Noble metal-loaded layered hydroxides exhibit high efficiency in electrocatalyzing water splitting.However,their widespread use as bifunctional electrocatalysts is hindered by low metal loading,inefficient yield,and c...Noble metal-loaded layered hydroxides exhibit high efficiency in electrocatalyzing water splitting.However,their widespread use as bifunctional electrocatalysts is hindered by low metal loading,inefficient yield,and complex synthesis processes.In this work,platinum atoms were anchored onto nickel-iron layered double hydroxide/carbon nanotube(LDH/CNT)hybrid electrocatalysts by using a straightforward milling technique with K_(2)Pt Cl_(6)·6H_(2)O as the Pt source.By adjusting the Pt-to-Fe ratio to 1/2 and 1/10,excellent electrocatalysts—Pt_(1/6)-Ni_(2/3)Fe_(1/3)-LDH/CNT and Pt_(1/30)-Ni_(2/3)Fe_(1/3)-LDH/CNT—were achieved with superior performance in hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),outperforming the corresponding commercial Pt/C(20 wt%)and Ru O_(2)electrocatalysts.The enhanced electrochemical performance is attributed to the modification of Pt's electronic structure,which exhibits electron-rich states for HER and electrondeficient states for OER,significantly boosting Pt's electrochemical activity.Furthermore,the simple milling technology for controlling Pt loading offers a promising approach for scaling up the production of electrocatalysts.展开更多
Strategy of anchoring alloy nanoparticles made up of the efficient catalytic element(e.g.,Ni,Fe)on dodecyl sulfate(DS^(-))-intercalated NiFe layered double hydroxides(DS^(-)-NiFe LDH)obtained by a convenient one-step ...Strategy of anchoring alloy nanoparticles made up of the efficient catalytic element(e.g.,Ni,Fe)on dodecyl sulfate(DS^(-))-intercalated NiFe layered double hydroxides(DS^(-)-NiFe LDH)obtained by a convenient one-step hydrothermal coprecipitation method for essentially enhancing oxygen evolution reaction(OER)performance was proposed.The results of structural characterization indicate Pt_(2)FeNi alloy nanoparticles evenly distribute on the surface of DS^(-)-NiFe LDH.The sizes of the Pt_(2)FeNi nanoparticles,closely related to their OER performance,could be wellcontrolled by adjusting the amount of H;PtCl;addition.The composite structure of as-prepared product was stable during processes of synthesis,exfoliation,self-assembly,and subsequent electrocatalytic OER.Rigorous electrochemical test proving the contributing catalytic active sites was located at the interface between Pt_(2)FeNi and DS^(-)-NiFe LDH,and the Ni and Fe were the major active elements while O atoms are adsorption sites.The formation of Pt_(2)FeNi nanoparticles could greatly prompt the reduction of Tafel slope.The best-performing Pt_(2)FeNi/DS^(-)-NiFe LDH with a Pt content of 0.98 wt%achieved low overpotential of 204 mV at 10 mA cm^(-2)and 262 mV at 50 mA cm^(-2).This work provides a convenient and effective strategy to create additional active sites for enhancing OER performance of NiFe LDH and make contribution to its wide application.展开更多
Rationally manipulating surface reconstruction of catalysts for water oxidation,inducing formation and dynamic accumulation of catalytically active centers still face numerous challenges.Herein,the introduction of[Cr(...Rationally manipulating surface reconstruction of catalysts for water oxidation,inducing formation and dynamic accumulation of catalytically active centers still face numerous challenges.Herein,the introduction of[Cr(C_(2)O_(4))_(3)]^(3-)into NiFe LDHs by intercalation engineering to promote surface reconstruction achieves an advanced oxygen evolution reaction(OER)activity.In view of the weak electronegativity of Cr^(3+) in[Cr(C_(2)O_(4))_(3)]^(3-),the intercalation of[Cr(C_(2)O_(4))_(3)]^(3-)is expected to result in an electron-rich structure of Fe sites in NiFe LDHs,and higher valence state of Ni can be formed with the charge transfer between Fe and Ni.The optimized electronic structure of NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs with more active Ni^(3+) species and the expedited dynamic generation of Ni^(3+) (Fe)OOH phase during the OER process contributed to its excellent catalytic property,revealed by in situ X-ray absorption spectroscopy,Raman spectroscopy,and quasi-in situ X-ray photoelectron spectroscopy.With the modulated electronic structure of metal sites,NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs exhibited promoted OER property with a lower overpotential of 236 mV at the current density of 10 mA cm^(-2).This work illustrates the intercalation of conjugated anion to dynamically construct desired Ni^(3+) sites with the optimal electronic environment for improved OER electrocatalysis.展开更多
