摘要：Pt based materials are the most efficient electrocatalysts for the oxygen reduction reaction(ORR)and methanol oxidation reaction(MOR)in fuel *** 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 ***,we report a new class of hierarchically skeletal Pt-Ni nanocrystals(HSNs)with a multi-layered structure,prepared by an inorganic acid-induced solvothermal *** 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 *** 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 ***,it displays enhanced stability,with only 21.6%mass activity loss after 10,000 cycles(0.6–1.0 V)for ***,the Pt-Ni HSNs show enhanced activity and anti-toxic ability in CO for *** 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 *** novel open and hierarchical structure of Pt-Ni alloy provides a promising approach for significant improvements of the activity of Pt based alloy electrocatalysts.

摘要：Chemically modified carbonaceous materials have attained utmost attention in the fields of renewable energy storage and conversion,due to the controllable physicochemical properties,tailorable micro-/nanostructures,and respectable ***,P-doped mesoporous carbons were synthesized by using F127 as the soft template,organophosphonic acid as the P source and phenolic resin as the carbon *** amounts of iron species were introduced to act as a graphitization *** synthesized carbons exhibit the well-defined wormhole-like pore structure featuring high specific surface area and homogenously doped P ***,introducing iron species during the synthesis process can optimize the textural properties and the degree of graphitization of carbon *** doping amount of P has an important effect on the porous structure and the defect degree,which correspondingly influence the active sites and the oxygen reduction reaction(ORR)*** resultant material presents superior catalytic activity for the ORR,together with remarkably enhanced durability and methanol tolerance in comparison with the commercial Platinum catalyst,demonstrating the possibility for its use in electrode materials and electronic nanodevices for metal-air batteries and fuel cells.

摘要：Rational designs of electrocatalytic active sites and architectures are of great importance to develop cost-efficient non-noble metal electrocatalysts towards efficient oxygen reduction reaction(ORR)for high-performance energy conversion and storage *** this work,active amorphous Fe-based nanoclusters(Fe NC)are elaborately embedded at the inner surface of balloonlike N-doped hollow carbon(Fe NC/Csphere)as an efficient ORR electrocatalyst with an ultrathin wall of about 10 *** evaluated for electrochemical performance,Fe NC/Csphere exhibits decent ORR activity with a diffusionlimited current density of~5.0 mA/cm^(2)and a half-wave potential of~0.81 V in alkaline solution,which is comparable with commercial Pt/C and superior to Fe nanoparticles supported on carbon sheet(Fe NP/C sheet)*** electrochemical analyses combined with electronic structure characterizations reveal that robust Fe-N interactions in amorphous Fe nanoclusters are helpful for the adsorption of surface oxygen-relative species,and the strong support effect of N-doped hollow carbon is benefitial for accelerating the interfacial electron transfer,which jointly contributes to improve ORR kinetics for Fe NC/Csphere.

摘要：The development of efficient and cost‐effective metal‐free electrocatalysts for oxygen reduction reaction(ORR)has become crucial for electrochemical energy ***,reasonably validating and precisely regulating the active sites for designing optimized materials are still ***,we report a precise and controllable tandem strategy to boost the ORR activity based on metal‐free covalent organic frameworks(MFCOFs)comprising imine‐N,thiophene‐S,or triazine‐*** these MFCOFs,post‐tandem BTT‐TAT‐COF structure displayed a more positive catalytic capability and excellent electrochemical stability,indicating that the synergistic catalysis of multiple active sites induced the ORR catalytic activity through the conjugated skeleton of the ***‐functional theory calculations suggest that the series‐connected backbone contained highly effective electrocatalytic active centers and provided synergistic *** importantly,this strategy highlights new opportunities for the advancement of efficient COF‐based metal‐free ORR catalysts.

摘要：The development of high‐performance nonprecious metal catalysts(NPMCs)to supersede Pt‐based catalysts for the oxygen reduction reaction(ORR)in polymer electrolyte membrane fuel cells is highly desirable but remains *** this paper,we present a pyrolysis strategy for spatial confinement and active‐site fixation using iron phthalocyanine(FePc),phthalocyanine(Pc)and Zn salts as *** the obtained carbon‐based NPMC with a hierarchically porous nanostructure of thin‐layered carbon nanosheets,nearly 100%of the total Fe species are Fe^(Ⅱ)‐N_(4) active *** contrast,pyrolyzing FePc alone forms Fe‐based nanoparticles embedded in amorphous carbon with only 5.9%Fe^(Ⅱ)‐N_(4) active *** experimental characterization and density functional theory calculations reveal that spatial confinement through the staggeredπ–πstacking of Pc macrocycles effectively prevents the demetallation of Fe atoms and the formation of Fe‐based nanoparticles via ***,Zn‐induced microporous defects allow the fixation of Fe^(Ⅱ)‐N_(4) active *** synergistic effect of staggered stacking confinement and microporous defect fixation results in a high density of atomic Fe^(Ⅱ)‐N_(4) active sites that can enhance the *** optimal Fe^(Ⅱ)‐N_(4)‐C electro‐catalyst outperforms a commercial Pt/C catalyst in terms of half‐wave potential,methanol toler‐ance,and long‐term stability in alkaline *** modulation strategy can greatly advance efforts to develop high‐performance NPMCs.

