This study examined the impact of CeO_(2)addition on the sulfur tolerance of Pd/beta zeolite catalyst in toluene catalytic oxidation.By preparing and assessing Ce-modified beta zeolite-supported Pd catalysts,it is fou...This study examined the impact of CeO_(2)addition on the sulfur tolerance of Pd/beta zeolite catalyst in toluene catalytic oxidation.By preparing and assessing Ce-modified beta zeolite-supported Pd catalysts,it is found that the toluene complete conversion over Pd/7.5Ce-beta zeolite occurs at 190℃,with a minimal increase of 20℃even after sulfur poisoning.It is shown that Ce-doping markedly enhances sulfur tolerance besides catalytic activity.The underlying mechanism involves CeO_(2)sites capturing sulfur species,thus safeguarding active Pd species from sulfur poisoning.It can be observed that Pd0active sites,which are crucial in the catalytic high activity,are still present in the most severely poisoned catalyst.Furthermore,Ce-modified catalyst exhibits a more stable pore structure and increased acid strength after sulfur poisoning,all of which are beneficial to improving the sulfur tolerance.Consequently,Pd/Ce-beta zeolite is a promising solution for processing sulfur-containing volatile organic compounds,offering valuable insights for developing effective and sustainable catalysts for environmental remediation.展开更多
Highly dispersed noble metals are acknowledged for its pivotal role in influencing the efficiency of catalysts during the HCHO oxidation process.Interestingly,in this work,an innovative approach was employed to augmen...Highly dispersed noble metals are acknowledged for its pivotal role in influencing the efficiency of catalysts during the HCHO oxidation process.Interestingly,in this work,an innovative approach was employed to augmenting the stabilization of noble metals on irreducible carriers supported noble metal catalyst(Pd/SiO_(2))by adding alkali metal potassium(K).A formidable promotion effect was observed when the K doping to Pd/SiO_(2) catalysts.It achieves a conversion rate of 93%for 270 ppmV of HCHO to harmless CO_(2) and H_(2)O at a weight hourly space velocity(WHSV)of 300,000 mL/(g·hr)at 25℃.Multiple characterization results illustrated that a strong interaction between added K and Pd species was formed after K addition,which not only stabilized Pd species on the carrier surface but alsomarkedly enhanced its dispersal on the SiO_(2) carrier.The increasing Pd dispersion induced more oxygen vacancies on the surfaces of the Pd/SiO_(2) catalysts.The formation of these oxygen vacancies can be attributed to the phenomenon of hydrogen spillover,which also contributed to elevating the electron density on the Pd sites.Meanwhile,the oxygen vacancies favored the O_(2) activation to formmore reactive oxygen species participating in the HCHO oxidation reaction,thus improving the performance of Pd/SiO_(2) catalysts displayed for HCHO oxidation.This study provides a simple strategy to design high-performance irreducible carriers supported noble metal catalysts for HCHO catalytic oxidation.展开更多
Layered transition metal hydroxides show distinct advantages in separately co-catalyzing CO_(2)reduction and H_(2)O oxidation at the electron-accumulating and hole-accumulating sites of wrapped heterojunction photocat...Layered transition metal hydroxides show distinct advantages in separately co-catalyzing CO_(2)reduction and H_(2)O oxidation at the electron-accumulating and hole-accumulating sites of wrapped heterojunction photocatalysts,while concurrently preventing side reactions and photocorrosion on the semiconductor surface.Herein,Ni-Co bimetallic hydroxides with varying Ni/Co molar ratios(Ni_(x)Co_(1-x)(OH)_(2),x=1,0.75,0.5,0.25,and 0)were grown in situ on a model 2D/2D S-scheme heterojunction composed of Cu_(2)O nanosheets and Fe_(2)O_(3)nanoplates to form a series of Cu_(2)O/Fe_(2)O_(3)@Ni_(x)Co_(1-x)(OH)_(2)(CF@NiCo)photocatalysts.The combined experimental and theoretical investigation demonstrates that incorporating an appropriate amount of Co into Ni(OH)_(2)not only modulates the energy band structure of Ni_(x)Co_(1-x)(OH)_(2),balances the electron-and hole-trapping abilities of the bifunctional cocatalyst and maximizes the charge separation efficiency of the heterojunction,but also regulates the d-band center of Ni_(x)Co_(1-x)(OH)_(2),reinforcing the adsorption and activation of CO_(2)and H_(2)O on the cocatalyst surface and lowering the rate-limiting barriers in the CO_(2)-to-CO and H_(2)O-to-O_(2)conversion.Benefiting from the Ni-Co synergy,the redox reactions proceed stoichiometrically.The optimized CF@Ni_(0.75)Co_(0.25)achieves CO and O_(2)yields of 552.7 and 313.0μmol gcat^(-1)h^(-1),respectively,11.3/9.9,1.6/1.7,and 4.5/5.9-fold higher than those of CF,CF@Ni,and CF@Co.This study offers valuable insights into the design of bifunctional noble-metal-free cocatalysts for high-performance artificial photosynthesis.展开更多
