysts for the hydrogen evolution reaction(HER)is essential for producing hydrogen from renewable energy sources.Herein,we report phosphated IrMo bimetallic clusters supported by macroporous nitrogen-doped carbon(IrMoP/MNC)as a highly efficient alkaline HER catalyst.The experimental and theoretical results demonstrate that P and Mo synergistically tune the electronic structure of atomically dispersed Ir to improve adsorption of the reactant H_(2)O and desorption of the product OH^(-).P itself serves as an active site and cooperates with the nearby Ir atom to significantly enhance the HER kinetics.Even with only 2.6 wt%Ir in the catalyst,IrMoP/MNC exhibits an ultralow overpotential of 14 mV at 10 mA cm^(-2),as well as an unprecedented high mass activity of 18.58 A mg Ir^(-1) at an overpotential of 100 mV,superior to commercial Pt/C and overwhelmingly better than other Ir-based electrocatalysts.This study demonstrates a multi-level design strategy to effectively improve the atom efficiency of a noble metal,involving spatial geometry,local electronic structure,and dual-atom synergy.

Inorganic microporous membranes for hydrogen separation:Challenges and solutions

Porous membrane separation is a competitive hydrogen purification technology due to the advantages of environmental friendliness,energy-saving,simple operation,and low cost.Benefiting from the booming development of materials science and chemical science,great progress has been made in H_(2) separation with porous membranes.This review focuses on the latest advances in the design and fabrication of H_(2) separation inorganic microporous membranes,with emphasis on the synthetic strategies to achieve structural integrity,continuity and stability.This review starts with a brief introduction to the membrane separation mechanisms,followed by an elaboration on the synthetic challenges and corresponding solutions of various high-performance inorganic microporous membranes based on zeolites,silica,carbon,and metal-organic frameworks(MOFs).At last,by highlighting the prospects of ultrathin two-dimensional(2D)porous membranes,we wish to shed some light on the further development of new materials and membranes for highly efficient hydrogen separation.