We report a facile way to prepare sulfur(S) doped Ni4/5 Fe1/5-layered double hydroxide(LDH) electrocatalysts for oxygen evolution reaction(OER). The influence of S doping amount on the OER activity of the resulted Ni ...We report a facile way to prepare sulfur(S) doped Ni4/5 Fe1/5-layered double hydroxide(LDH) electrocatalysts for oxygen evolution reaction(OER). The influence of S doping amount on the OER activity of the resulted Ni Fe-LDHs was studied and the optimal surface S content was ca. 0.43 at%. The developed S-doped Ni Fe-LDH exhibits excellent OER catalyst activity in 1.0 M KOH with overpotential of only 257 m V at the current density of 10 m A cm^-2. Moreover, the catalyst could maintain high activity after 30 h stability test. The high activity of the S-doped Ni Fe-LDH catalysts may originate from the synergistic effect between S and the Fe sites. This work provides a simple but efficient way to improve the OER performance of transition metal oxides/(oxy)hydroxides.展开更多
Monolithic catalysts for CO_(2) methanation have become an active research area for the industrial development of Power-to-Gas technology.In this study,we developed a facile and reproducible synthesis strategy for the...Monolithic catalysts for CO_(2) methanation have become an active research area for the industrial development of Power-to-Gas technology.In this study,we developed a facile and reproducible synthesis strategy for the preparation of structured NiFe catalysts on washcoated cordierite monoliths for CO_(2) methanation.The NiFe catalysts were derived from in-situ grown layered double hydroxides(LDHs)via urea hydrolysis.The influence of different washcoat materials,i.e.,alumina and silica colloidal suspensions on the formation of LDHs layer was investigated,together with the impact of total metal concentration.NiFe LDHs were precipitated on the exterior surface of cordierite washcoated with alumina,while it was found to deposit further inside the channel wall of monolith washcoated with silica due to different intrinsic properties of the colloidal solutions.On the other hand,the thickness of in-situ grown LDHs layers and the catalyst loading could be increased by high metal concentration.The best monolithic catalyst(COR-AluCC-0.5M)was robust,having a thin and well-adhered catalytic layer on the cordierite substrate.As a result,high methane yield was obtained from CO_(2) methanation at high flow rate on this structured NiFe catalysts.The monolithic catalysts appeared as promising structured catalysts for the development of industrial methanation reactor.展开更多
The dynamic surface self-reconstruction behavior in local structure correlates with oxygen evolution reaction(OER)performance,which has become an effective strategy for constructing the catalytic active phase.However,...The dynamic surface self-reconstruction behavior in local structure correlates with oxygen evolution reaction(OER)performance,which has become an effective strategy for constructing the catalytic active phase.However,it remains a challenge to understand the mechanisms of reconstruction and to accomplish it fast and deeply.Here,we reported a photo-promoted rapid reconstruction(PRR)process on Ag nanoparticle-loaded amorphous Ni-Fe hydroxide nanosheets on carbon cloth for enhanced OER.The photogenerated holes generated by Ag in conjunction with the anodic potential contributed to a thorough reconstruction of the amorphous substrate.The valence state of unsaturated coordinated Fe atoms,which serve as active sites,is significantly increased,while the corresponding crystalline substrate shows little change.The different structural evolutions of amorphous and crystalline substrates during reconstruction lead to diverse pathways of OER.This PRR utilizing loaded noble metal nanoparticles can accelerate the generation of active species in the substrate and increase the electrical conductivity,which provides a new inspiration to develop efficient catalysts via reconstruction strategies.展开更多
To achieve palm oil conversion along with a high yield of long‐chain alkane,a series of NiFe layered double oxide catalysts were prepared and employed in the deoxygenation of palm oil.The layered structure of these c...To achieve palm oil conversion along with a high yield of long‐chain alkane,a series of NiFe layered double oxide catalysts were prepared and employed in the deoxygenation of palm oil.The layered structure of these catalysts was confirmed by XRD and SEM analyses,and Ni and Fe species existed primarily in the forms of Ni^(2+)and Fe^(3+),respectively.It was found that Ni/Fe molar ratio influenced the H_(2)reducibility and surface properties of NiFe catalysts.Specifically,Ni_(2)Fe‐LDO and Ni_(3)Fe‐LDO exhibited higher reducibility under H_(2)atmosphere.Moreover,the Ni_(2)Fe‐LDO catalyst contained a higher concentration of surface oxygen species(Osurf).Deoxygenation results demonstrated that the Ni_(2)Fe‐LDO catalyst achieved superior palm oil conversion,higher liquid product yield and enhanced selectivity toward C_(15)–C_(18)hydrocarbons compared to other catalysts.This improved performance was attributed to its higher hydrogen dissociation activity and enhanced adsorption capacity for palm oil molecules.Furthermore,reaction condition studies revealed that palm oil was completely converted,yielding 86.8%liquid product with 81.8%selectivity of C_(15)–C_(18)hydrocarbons at 350℃under 7 MPa H_(2)pressure.This finding provides an insight into the development of efficient catalysts for the deoxygenation of fatty compounds to biofuels.展开更多