The expandable graphite(EG)modified TiO_(2) nanocomposites were prepared by the high shearmethod using the TiO_(2) nanoparticles(NPs)and EG as precursors,in which the amount of EG doped in TiO_(2) was 10 wt.%.Followed...The expandable graphite(EG)modified TiO_(2) nanocomposites were prepared by the high shearmethod using the TiO_(2) nanoparticles(NPs)and EG as precursors,in which the amount of EG doped in TiO_(2) was 10 wt.%.Followed by the impregnation method,adjusting the pH of the solution to 10,and using the electrostatic adsorption to achieve spatial confinement,the Pt elementswere mainly distributed on the exposed TiO_(2),thus generating the Pt/10EG-TiO_(2)-10 catalyst.The best CO oxidation activity with the excellent resistance to H_(2)O and SO_(2) was obtained over the Pt/10EG-TiO_(2)-10 catalyst:CO conversion after 36 hr of the reaction was ca.85%under the harsh condition of 10 vol.%H_(2)O and 100 ppm SO_(2) at a high gaseous hourly space velocity(GHSV)of 400,000 hr−1.Physicochemical properties of the catalystswere characterized by various techniques.The results showed that the electrostatic adsorption,which riveted the Pt elements mainly on the exposed TiO_(2) of the support surface,reduced the dispersion of Pt NPs on EG and achieved the effective dispersion of Pt NPs,hence significantly improving CO oxidation activity over the Pt/10EG-TiO_(2)-10 catalyst.The 10 wt.%EG doped in TiO_(2) caused the TiO_(2) support to form a more hydrophobic surface,which reduced the adsorption of H_(2)O and SO_(2) on the catalyst,greatly inhibited deposition of the TiOSO_(4) and formation of the PtSO4 species as well as suppressed the oxidation of SO_(2),thus resulting in an improvement in the resistance to H_(2)O and SO_(2) of the Pt/10EG-TiO_(2)-10 catalyst.展开更多
Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+d...Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.展开更多
Formaldehyde(HCHO)is a significant indoor pollutant found in various sources and poses potential health risks to humans.Noble metal catalysts show efficient and stable catalytic activity for ambient-temperature HCHO o...Formaldehyde(HCHO)is a significant indoor pollutant found in various sources and poses potential health risks to humans.Noble metal catalysts show efficient and stable catalytic activity for ambient-temperature HCHO oxidation,yet suffer from low metal utilization.Efforts focus on designing catalysts with enhanced intrinsic activity and reduced noble metal loading.In this study,we developed a simple pretreatment method using ammonia solution on SiO_(2)carrier to enhance the activity of the Pd/SiO_(2)catalyst for HCHO oxidation.After the carrier was pretreated with an ammonia solution,a significant promoting effect was observed on the Pd/SiO_(2)(NH_(3)·H_(2)O)-R catalyst.It achieved almost complete oxidation of 150 ppmV of HCHO at 25℃,much better than the Pd/SiO_(2)-R(5%HCHO conversion rate).Multiple characterization results indicated that the ammonia solution pretreatment of the SiO_(2)carrier increased the surface defects,facilitating the anchoring of Pd nanoparticles and increasing their dispersion.The increase dispersion of Pd resulted in the generation of additional oxygen vacancies on the catalyst surfaces.The increased in oxygen vacancies on the catalyst was beneficial for enhancing the catalyst's ability to activate H_(2)O to form surface hydroxyl groups,thereby accelerating the catalytic oxidation process of HCHO.The reaction mechanism of HCHO on the Pd/SiO_(2)(NH_(3)·H_(2)O)-R catalyst mainly follows an efficient pathway:firstly,the HCHO being oxidized by surface active hydroxyl groups to formate;subsequently,the formate being oxidized by hydroxyl groups to H_(2)O and CO_(2).This study provides a promising strategy for designing high-performance noble metal catalysts for HCHO catalytic oxidation.展开更多
