The construction of efficient and durable electrocatalysts with highly dispersed metal clusters and hydrophilic surface for alkaline hydrogen evolution reaction(HER)remains a great challenge.Herein,we prepared hydroph...The construction of efficient and durable electrocatalysts with highly dispersed metal clusters and hydrophilic surface for alkaline hydrogen evolution reaction(HER)remains a great challenge.Herein,we prepared hydrophilic nanocomposites of Ru clusters(~1.30 nm)anchored on Na^(+),K^(+)-decorated porous carbon(Ru/Na^(+),K^(+)-PC)through hydrothermal method and subsequent annealing treatment at 500℃.The Ru/Na^(+),K^(+)-PC exhibits ultralow overpotential of 7 mV at 10 mA·cm^(-2),mass activity of 15.7 A·mgRu^(-1)at 100 mV,and long-term durability of 20,000 cycles potential cycling and 200 h chronopotentiometric measurement with a negligible decrease in activity,much superior to benchmarked commercial Pt/C.Density functional theory based calculations show that the energy barrier of H-OH bond breaking is efficiently reduced due to the presence of Na and K ions,thus favoring the Volmer step.Furthermore,the Ru/Na^(+),K^(+)-PC effectively employs solar energy for obtaining H_(2)in both alkaline water and seawater electrolyzer.This finding provides a new strategy to construct high-performance and cost-effective alkaline HER electrocatalyst.展开更多
It is challenging and desirable to construct Pt-based nanocomposites with oxygen storage function as efficient oxygen reduction reaction(ORR)catalysts for practical proton exchange membrane fuel cells(PEMFCs).Herein,w...It is challenging and desirable to construct Pt-based nanocomposites with oxygen storage function as efficient oxygen reduction reaction(ORR)catalysts for practical proton exchange membrane fuel cells(PEMFCs).Herein,we achieve novel porous nanocomposites of PtCu_(3) nanoalloys-embedded in the PWO_(x) matrix(PtCu_(3)@PWO_(x)),which has an oxygen container feature.The PtCu_(3)@PWO_(x)/C exhibits an ultrahigh mass activity(MA)of 3.94 A·mgPt−1 for ORR,which is 26.3 times as high as the commercial Pt/C and the highest value ever reported for PtCu-based binary system.Theoretical calculations reveal that the compressive strain and d-band center downshift of Pt intrinsically contribute to the excellent ORR performance.In H_(2)-air PEMFCs at room temperature,furthermore,the PtCu_(3)@PWO_(x)/C delivers a high power density(218.6 mW·cm^(−2)),much superior to commercial Pt/C(131.6 mW·cm^(−2)).In H_(2)-O_(2) PEMFCs,PtCu_(3)@PWO_(x)/C outputs a maximum power density of 420.1 mW·cm^(−2).This work provides an effective idea for designing oxygen-storing ORR catalysts used for practical room-temperature H_(2)-air fuel cells.展开更多
Developing highly stable and active non-Pt oxygen reduction reaction(ORR)electrocatalysts for power generation device raises great concerns and remains a challenge.Here,we report novel truncated Pd tetrahedrons(T-Pd-T...Developing highly stable and active non-Pt oxygen reduction reaction(ORR)electrocatalysts for power generation device raises great concerns and remains a challenge.Here,we report novel truncated Pd tetrahedrons(T-Pd-Ths)enclosed by{111}facets with excellent uniformity,which have both low-coordinated surface sites and distinct lattice distortions that would induce“local strain”.In alkaline electrolyte,the T-Pd-Ths/C achieves remarkable ORR specific/mass activity(SA/MA)of 2.46 mA·cm^(−2)/1.69 A·mgPd^(−1),which is 12.3/16.9 and 10.7/14.1 times higher than commercial Pd/C and Pt/C,respectively.The T-Pd-Ths/C also exhibits high in-situ carbon monoxide(CO)tolerance and 50,000 cycles durability with an activity loss of 7.69%and morphological stability.The rotating ring-disk electrode(RRDE)measurements show that a 4-electron process occurs on T-PdThs/C.Theoretical calculations demonstrate that the low-coordinated surface sites contribute largely to the enhancement of ORR activity.In actual direct methanol fuel cell(DMFC)device,the T-Pd-Ths/C delivers superior open-circuit voltage(OCV)and peak power density(PPD)to commercial Pt/C from 25 to 80℃,and the maximum PPD can reach up to 163.7 mW·cm−2.This study demonstrates that the T-Pd-Ths/C holds promise as alternatives to Pt for ORR in DMFC device.展开更多