CoFe bimetallic hydroxides(CoFe BMHs)find wide applications as excellent catalysts in the field of water splitting.However,no study has systematically investigated the influence of the morphologies of CoFe BMHs on cat...CoFe bimetallic hydroxides(CoFe BMHs)find wide applications as excellent catalysts in the field of water splitting.However,no study has systematically investigated the influence of the morphologies of CoFe BMHs on catalyst performance.In this study,CoFe BMH nanoflowers(CoFe BMH NFs),CoFe BMH nanosheets(CoFe BMH NSHs),CoFe BMH nanorods(CoFe BMH NRs),and CoFe BMH nanospheres(CoFe BMH NSPs)were prepared on nickel foam via a hydrothermal method.CoFe BMH NSHs exhibited the most beneficial catalytic activity.At a current density of 100 mA·cm^(-2),its overpotential for oxygen evolution reaction(OER)was 282 mV,and the overall water splitting voltage was 2.05 V.The double-layer charging capacitance(Cdl)value of CoFe BMH NSHs was the largest in CoFe BMHs,which proves that CoFe BMH NSHs have the largest active area.Furthermore,the active site in the OER process was metal oxyhydroxide(MOOH)through in situ Raman characterization,and the generation of the active substance was an irreversible process.This work provides important insights into the design of catalyst morphologies and offers valuable guidelines for the enhancement of the performance of other catalysts.展开更多
Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.H...Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.Herein,we find that oxygen vacancies can significantly boost the capacity,electrochemical kinetics,and structure stability of LDHs.The corresponding structure-performance relationship and energy storage mechanism are elaborated through exhaustive in/ex-situ experimental characterizations and density functional theory(DFT)calculations.Specially,in-situ Raman and DFT calculations reveal that oxygen vacancies elevate orbital energy of O 2p and electron density of O atoms,thereby enhancing the orbital hybridization of O 2p with Ni/Co 3d.This facilitates electron transfer between O and adjacent Ni/Co atoms and improves the covalency of Ni–O and Co–O bonds,which activates Ni/Co atoms to release more capacity and stabilizes the Ov-NiCo-LDH structure.Moreover,the distribution of relaxation times(DRT)and molecular dynamics(MD)simulations disclose that the enhanced d-p orbital hybridization optimizes the electronic structure of Ov-NiCo-LDH,which distinctly reduces the diffusion energy barriers of Mg^(2+)and improves the charge transfer kinetics of Ov-NiCo-LDH.Consequently,the assembled Ov-NiCo-LDH//active carbon(AC)and Ov-NiCo-LDH//perylenediimide(PTCDI)AMIBs can both deliver high specific discharge capacity(182.7 and 59.4 mAh g^(−1)at 0.5 A g^(−1),respectively)and long-term cycling stability(85.4%and 89.0%of capacity retentions after 2500 and 2400 cycles at 1.0 A g^(−1),respectively).In addition,the practical prospects for Ov-NiCo-LDH-based AMIBs have been demonstrated in different application scenarios.This work not only provides an effective strategy for obtaining high-performance cathodes of AMIBs,but also fundamentally elucidates the inherent mechanisms.展开更多
NiFe(oxy)hydroxide(NiFeOOH)has been widely studied as a catalyst for oxygen evolution reaction(OER),but its activity is still not satisfactory.Although metal doping has been employed as a promising strategy for addres...NiFe(oxy)hydroxide(NiFeOOH)has been widely studied as a catalyst for oxygen evolution reaction(OER),but its activity is still not satisfactory.Although metal doping has been employed as a promising strategy for addressing this issue,the instability and leaching of the high-valence dopant metals remain considerable challenges.Herein,an array of Cr-doped NiFeOOH nanosheets was in situ synthesized on nickel foam via a one-step hydrothermal method.The doping of NiFeOOH with Cr was found to induce partial electron transfer from Ni and Fe to Cr atoms,thereby modulating the electronic structure of the catalyst and enhancing its intrinsic activity.Electrochemical and in situ Raman spectroscopy analyses showed that Fe active sites with lower charge density enhance the adsorption of^(*) OH and reduce the formation energy barrier of the*OOH intermediate during OER,thereby accelerating the OER.Moreover,Fe was found to promote the transfer of additional electrons to Cr,leading to electron accumulation at Cr sites.This electron accumulation effectively prevents Cr from excessive oxidation and leaching under anode potentials,thereby maintaining the structural stability of the catalyst.The optimized Cr-doped NiFeOOH self-supported electrode exhibited a current density of 50 mA/cm^(2) with an overpotential of only 239 mV and remained stable for 100 h at 600 mA/cm^(2) in 1 mol/L KOH.展开更多