The oxidation behavior of Ni-based superalloy GH4742 exposed to water vapor was investigated at 900-1100℃for 50 h in Ar+20%H_(2)O,with Ar+20%O_(2)included for comparison.The presence of H_(2)O is adverse to formation...The oxidation behavior of Ni-based superalloy GH4742 exposed to water vapor was investigated at 900-1100℃for 50 h in Ar+20%H_(2)O,with Ar+20%O_(2)included for comparison.The presence of H_(2)O is adverse to formation of continuous Cr_(2)O_(3)oxide layer but contributes to generation of big voids.Based on this,Ni^(2+)and Co^(2+)are more easily to diffuse towards the outermost oxide layer(OOL),forming non-protective Ni-and Co-rich oxides with high proportion.This leads to a higher weight gain in Ar+20%H_(2)O than that in Ar+20%O_(2).At elevated temperatures,the spallation of oxide scale occurs while the consumption of Cr is reduced in Ar+20%H_(2)O,and the contents of Ni-and Co-rich oxides at this moment are reduced in the OOL.The oxidation mechanism was also discussed.展开更多
The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and...The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and Cu_(2)O/Ni O/NF electrodes via in situ pulsed laser irradiation in liquids(PLIL)for the bifunctional electrocatalysis of oxygen evolution reaction(OER)and furfural oxidation reaction(FOR),respectively.Simultaneous oxidation of NF surface to NiO and deposition of CoO and/or Cu_(2)O on NF during PLIL offer distinct advantages for enhancing both the OER and FOR.CoO/NiO/NF electrocatalyst provides a consistently low overpotential of~359 m V(OER)at 10 m A/cm^(2),achieving the maximum FA yield(~16.37 m M)with 61.5%selectivity,79.5%carbon balance,and a remarkable Faradaic efficiency of~90.1%during 2 h of FOR at 1.43 V(vs.reversible hydrogen electrode).Mechanistic pathway via in situ electrochemical-Raman spectroscopy on CoO/NiO/NF reveals the involvement of phase transition intermediates(NiOOH and CoOOH)as surface-active centers during electrochemical oxidation.The carbonyl carbon in FF is attacked by hydroxyl groups to form unstable hydrates that subsequently undergo further oxidation to yield FA products.This method holds promise for large-scale applications,enabling simultaneous production of renewable building materials and fuel.展开更多
The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene(NMST)to 2-nitro-4-methylsulfonyl benzoic acid(NMSBA)with atmospheric air or molecular oxygen in alkaline medium prese...The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene(NMST)to 2-nitro-4-methylsulfonyl benzoic acid(NMSBA)with atmospheric air or molecular oxygen in alkaline medium presents a significant challenge for the chemical industry.Here,we report the synthesis of FeOOH/Fe_(3)O_(4)/metal-organic framework(MOF)polygonal mesopores microflower templated from a MIL-88B(Fe)at room temperature,which exposes polygonal mesopores with atomistic edge steps and lattice defects.The obtained FeOOH/Fe_(3)O_(4)/MOF catalyst was adsorbed onto glass beads and then introduced into the microchannel reactor.In the alkaline environment,oxygen was used as oxidant to catalyze the oxidation of NMST to NMSBA,showing impressive performance.This sustainable system utilizes oxygen as a clean oxidant in an inexpensive and environmentally friendly NaOH/methanol mixture.The position and type of substituent critically affect the products.Additionally,this sustainable protocol enabled gram-scale preparation of carboxylic acid and benzyl alcohol derivatives with high chemoselectivities.Finally,the reactions can be conducted in a pressure reactor,which can conserve oxygen and prevent solvent loss.Moreover,compared with the traditional batch reactor,the self-built microchannel reactor can accelerate the reaction rate,shorten the reaction time,and enhance the selectivity of catalytic oxidation reactions.This approach contributes to environmental protection and holds potential for industrial applications.展开更多
