Exploration of bifunctional electrocatalysts toward effective oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is pivotal for developing high-efficiency and rechargeable metal-air batteries but remains ...Exploration of bifunctional electrocatalysts toward effective oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is pivotal for developing high-efficiency and rechargeable metal-air batteries but remains great challenging.Here we elaborately synthesize lamellar-assembled PdNi super-nanosheets(SNSs)with an optimized Pd/Ni molar ratio to serve as attractive ORR and OER bifunctional electrocatalysts for rechargeable high-powered Zn-air batteries(ZABs).The products are layer-by-layer stackings of ultrathin PdNi nanosheet motifs.On the drastically extended two-dimensional(2D)surface,the inserted Ni atoms can substantially lower down the d-band center of surface Pd toward improved ORR kinetics and concurrently create oxytropic NiOx sites to adsorb–OH groups for promoting the reverse OER electrocatalysis.Specifically,the ORR mass activity and specific activity of the primary Pd_(92)Ni_(8)SNSs attain 2.5 A·mg^(−1)and 3.15 mA·cm^(−2),which are respectively 14 and 9 times those of commercial Pt/C.Meanwhile,the OER activity and stability of Pd_(92)Ni_(8)SNSs/C distinctly outperform those of the RuO_(2)benchmark,suggesting excellent reversible oxygen electrocatalysis.The power density of the ZAB with Pd_(92)Ni_(8)SNSs/C as the air cathode is 2.7 times higher than that by Pt/C benchmark.Significantly,it can last for over 150 h without significant performance degradation during the charge–discharge cycle test.This work showcases a feasible strategy for developing self-assembled multimetallic 2D nanomaterials with excellent bifunctional catalytic performances toward energy conversion applications.展开更多
In wet chemical syntheses of noble metal nanocrystals,surfactants play crucial roles in regulating their morphology.To date,more attention has been paid to the effect of the surfactant on the surface energy of crystal...In wet chemical syntheses of noble metal nanocrystals,surfactants play crucial roles in regulating their morphology.To date,more attention has been paid to the effect of the surfactant on the surface energy of crystal facets,while less attention has been paid to its effect on the growth kinetics.In this paper,using the growth of Au-Pd alloy nanocrystals as an example,we demonstrate that different concentration of surfactant hexadecyltrimethyl ammonium chloride(CTAC)may cause the different packing density of CTA+bilayers on different sites(face,edge or vertex)of crystallite surface,which would change the crystal growth kinetics and result in preferential crystal growth along the edge or vertex of crystallites.The unique shape evolution from trisoctahedron to excavated rhombic dodecahedron and multipod structure for Au-Pd alloy nanocrystals was successfully achieved by simply adjusting the concentration of CTAC.These results help to understand the effect of surfactants on the shape evolution of nanocrystals and open up avenues to the rational synthesis of nanocrystals with the thermodynamically unfavorable morphologies.展开更多
Seed-mediated growth is the most general way to controllably synthesize bimetal nano-heterostructures. Despite successful instances through trial and error were reported, the way for second metal depositing on the see...Seed-mediated growth is the most general way to controllably synthesize bimetal nano-heterostructures. Despite successful instances through trial and error were reported, the way for second metal depositing on the seed. namely whether the symmetry of resulted nano-heterostructure follows the original crystal symmetry of seed metal, remains an unpredictable issue to date. In this work, we propose that the ther- modynamic factor, i.e., the difference of equilibrium electrochemical potentials (corresponding to their Fermi levels) of two metals in the growth solution, plays a key role for the symmetry breaking of bimetal nano-heterostructures during the seed-mediated growth. As a proof-of-principle experiment, by revers- ing the relative position of Fermi levels of the Pd nanocube seeds and the second metal Au with changing the concentration of reductant (L-ascorbic acid) in the growth solution, the structure of as-prepared prod- ucts successfully evolved from centrosymmetric Pd@Au core-shell trisoctabedra to asymmetric Pd-Au hetero-dimers. The idea was further demonstrated by the growth of Ag on the Pd seeds. The present work intends to reveal the origin of symmetry breaking in the seed-mediated growth of nano-heterostructures from the viewpoint of thermodynamics, and these new insights will in turn help to achieve rational con- struction of bimetal nano-heterostructures with soecific functions.展开更多
基金supported by the National Natural Science Foundation of China(No.22171093)the Natural Science Foundation of Fujian Province(Nos.2022J05058 and 2022J02008)the Scientific Research Funds of Huaqiao University(No.605-50Y21048).