摘要：Two-dimensional(2D)MXene and single-atom(SA)catalysts are two frontier research fields in catalysis.2D materials with unique geometric and electronic structures can modulate the catalytic performance of supported SAs,which,in turn,affect the intrinsic activity of 2D *** functional theory calculations were used to systematically explore the potential of O-terminated V2C MXene(V_(2)CO_(2))-supported transition metal(TM)SAs,including a series of 3d,4d,and 5d metals,as oxygen reduction reaction(ORR)and hydrogen oxidation reaction(HOR)*** combination of TM SAs and V_(2)CO_(2)changes their electronic structure and enriches the active sites,and consequently regulates the intermediate adsorption energy and catalytic activity for ORR and *** the investigated TM-V_(2)CO_(2)models,Sc-,Mn-,Rh-,and PtMCCh showed high ORR activity,while Sc-,Ti-,V-,Cr-,and Mn-V_(2)CO_(2)exhibited high HOR ***,Mn-and Sc-V_(2)CO_(2)are expected to serve as highly efficient and cost-effective bifunctional catalysts for fuel cells because of their high catalytic activity and *** work provides theoretical guidance for the rational design of efficient ORR and HOR bifunctional catalysts.

摘要：Metal‐organic frameworks(MOFs)are a series of highly porous crystalline materials,which are built from inorganic metal nodes and organic linkers through coordination *** unique porous structural features(such as high porosity,high surface areas,and highly ordered nanoporous structures)and designable structures and compositions have facilitated their use in gas capture,separation,catalysis,and energy storage and ***,the design and synthesis of pure MOFs and their derivatives have opened new routes to develop highly efficient electrocatalysts toward oxygen reduction reactions(ORR)and oxygen evolution reactions(OER),which are the core electrode reactions in many energy storage and conversion techniques,such as metal‐air batteries and fuel *** review first discusses recent progress in the synthesis and the electrocatalytic applications of pure MOF‐based electrocatalysts toward ORR or OER,including pure MOFs,MOFs decorated with active species,and MOFs incorporated with conductive *** following section focuses on the advancements of the design and preparation of various MOF‐derived materials-such as inorganic nano‐(or micro‐)structures/porous carbon composites,pure porous carbons,pure inorganic nano‐(or micro‐)structured materials,and single‐atom electrocatalysts-and their applications in oxygen ***,we present a conclusion and an outlook for some general design strategies and future research directions of MOF‐based oxygen electrocatalysts.

摘要：Water-based rechargeable metal-air batteries play an important role in the storage and conversion of renewable electric ***,the sluggish kinetics of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)have limited the practical application of rechargeable metal-air *** of reviews were focused on single functional electrocatalysts while few on bifunctional *** is indispensable but challenging to design a bifunctional electrocatalyst that is active and stable to the two ***,attempts to develop high active bifunctional electrocatalysts for both ORR and OER increase *** work is focused on the micro-nano design of advanced structures to improve the performance of bifunctional ***-metal materials,carbon materials and composite materials,and the methods developed to prepare micro-nano structures,such as electrochemical methods,chemical vapor deposition,hydrothermal methods and template methods are reported in ***,many strategies,such as adjustments of electronic structures,oxygen defects,metal-oxygen bonds,interfacial strain,nano composites,heteroatom doping etc.,have been used extensively to design bifunctional *** well understand the achievements in the recent literatures,this review focuses on the micro-nano structural design of materials,and the related methods and strategies are classed into two groups for the improvement of intrinsic and apparent *** fine adjustment of nano structures and an in-depth understanding of the reaction mechanism are also discussed briefly.

摘要：长寿命溶解氧海水电池是深远海观测能源网络的重要组成单元,但海水贫氧复杂环境对设计高性能氧还原催化剂提出了重要挑战.本文以酞菁铁为模型催化剂,通过理论计算与实验验证,提出了活性位点电子轴向拉伸可大幅提升催化剂在极端贫氧环境中的氧还原活性和稳定性.该研究为构建高性能海水电池提供了材料学解决方案,同时为极端环境下催化剂的变革性设计提供了新的思路.

摘要：Nano‐catalysis plays a vital role in the chemical transformations and significantly impacts the booming modern chemical *** rapid technological enhancements have resulted in serious energy and environmental issues,which are currently spurring the exploration of the novel nano‐catalysts in diverse *** order to develop the efficient nano‐catalysts,it is essential to understand their fundamental physicochemical properties,including the coordination structures of the active centers and substrate‐adsorbate ***,the nano‐catalyst design with precise manipulation at the atomic level can be *** this account,we have summarized our extensive investigation of the factors impacting nano‐catalysis,along with the synthetic strategies developed to prepare the nano‐catalysts for applications in electrocatalysis,photocatalysis and ***,a brief conclusion and future research directions on nano‐catalysis have also been presented.