Herein,a first-principles investigation was innovatively conducted to research the surface oxidation of ZnS-like sphalerite in the absence and presence of H_(2)O .The findings showed that single O_(2) was preferred to...Herein,a first-principles investigation was innovatively conducted to research the surface oxidation of ZnS-like sphalerite in the absence and presence of H_(2)O .The findings showed that single O_(2) was preferred to be dissociated adsorption on sphalerite surface by generating SAO and Zn AO bonds,and the S atom on the surface was the most energy-supported site for O_(2) adsorption,on which a≡Zn-O-S-O-Zn≡structure will be formed.However,dissociated adsorption of single H_(2)O will not happen.It was preferred to be adsorbed on the top Zn atom on sphalerite surface in molecular form through Zn-O bond.Besides,sphalerite oxidation can occur as if O_(2) was present regardless of the presence of H_(2)O ,and when H_(2)O and O_(2) coexisted,the formation of sulfur oxide(SO_(2) )needed a lower energy barrier and it was easier to form on sphalerite surface than that only O_(2) existed.In the absence of H_(2)O ,when SO_(2) was generated,further oxidation of which would form neutral zinc sulfate.In the presence of H_(2)O ,the formation of SO_(2) on sphalerite surface was easier and the rate of further oxidation to form sulfate was also greater.Consequently,the occurrence of sphalerite oxidation was accelerated.展开更多
The problem of water and sulfur poisoning in flue gas atmosphere remains a significant obstacle for low-temperature deNO_(x) catalysts.This study investigated the sulfation mechanism of the CoMn_(2)O_(4)/CeTiO_(x)(CMC...The problem of water and sulfur poisoning in flue gas atmosphere remains a significant obstacle for low-temperature deNO_(x) catalysts.This study investigated the sulfation mechanism of the CoMn_(2)O_(4)/CeTiO_(x)(CMCT)catalyst during the selective catalytic reduction of NO_(x) with NH3 under conditions containing H2O and SO_(2) at 150℃.Employing a comprehensive suite of time-resolved analysis and characterization techniques,the evolution of sulfate species was systematically categorized into three stages:initial rapid surface sulfate accumulation,the transformation of surface sulfates to bulk metal sulfates,and partial sulfates decomposition after the removal of H2O and SO_(2).These findings indicate that bulk metal sulfates irreversibly deactivate the catalyst by distorting active component lattices and consuming oxygen vacancies,whereas surface sulfates(including ammonium sulfates and surface-coordinated metal sulfates)cause reversible performance loss through decomposition.Furthermore,the competitive adsorption of H2O and SO_(2) significantly influences the catalytic efficiency,with H2O suppressing SO_(2) adsorption while simultaneously enhancing the formation of Brönsted acid sites.This research underscores the critical role of sulfate dynamics on catalyst performance,revealing the enhanced SO_(2) resistance of the Eley-Rideal mechanism facilitated by the Ce-Ti support relative to the Langmuir-Hinshelwood pathway.Collectively,the study unravels the complex interplay of sulfate dynamics influencing catalyst performance and provides potential approaches to mitigate deactivation in demanding atmospheric conditions.展开更多
P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phas...P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.展开更多
基金Project supported by Zhejiang Public Welfare Technology Research Project(LGG19B070003)the National Natural Science Foundation of China(21902069)。
文摘This study examined the impact of CeO_(2)addition on the sulfur tolerance of Pd/beta zeolite catalyst in toluene catalytic oxidation.By preparing and assessing Ce-modified beta zeolite-supported Pd catalysts,it is found that the toluene complete conversion over Pd/7.5Ce-beta zeolite occurs at 190℃,with a minimal increase of 20℃even after sulfur poisoning.It is shown that Ce-doping markedly enhances sulfur tolerance besides catalytic activity.The underlying mechanism involves CeO_(2)sites capturing sulfur species,thus safeguarding active Pd species from sulfur poisoning.It can be observed that Pd0active sites,which are crucial in the catalytic high activity,are still present in the most severely poisoned catalyst.Furthermore,Ce-modified catalyst exhibits a more stable pore structure and increased acid strength after sulfur poisoning,all of which are beneficial to improving the sulfur tolerance.Consequently,Pd/Ce-beta zeolite is a promising solution for processing sulfur-containing volatile organic compounds,offering valuable insights for developing effective and sustainable catalysts for environmental remediation.
基金supported by the Youth Innovation Promotion Association,CAS(No.2020310)Sanming University(No.23YG05).