Electrically driven water splitting is an efficient method for green hydrogen production;however,its practical application is substantially constrained by the kinetically sluggish anodic oxygen evolution reaction(OER)...Electrically driven water splitting is an efficient method for green hydrogen production;however,its practical application is substantially constrained by the kinetically sluggish anodic oxygen evolution reaction(OER).Ruthenium(Ru)and its oxides are widely recognized as highly active OER catalysts.Although Ru is significantly cheaper than iridium(Ir),further reducing its content remains desirable.Herein,atomically dispersed Ru is doped into iron-nickel layered double hydroxides(Ru-FeNi-LDH)to decrease the Ru usage.We found that the Ru doping limit is roughly 9 wt%,and the Ru doping content significantly alters the OER kinetics-note that the high Ru concentration remarkably damages the Ru-FeNi-LDH structure and leads to agglomeration formation.By optimizing the Ru doping content to 3.3 wt%,the Ru-FeNi-LDH presents a low overpotential of 230 mV to reach a current density of 10 mA cm^(-2) in 1 M KOH,which is far better than the reference FeNi-LDH(280 mV)and RuO_(2)(350 mV).In the overall water splitting test,the current density of 10 mA cm^(-2) can be reached at a low voltage of 1.52 V,with stable operation for 80 h.Interestingly,Ru and Fe form an asymmetric Ru-Fe dipole,which is likely doped together into the LDH because the content of Fe instead of Ni is dependent on Ru content in experimental results.The electron-deficient feature of the Ru-Fe dipole thus facilitates the OER process.This work demonstrates a dual-transition metal synergy,providing a design strategy for OER and related catalysts.展开更多
The reasonable development and design of high-efficiency and low-cost electrocatalysts for hydrogen evolution reaction(HER)under industrial current densities are imperative for achieving carbon neutrality,while also p...The reasonable development and design of high-efficiency and low-cost electrocatalysts for hydrogen evolution reaction(HER)under industrial current densities are imperative for achieving carbon neutrality,while also posing challenges.In this study,an efficient electrocatalyst is successfully constructed through electrodeposition methods,which consists of monodispersed Pt loaded on amorphous/crystalline nickel–iron layered double hydroxide(Pt-SAs/ac-NiFe LDH).The Pt-SAs/ac-NiFe LDH demonstrates an elevated mass activity of 17.66 A mg_(Pt)^(−1)and a significant turnover frequency of 17.90 s^(−1)for HER in alkaline conditions under the overpotential of 100 mV.Meanwhile,for alkaline freshwater and seawater,Pt-SAs/ac-NiFe LDH exhibits ultra-low overpotentials of 141 and 138 mV to reach 1000 mA cm^(−2),respectively.Remarkably,it maintains stable operation for 100 h at 500 mA cm^(−2),showcasing its robustness and reliability.In situ Raman spectra reveal that Pt single atoms(Pt-SAs)accelerate interfacial water dissociation,thereby enhancing the HER kinetics in Pt-SAs/ac-NiFe LDH.Furthermore,theoretical calculation results show significant electronic interaction between the Pt-SAs and the ac-NiFe LDH support.The interaction significantly enhances water adsorption and dissociation,and balances the adsorption/desorption of hydrogen intermediates,ultimately improving HER performance.This research provides a viable method for designing efficient HER catalysts for water electrolysis in alkaline freshwater and seawater under industrial current densities.展开更多
基金supported by the Natural Science Foundation of Henan(242300421230)the Young Teacher Fundamental Research Cultivation Program of Zhengzhou University(JC23557030)the National Natural Science Foundation of China(U21A20281 and 22208322)。
文摘Noble metal-loaded layered hydroxides exhibit high efficiency in electrocatalyzing water splitting.However,their widespread use as bifunctional electrocatalysts is hindered by low metal loading,inefficient yield,and complex synthesis processes.In this work,platinum atoms were anchored onto nickel-iron layered double hydroxide/carbon nanotube(LDH/CNT)hybrid electrocatalysts by using a straightforward milling technique with K_(2)Pt Cl_(6)·6H_(2)O as the Pt source.By adjusting the Pt-to-Fe ratio to 1/2 and 1/10,excellent electrocatalysts—Pt_(1/6)-Ni_(2/3)Fe_(1/3)-LDH/CNT and Pt_(1/30)-Ni_(2/3)Fe_(1/3)-LDH/CNT—were achieved with superior performance in hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),outperforming the corresponding commercial Pt/C(20 wt%)and Ru O_(2)electrocatalysts.The enhanced electrochemical performance is attributed to the modification of Pt's electronic structure,which exhibits electron-rich states for HER and electrondeficient states for OER,significantly boosting Pt's electrochemical activity.Furthermore,the simple milling technology for controlling Pt loading offers a promising approach for scaling up the production of electrocatalysts.