The generalized stacking fault (GSF) energies and surface energies of magnesium and its alloys with alloying atoms X- C, B, N, O and vacancy have been investigated using the first-principles methods. It is found tha...The generalized stacking fault (GSF) energies and surface energies of magnesium and its alloys with alloying atoms X- C, B, N, O and vacancy have been investigated using the first-principles methods. It is found that the predominant reducing effects of the alloying atoms and vacancy on the stacking fault energy are resulted from the position of them in the 1st layer near the slip plane. The stacking fault energies are nearly the same as the pure magnesium while the alloying atoms and vacancy are placed in the 2nd, 3rd, 4th, 5th and 6th layers. It has been shown that O strongly reduces the GSF energy of Mg. The alloying atoms C, B and N increase the surface energy, but O and vacancy reduce the surface energy of Mg. The ductilities of Mg and Mg alloys have been discussed based on the Rice criterion by using the ratio between surface energy and unstable stacking fault energy.展开更多
基金This work was supported by the National Natural Science Foundation of China(No.21571038)Education Department of Guizhou Province(No.2021312)+4 种基金Foundation of Guizhou Province(No.2019-5666)State Key Laboratory of Coal Mine Disaster Dynamics and Control(Chongqing University,No.2011DA105287-ZR202101)Science Foundation for After graduated Students of Guizhou Province(No.YJSKYJJ2021023)State Key Laboratory of Physical Chemistry of Solid Surfaces(Xiamen University,No.202009)the Open Fund of the Key Lab of Organic Optoelectronics and Molecular Engineering(Tsinghua University).
文摘The construction of efficient and durable electrocatalysts with highly dispersed metal clusters and hydrophilic surface for alkaline hydrogen evolution reaction(HER)remains a great challenge.Herein,we prepared hydrophilic nanocomposites of Ru clusters(~1.30 nm)anchored on Na^(+),K^(+)-decorated porous carbon(Ru/Na^(+),K^(+)-PC)through hydrothermal method and subsequent annealing treatment at 500℃.The Ru/Na^(+),K^(+)-PC exhibits ultralow overpotential of 7 mV at 10 mA·cm^(-2),mass activity of 15.7 A·mgRu^(-1)at 100 mV,and long-term durability of 20,000 cycles potential cycling and 200 h chronopotentiometric measurement with a negligible decrease in activity,much superior to benchmarked commercial Pt/C.Density functional theory based calculations show that the energy barrier of H-OH bond breaking is efficiently reduced due to the presence of Na and K ions,thus favoring the Volmer step.Furthermore,the Ru/Na^(+),K^(+)-PC effectively employs solar energy for obtaining H_(2)in both alkaline water and seawater electrolyzer.This finding provides a new strategy to construct high-performance and cost-effective alkaline HER electrocatalyst.
基金supported by the National Natural Science Foundation of China(No.21571038)Foundation of Guizhou Province(No.2019-5666)+3 种基金Education Department of Guizhou Province(No.2021312)State Key Laboratory of Coal Mine Disaster Dynamics and Control(Chongqing University,No.2011DA105287-ZR202101)State Key Laboratory of Physica Chemistry of Solid Surfaces(Xiamen University,No.202009)the Open Fund of the Key Lab of Organic Optoelectronics&Molecular Engineering(Tsinghua University).