文摘Highly dispersed noble metals are acknowledged for its pivotal role in influencing the efficiency of catalysts during the HCHO oxidation process.Interestingly,in this work,an innovative approach was employed to augmenting the stabilization of noble metals on irreducible carriers supported noble metal catalyst(Pd/SiO_(2))by adding alkali metal potassium(K).A formidable promotion effect was observed when the K doping to Pd/SiO_(2) catalysts.It achieves a conversion rate of 93%for 270 ppmV of HCHO to harmless CO_(2) and H_(2)O at a weight hourly space velocity(WHSV)of 300,000 mL/(g·hr)at 25℃.Multiple characterization results illustrated that a strong interaction between added K and Pd species was formed after K addition,which not only stabilized Pd species on the carrier surface but alsomarkedly enhanced its dispersal on the SiO_(2) carrier.The increasing Pd dispersion induced more oxygen vacancies on the surfaces of the Pd/SiO_(2) catalysts.The formation of these oxygen vacancies can be attributed to the phenomenon of hydrogen spillover,which also contributed to elevating the electron density on the Pd sites.Meanwhile,the oxygen vacancies favored the O_(2) activation to formmore reactive oxygen species participating in the HCHO oxidation reaction,thus improving the performance of Pd/SiO_(2) catalysts displayed for HCHO oxidation.This study provides a simple strategy to design high-performance irreducible carriers supported noble metal catalysts for HCHO catalytic oxidation.
文摘Layered transition metal hydroxides show distinct advantages in separately co-catalyzing CO_(2)reduction and H_(2)O oxidation at the electron-accumulating and hole-accumulating sites of wrapped heterojunction photocatalysts,while concurrently preventing side reactions and photocorrosion on the semiconductor surface.Herein,Ni-Co bimetallic hydroxides with varying Ni/Co molar ratios(Ni_(x)Co_(1-x)(OH)_(2),x=1,0.75,0.5,0.25,and 0)were grown in situ on a model 2D/2D S-scheme heterojunction composed of Cu_(2)O nanosheets and Fe_(2)O_(3)nanoplates to form a series of Cu_(2)O/Fe_(2)O_(3)@Ni_(x)Co_(1-x)(OH)_(2)(CF@NiCo)photocatalysts.The combined experimental and theoretical investigation demonstrates that incorporating an appropriate amount of Co into Ni(OH)_(2)not only modulates the energy band structure of Ni_(x)Co_(1-x)(OH)_(2),balances the electron-and hole-trapping abilities of the bifunctional cocatalyst and maximizes the charge separation efficiency of the heterojunction,but also regulates the d-band center of Ni_(x)Co_(1-x)(OH)_(2),reinforcing the adsorption and activation of CO_(2)and H_(2)O on the cocatalyst surface and lowering the rate-limiting barriers in the CO_(2)-to-CO and H_(2)O-to-O_(2)conversion.Benefiting from the Ni-Co synergy,the redox reactions proceed stoichiometrically.The optimized CF@Ni_(0.75)Co_(0.25)achieves CO and O_(2)yields of 552.7 and 313.0μmol gcat^(-1)h^(-1),respectively,11.3/9.9,1.6/1.7,and 4.5/5.9-fold higher than those of CF,CF@Ni,and CF@Co.This study offers valuable insights into the design of bifunctional noble-metal-free cocatalysts for high-performance artificial photosynthesis.
基金supported by the National Key R&D Program of China (No.2017YFC0210303).
文摘The expandable graphite(EG)modified TiO_(2) nanocomposites were prepared by the high shearmethod using the TiO_(2) nanoparticles(NPs)and EG as precursors,in which the amount of EG doped in TiO_(2) was 10 wt.%.Followed by the impregnation method,adjusting the pH of the solution to 10,and using the electrostatic adsorption to achieve spatial confinement,the Pt elementswere mainly distributed on the exposed TiO_(2),thus generating the Pt/10EG-TiO_(2)-10 catalyst.The best CO oxidation activity with the excellent resistance to H_(2)O and SO_(2) was obtained over the Pt/10EG-TiO_(2)-10 catalyst:CO conversion after 36 hr of the reaction was ca.85%under the harsh condition of 10 vol.%H_(2)O and 100 ppm SO_(2) at a high gaseous hourly space velocity(GHSV)of 400,000 hr−1.Physicochemical properties of the catalystswere characterized by various techniques.The results showed that the electrostatic adsorption,which riveted the Pt elements mainly on the exposed TiO_(2) of the support surface,reduced the dispersion of Pt NPs on EG and achieved the effective dispersion of Pt NPs,hence significantly improving CO oxidation activity over the Pt/10EG-TiO_(2)-10 catalyst.The 10 wt.%EG doped in TiO_(2) caused the TiO_(2) support to form a more hydrophobic surface,which reduced the adsorption of H_(2)O and SO_(2) on the catalyst,greatly inhibited deposition of the TiOSO_(4) and formation of the PtSO4 species as well as suppressed the oxidation of SO_(2),thus resulting in an improvement in the resistance to H_(2)O and SO_(2) of the Pt/10EG-TiO_(2)-10 catalyst.