基金the financial support by the National Natural Science Foundation of China(51874357,51872333,U20A20123)Innovative Research Group of Hunan Provincial Natural Science Foundation of China(2019JJ10006)support from Shenghua Scholar Program of Central South University.R.M.acknowledges support from JSPS KAKENNHI(18H03869)。
文摘Strategy of anchoring alloy nanoparticles made up of the efficient catalytic element(e.g.,Ni,Fe)on dodecyl sulfate(DS^(-))-intercalated NiFe layered double hydroxides(DS^(-)-NiFe LDH)obtained by a convenient one-step hydrothermal coprecipitation method for essentially enhancing oxygen evolution reaction(OER)performance was proposed.The results of structural characterization indicate Pt_(2)FeNi alloy nanoparticles evenly distribute on the surface of DS^(-)-NiFe LDH.The sizes of the Pt_(2)FeNi nanoparticles,closely related to their OER performance,could be wellcontrolled by adjusting the amount of H;PtCl;addition.The composite structure of as-prepared product was stable during processes of synthesis,exfoliation,self-assembly,and subsequent electrocatalytic OER.Rigorous electrochemical test proving the contributing catalytic active sites was located at the interface between Pt_(2)FeNi and DS^(-)-NiFe LDH,and the Ni and Fe were the major active elements while O atoms are adsorption sites.The formation of Pt_(2)FeNi nanoparticles could greatly prompt the reduction of Tafel slope.The best-performing Pt_(2)FeNi/DS^(-)-NiFe LDH with a Pt content of 0.98 wt%achieved low overpotential of 204 mV at 10 mA cm^(-2)and 262 mV at 50 mA cm^(-2).This work provides a convenient and effective strategy to create additional active sites for enhancing OER performance of NiFe LDH and make contribution to its wide application.
基金support from the National Natural Science Foundation of China(51402100,21905088,21573066 and U19A2017)the Provincial Natural Science Foundation of Hunan(2020JJ5044,2022JJ10006)。
文摘Rationally manipulating surface reconstruction of catalysts for water oxidation,inducing formation and dynamic accumulation of catalytically active centers still face numerous challenges.Herein,the introduction of[Cr(C_(2)O_(4))_(3)]^(3-)into NiFe LDHs by intercalation engineering to promote surface reconstruction achieves an advanced oxygen evolution reaction(OER)activity.In view of the weak electronegativity of Cr^(3+) in[Cr(C_(2)O_(4))_(3)]^(3-),the intercalation of[Cr(C_(2)O_(4))_(3)]^(3-)is expected to result in an electron-rich structure of Fe sites in NiFe LDHs,and higher valence state of Ni can be formed with the charge transfer between Fe and Ni.The optimized electronic structure of NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs with more active Ni^(3+) species and the expedited dynamic generation of Ni^(3+) (Fe)OOH phase during the OER process contributed to its excellent catalytic property,revealed by in situ X-ray absorption spectroscopy,Raman spectroscopy,and quasi-in situ X-ray photoelectron spectroscopy.With the modulated electronic structure of metal sites,NiFe-[Cr(C_(2)O_(4))_(3)]^(3-)-LDHs exhibited promoted OER property with a lower overpotential of 236 mV at the current density of 10 mA cm^(-2).This work illustrates the intercalation of conjugated anion to dynamically construct desired Ni^(3+) sites with the optimal electronic environment for improved OER electrocatalysis.