文摘It is challenging and desirable to construct Pt-based nanocomposites with oxygen storage function as efficient oxygen reduction reaction(ORR)catalysts for practical proton exchange membrane fuel cells(PEMFCs).Herein,we achieve novel porous nanocomposites of PtCu_(3) nanoalloys-embedded in the PWO_(x) matrix(PtCu_(3)@PWO_(x)),which has an oxygen container feature.The PtCu_(3)@PWO_(x)/C exhibits an ultrahigh mass activity(MA)of 3.94 A·mgPt−1 for ORR,which is 26.3 times as high as the commercial Pt/C and the highest value ever reported for PtCu-based binary system.Theoretical calculations reveal that the compressive strain and d-band center downshift of Pt intrinsically contribute to the excellent ORR performance.In H_(2)-air PEMFCs at room temperature,furthermore,the PtCu_(3)@PWO_(x)/C delivers a high power density(218.6 mW·cm^(−2)),much superior to commercial Pt/C(131.6 mW·cm^(−2)).In H_(2)-O_(2) PEMFCs,PtCu_(3)@PWO_(x)/C outputs a maximum power density of 420.1 mW·cm^(−2).This work provides an effective idea for designing oxygen-storing ORR catalysts used for practical room-temperature H_(2)-air fuel cells.
基金the National Natural Science Foundation of China(No.21571038)Education Department of Guizhou Province(No.2021312)+4 种基金Foundation of Guizhou Province(No.2019-5666)Science Foundation for Aftergraduated Students of Guizhou Province(No.YJSCXJH2020045)State Key Laboratory of Coal Mine Disaster Dynamics and Control(Chongqing University,No.2011DA105287-ZR202101)State Key Laboratory of Physical Chemistry of Solid Surfaces(Xiamen University,No.202009)the Open Fund of the Key Lab of Organic Optoelectronics&Molecular Engineering(Tsinghua University)。
文摘Developing highly stable and active non-Pt oxygen reduction reaction(ORR)electrocatalysts for power generation device raises great concerns and remains a challenge.Here,we report novel truncated Pd tetrahedrons(T-Pd-Ths)enclosed by{111}facets with excellent uniformity,which have both low-coordinated surface sites and distinct lattice distortions that would induce“local strain”.In alkaline electrolyte,the T-Pd-Ths/C achieves remarkable ORR specific/mass activity(SA/MA)of 2.46 mA·cm^(−2)/1.69 A·mgPd^(−1),which is 12.3/16.9 and 10.7/14.1 times higher than commercial Pd/C and Pt/C,respectively.The T-Pd-Ths/C also exhibits high in-situ carbon monoxide(CO)tolerance and 50,000 cycles durability with an activity loss of 7.69%and morphological stability.The rotating ring-disk electrode(RRDE)measurements show that a 4-electron process occurs on T-PdThs/C.Theoretical calculations demonstrate that the low-coordinated surface sites contribute largely to the enhancement of ORR activity.In actual direct methanol fuel cell(DMFC)device,the T-Pd-Ths/C delivers superior open-circuit voltage(OCV)and peak power density(PPD)to commercial Pt/C from 25 to 80℃,and the maximum PPD can reach up to 163.7 mW·cm−2.This study demonstrates that the T-Pd-Ths/C holds promise as alternatives to Pt for ORR in DMFC device.
基金The work was supported by the National Natural Science Foundation of China (Grant No. 11104361) and Project No. CQDXWL2012015 supported by the Fundamental Research Funds for the Central Universities.
文摘The generalized stacking fault (GSF) energies and surface energies of magnesium and its alloys with alloying atoms X- C, B, N, O and vacancy have been investigated using the first-principles methods. It is found that the predominant reducing effects of the alloying atoms and vacancy on the stacking fault energy are resulted from the position of them in the 1st layer near the slip plane. The stacking fault energies are nearly the same as the pure magnesium while the alloying atoms and vacancy are placed in the 2nd, 3rd, 4th, 5th and 6th layers. It has been shown that O strongly reduces the GSF energy of Mg. The alloying atoms C, B and N increase the surface energy, but O and vacancy reduce the surface energy of Mg. The ductilities of Mg and Mg alloys have been discussed based on the Rice criterion by using the ratio between surface energy and unstable stacking fault energy.