文摘Exploration of bifunctional electrocatalysts toward effective oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is pivotal for developing high-efficiency and rechargeable metal-air batteries but remains great challenging.Here we elaborately synthesize lamellar-assembled PdNi super-nanosheets(SNSs)with an optimized Pd/Ni molar ratio to serve as attractive ORR and OER bifunctional electrocatalysts for rechargeable high-powered Zn-air batteries(ZABs).The products are layer-by-layer stackings of ultrathin PdNi nanosheet motifs.On the drastically extended two-dimensional(2D)surface,the inserted Ni atoms can substantially lower down the d-band center of surface Pd toward improved ORR kinetics and concurrently create oxytropic NiOx sites to adsorb–OH groups for promoting the reverse OER electrocatalysis.Specifically,the ORR mass activity and specific activity of the primary Pd_(92)Ni_(8)SNSs attain 2.5 A·mg^(−1)and 3.15 mA·cm^(−2),which are respectively 14 and 9 times those of commercial Pt/C.Meanwhile,the OER activity and stability of Pd_(92)Ni_(8)SNSs/C distinctly outperform those of the RuO_(2)benchmark,suggesting excellent reversible oxygen electrocatalysis.The power density of the ZAB with Pd_(92)Ni_(8)SNSs/C as the air cathode is 2.7 times higher than that by Pt/C benchmark.Significantly,it can last for over 150 h without significant performance degradation during the charge–discharge cycle test.This work showcases a feasible strategy for developing self-assembled multimetallic 2D nanomaterials with excellent bifunctional catalytic performances toward energy conversion applications.
基金supported by the National Basic Research Program of China (2015CB932301)the National Key Research and Development Program of China (2017YFA0206801)the National Natural Science Foundation of China (21333008, 21773190 and J1310024)
文摘In wet chemical syntheses of noble metal nanocrystals,surfactants play crucial roles in regulating their morphology.To date,more attention has been paid to the effect of the surfactant on the surface energy of crystal facets,while less attention has been paid to its effect on the growth kinetics.In this paper,using the growth of Au-Pd alloy nanocrystals as an example,we demonstrate that different concentration of surfactant hexadecyltrimethyl ammonium chloride(CTAC)may cause the different packing density of CTA+bilayers on different sites(face,edge or vertex)of crystallite surface,which would change the crystal growth kinetics and result in preferential crystal growth along the edge or vertex of crystallites.The unique shape evolution from trisoctahedron to excavated rhombic dodecahedron and multipod structure for Au-Pd alloy nanocrystals was successfully achieved by simply adjusting the concentration of CTAC.These results help to understand the effect of surfactants on the shape evolution of nanocrystals and open up avenues to the rational synthesis of nanocrystals with the thermodynamically unfavorable morphologies.
基金supported by the National Basic Research Program of China(2015CB93230)the National Key Research and Development Program of China(2017YFA0206801)+1 种基金the National Natural Science Foundation of China(21333008,21671163,21721001,and 21773190)the Fundamental Research Funds for the Central Universities(20720160026)
文摘Seed-mediated growth is the most general way to controllably synthesize bimetal nano-heterostructures. Despite successful instances through trial and error were reported, the way for second metal depositing on the seed. namely whether the symmetry of resulted nano-heterostructure follows the original crystal symmetry of seed metal, remains an unpredictable issue to date. In this work, we propose that the ther- modynamic factor, i.e., the difference of equilibrium electrochemical potentials (corresponding to their Fermi levels) of two metals in the growth solution, plays a key role for the symmetry breaking of bimetal nano-heterostructures during the seed-mediated growth. As a proof-of-principle experiment, by revers- ing the relative position of Fermi levels of the Pd nanocube seeds and the second metal Au with changing the concentration of reductant (L-ascorbic acid) in the growth solution, the structure of as-prepared prod- ucts successfully evolved from centrosymmetric Pd@Au core-shell trisoctabedra to asymmetric Pd-Au hetero-dimers. The idea was further demonstrated by the growth of Ag on the Pd seeds. The present work intends to reveal the origin of symmetry breaking in the seed-mediated growth of nano-heterostructures from the viewpoint of thermodynamics, and these new insights will in turn help to achieve rational con- struction of bimetal nano-heterostructures with soecific functions.