文摘We report a facile way to prepare sulfur(S) doped Ni4/5 Fe1/5-layered double hydroxide(LDH) electrocatalysts for oxygen evolution reaction(OER). The influence of S doping amount on the OER activity of the resulted Ni Fe-LDHs was studied and the optimal surface S content was ca. 0.43 at%. The developed S-doped Ni Fe-LDH exhibits excellent OER catalyst activity in 1.0 M KOH with overpotential of only 257 m V at the current density of 10 m A cm^-2. Moreover, the catalyst could maintain high activity after 30 h stability test. The high activity of the S-doped Ni Fe-LDH catalysts may originate from the synergistic effect between S and the Fe sites. This work provides a simple but efficient way to improve the OER performance of transition metal oxides/(oxy)hydroxides.
文摘Monolithic catalysts for CO_(2) methanation have become an active research area for the industrial development of Power-to-Gas technology.In this study,we developed a facile and reproducible synthesis strategy for the preparation of structured NiFe catalysts on washcoated cordierite monoliths for CO_(2) methanation.The NiFe catalysts were derived from in-situ grown layered double hydroxides(LDHs)via urea hydrolysis.The influence of different washcoat materials,i.e.,alumina and silica colloidal suspensions on the formation of LDHs layer was investigated,together with the impact of total metal concentration.NiFe LDHs were precipitated on the exterior surface of cordierite washcoated with alumina,while it was found to deposit further inside the channel wall of monolith washcoated with silica due to different intrinsic properties of the colloidal solutions.On the other hand,the thickness of in-situ grown LDHs layers and the catalyst loading could be increased by high metal concentration.The best monolithic catalyst(COR-AluCC-0.5M)was robust,having a thin and well-adhered catalytic layer on the cordierite substrate.As a result,high methane yield was obtained from CO_(2) methanation at high flow rate on this structured NiFe catalysts.The monolithic catalysts appeared as promising structured catalysts for the development of industrial methanation reactor.
基金This work was supported by the National Natural Science Foundation of China(52073008,52272181)the China Postdoctoral Science Foundation(2023T160036).
文摘The dynamic surface self-reconstruction behavior in local structure correlates with oxygen evolution reaction(OER)performance,which has become an effective strategy for constructing the catalytic active phase.However,it remains a challenge to understand the mechanisms of reconstruction and to accomplish it fast and deeply.Here,we reported a photo-promoted rapid reconstruction(PRR)process on Ag nanoparticle-loaded amorphous Ni-Fe hydroxide nanosheets on carbon cloth for enhanced OER.The photogenerated holes generated by Ag in conjunction with the anodic potential contributed to a thorough reconstruction of the amorphous substrate.The valence state of unsaturated coordinated Fe atoms,which serve as active sites,is significantly increased,while the corresponding crystalline substrate shows little change.The different structural evolutions of amorphous and crystalline substrates during reconstruction lead to diverse pathways of OER.This PRR utilizing loaded noble metal nanoparticles can accelerate the generation of active species in the substrate and increase the electrical conductivity,which provides a new inspiration to develop efficient catalysts via reconstruction strategies.
基金National Natural Science Foundation of China(22278084)State Key Laboratory of Heavy Oil Processing(SKLHOP202402003)for financing this research.
文摘To achieve palm oil conversion along with a high yield of long‐chain alkane,a series of NiFe layered double oxide catalysts were prepared and employed in the deoxygenation of palm oil.The layered structure of these catalysts was confirmed by XRD and SEM analyses,and Ni and Fe species existed primarily in the forms of Ni^(2+)and Fe^(3+),respectively.It was found that Ni/Fe molar ratio influenced the H_(2)reducibility and surface properties of NiFe catalysts.Specifically,Ni_(2)Fe‐LDO and Ni_(3)Fe‐LDO exhibited higher reducibility under H_(2)atmosphere.Moreover,the Ni_(2)Fe‐LDO catalyst contained a higher concentration of surface oxygen species(Osurf).Deoxygenation results demonstrated that the Ni_(2)Fe‐LDO catalyst achieved superior palm oil conversion,higher liquid product yield and enhanced selectivity toward C_(15)–C_(18)hydrocarbons compared to other catalysts.This improved performance was attributed to its higher hydrogen dissociation activity and enhanced adsorption capacity for palm oil molecules.Furthermore,reaction condition studies revealed that palm oil was completely converted,yielding 86.8%liquid product with 81.8%selectivity of C_(15)–C_(18)hydrocarbons at 350℃under 7 MPa H_(2)pressure.This finding provides an insight into the development of efficient catalysts for the deoxygenation of fatty compounds to biofuels.
基金supported by the National Science Fund for Distinguished Young Scholars(No.52025041)the National Natural Science Foundation of China(Nos.52474319,52250091,U2341267,and 52450003)+1 种基金the Fundamental Research Funds for the Central Universities(No.FRF-TP-20-02C2)supported by the Interdisciplinary Research Project for Young Teachers of USTB,China(Fundamental Research Funds for the Central Universities)(No.FRF-IDRY-GD23-003).
文摘CoFe bimetallic hydroxides(CoFe BMHs)find wide applications as excellent catalysts in the field of water splitting.However,no study has systematically investigated the influence of the morphologies of CoFe BMHs on catalyst performance.In this study,CoFe BMH nanoflowers(CoFe BMH NFs),CoFe BMH nanosheets(CoFe BMH NSHs),CoFe BMH nanorods(CoFe BMH NRs),and CoFe BMH nanospheres(CoFe BMH NSPs)were prepared on nickel foam via a hydrothermal method.CoFe BMH NSHs exhibited the most beneficial catalytic activity.At a current density of 100 mA·cm^(-2),its overpotential for oxygen evolution reaction(OER)was 282 mV,and the overall water splitting voltage was 2.05 V.The double-layer charging capacitance(Cdl)value of CoFe BMH NSHs was the largest in CoFe BMHs,which proves that CoFe BMH NSHs have the largest active area.Furthermore,the active site in the OER process was metal oxyhydroxide(MOOH)through in situ Raman characterization,and the generation of the active substance was an irreversible process.This work provides important insights into the design of catalyst morphologies and offers valuable guidelines for the enhancement of the performance of other catalysts.
基金financial support of the National Natural Science Foundation of China (22379063)
文摘Layered double hydroxides(LDHs)are potential cathode materials for aqueous magnesium-ion batteries(AMIBs).However,the low capacity and sluggish kinetics significantly limit their electrochemical performance in AMIBs.Herein,we find that oxygen vacancies can significantly boost the capacity,electrochemical kinetics,and structure stability of LDHs.The corresponding structure-performance relationship and energy storage mechanism are elaborated through exhaustive in/ex-situ experimental characterizations and density functional theory(DFT)calculations.Specially,in-situ Raman and DFT calculations reveal that oxygen vacancies elevate orbital energy of O 2p and electron density of O atoms,thereby enhancing the orbital hybridization of O 2p with Ni/Co 3d.This facilitates electron transfer between O and adjacent Ni/Co atoms and improves the covalency of Ni–O and Co–O bonds,which activates Ni/Co atoms to release more capacity and stabilizes the Ov-NiCo-LDH structure.Moreover,the distribution of relaxation times(DRT)and molecular dynamics(MD)simulations disclose that the enhanced d-p orbital hybridization optimizes the electronic structure of Ov-NiCo-LDH,which distinctly reduces the diffusion energy barriers of Mg^(2+)and improves the charge transfer kinetics of Ov-NiCo-LDH.Consequently,the assembled Ov-NiCo-LDH//active carbon(AC)and Ov-NiCo-LDH//perylenediimide(PTCDI)AMIBs can both deliver high specific discharge capacity(182.7 and 59.4 mAh g^(−1)at 0.5 A g^(−1),respectively)and long-term cycling stability(85.4%and 89.0%of capacity retentions after 2500 and 2400 cycles at 1.0 A g^(−1),respectively).In addition,the practical prospects for Ov-NiCo-LDH-based AMIBs have been demonstrated in different application scenarios.This work not only provides an effective strategy for obtaining high-performance cathodes of AMIBs,but also fundamentally elucidates the inherent mechanisms.
基金supported by the National Natural Science Foundation of China(Nos.51822106 and 52002318).
文摘NiFe(oxy)hydroxide(NiFeOOH)has been widely studied as a catalyst for oxygen evolution reaction(OER),but its activity is still not satisfactory.Although metal doping has been employed as a promising strategy for addressing this issue,the instability and leaching of the high-valence dopant metals remain considerable challenges.Herein,an array of Cr-doped NiFeOOH nanosheets was in situ synthesized on nickel foam via a one-step hydrothermal method.The doping of NiFeOOH with Cr was found to induce partial electron transfer from Ni and Fe to Cr atoms,thereby modulating the electronic structure of the catalyst and enhancing its intrinsic activity.Electrochemical and in situ Raman spectroscopy analyses showed that Fe active sites with lower charge density enhance the adsorption of^(*) OH and reduce the formation energy barrier of the*OOH intermediate during OER,thereby accelerating the OER.Moreover,Fe was found to promote the transfer of additional electrons to Cr,leading to electron accumulation at Cr sites.This electron accumulation effectively prevents Cr from excessive oxidation and leaching under anode potentials,thereby maintaining the structural stability of the catalyst.The optimized Cr-doped NiFeOOH self-supported electrode exhibited a current density of 50 mA/cm^(2) with an overpotential of only 239 mV and remained stable for 100 h at 600 mA/cm^(2) in 1 mol/L KOH.
基金supported by Guangdong Basic and Applied Basic Research Foundation(2022B1515120079)Tertiary Education Scientific research project of Guangzhou Municipal Education Bureau(2024312194)+1 种基金the Science and Technology Projects in Guangzhou(2024A03J0308)the Outstanding Youth Project of Natural Science Foundation of Guangdong Province(2022B1515020020).
文摘Electrically driven water splitting is an efficient method for green hydrogen production;however,its practical application is substantially constrained by the kinetically sluggish anodic oxygen evolution reaction(OER).Ruthenium(Ru)and its oxides are widely recognized as highly active OER catalysts.Although Ru is significantly cheaper than iridium(Ir),further reducing its content remains desirable.Herein,atomically dispersed Ru is doped into iron-nickel layered double hydroxides(Ru-FeNi-LDH)to decrease the Ru usage.We found that the Ru doping limit is roughly 9 wt%,and the Ru doping content significantly alters the OER kinetics-note that the high Ru concentration remarkably damages the Ru-FeNi-LDH structure and leads to agglomeration formation.By optimizing the Ru doping content to 3.3 wt%,the Ru-FeNi-LDH presents a low overpotential of 230 mV to reach a current density of 10 mA cm^(-2) in 1 M KOH,which is far better than the reference FeNi-LDH(280 mV)and RuO_(2)(350 mV).In the overall water splitting test,the current density of 10 mA cm^(-2) can be reached at a low voltage of 1.52 V,with stable operation for 80 h.Interestingly,Ru and Fe form an asymmetric Ru-Fe dipole,which is likely doped together into the LDH because the content of Fe instead of Ni is dependent on Ru content in experimental results.The electron-deficient feature of the Ru-Fe dipole thus facilitates the OER process.This work demonstrates a dual-transition metal synergy,providing a design strategy for OER and related catalysts.
基金funded by the National Key Research and Development Program of China(2022YFB3803600)the National Natural Science Foundation of China(22368050,22378346)+4 种基金the Key Research and Development Program of Yunnan Province(202302AF080002)Yunnan Basic Applied Research Project(202401AT070460,202401AU070229)Xingdian Talent Support Program Project in Yunnan Province,the Scientific Research Fund Project of Yunnan Education Department(2024J0014,2024J0013)the Open Project of Yunnan Precious Metals Laboratory Co.,Ltd(YPML-2023050259,YPML-2023050260,YPML-20240502008)the Scientific Research and Innovation Project of Postgraduate Students in the Academic Degree of Yunnan University.
文摘The reasonable development and design of high-efficiency and low-cost electrocatalysts for hydrogen evolution reaction(HER)under industrial current densities are imperative for achieving carbon neutrality,while also posing challenges.In this study,an efficient electrocatalyst is successfully constructed through electrodeposition methods,which consists of monodispersed Pt loaded on amorphous/crystalline nickel–iron layered double hydroxide(Pt-SAs/ac-NiFe LDH).The Pt-SAs/ac-NiFe LDH demonstrates an elevated mass activity of 17.66 A mg_(Pt)^(−1)and a significant turnover frequency of 17.90 s^(−1)for HER in alkaline conditions under the overpotential of 100 mV.Meanwhile,for alkaline freshwater and seawater,Pt-SAs/ac-NiFe LDH exhibits ultra-low overpotentials of 141 and 138 mV to reach 1000 mA cm^(−2),respectively.Remarkably,it maintains stable operation for 100 h at 500 mA cm^(−2),showcasing its robustness and reliability.In situ Raman spectra reveal that Pt single atoms(Pt-SAs)accelerate interfacial water dissociation,thereby enhancing the HER kinetics in Pt-SAs/ac-NiFe LDH.Furthermore,theoretical calculation results show significant electronic interaction between the Pt-SAs and the ac-NiFe LDH support.The interaction significantly enhances water adsorption and dissociation,and balances the adsorption/desorption of hydrogen intermediates,ultimately improving HER performance.This research provides a viable method for designing efficient HER catalysts for water electrolysis in alkaline freshwater and seawater under industrial current densities.