基金supported by the National Natural Science Foundation of China(No.21805018)by Sichuan Science and Technology Program(Nos.2022ZHCG0018,2023NSFSC0117 and 2023ZHCG0060)Yibin Science and Technology Program(No.2022JB005)and China Postdoctoral Science Foundation(No.2022M722704).
文摘Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.
基金supported by the Sanming University(No.23YG05)the Science Foundation of Fujian Province(No.2023J011027).
文摘Formaldehyde(HCHO)is a significant indoor pollutant found in various sources and poses potential health risks to humans.Noble metal catalysts show efficient and stable catalytic activity for ambient-temperature HCHO oxidation,yet suffer from low metal utilization.Efforts focus on designing catalysts with enhanced intrinsic activity and reduced noble metal loading.In this study,we developed a simple pretreatment method using ammonia solution on SiO_(2)carrier to enhance the activity of the Pd/SiO_(2)catalyst for HCHO oxidation.After the carrier was pretreated with an ammonia solution,a significant promoting effect was observed on the Pd/SiO_(2)(NH_(3)·H_(2)O)-R catalyst.It achieved almost complete oxidation of 150 ppmV of HCHO at 25℃,much better than the Pd/SiO_(2)-R(5%HCHO conversion rate).Multiple characterization results indicated that the ammonia solution pretreatment of the SiO_(2)carrier increased the surface defects,facilitating the anchoring of Pd nanoparticles and increasing their dispersion.The increase dispersion of Pd resulted in the generation of additional oxygen vacancies on the catalyst surfaces.The increased in oxygen vacancies on the catalyst was beneficial for enhancing the catalyst's ability to activate H_(2)O to form surface hydroxyl groups,thereby accelerating the catalytic oxidation process of HCHO.The reaction mechanism of HCHO on the Pd/SiO_(2)(NH_(3)·H_(2)O)-R catalyst mainly follows an efficient pathway:firstly,the HCHO being oxidized by surface active hydroxyl groups to formate;subsequently,the formate being oxidized by hydroxyl groups to H_(2)O and CO_(2).This study provides a promising strategy for designing high-performance noble metal catalysts for HCHO catalytic oxidation.
基金supported by the National Key R&D Program of China(No.2021YFB3700400)National Natural Science Foundation of China(Nos.52074030,51904021,52174294).
文摘The oxidation behavior of Ni-based superalloy GH4742 exposed to water vapor was investigated at 900-1100℃for 50 h in Ar+20%H_(2)O,with Ar+20%O_(2)included for comparison.The presence of H_(2)O is adverse to formation of continuous Cr_(2)O_(3)oxide layer but contributes to generation of big voids.Based on this,Ni^(2+)and Co^(2+)are more easily to diffuse towards the outermost oxide layer(OOL),forming non-protective Ni-and Co-rich oxides with high proportion.This leads to a higher weight gain in Ar+20%H_(2)O than that in Ar+20%O_(2).At elevated temperatures,the spallation of oxide scale occurs while the consumption of Cr is reduced in Ar+20%H_(2)O,and the contents of Ni-and Co-rich oxides at this moment are reduced in the OOL.The oxidation mechanism was also discussed.
基金supported by the Korea Basic Science Institute(National research Facilities and Equipment Center)grant funded by the Ministry of Education(2019R1A6C1010042,2021R1A6C103A427)the financial support from the National Research Foundation of Korea(NRF)(2022R1A2C2010686,2022R1A4A3033528,2021R1I1A1A01060380,2021R1C1C2010726,2019H1D3A1A01071209)。
文摘The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and Cu_(2)O/Ni O/NF electrodes via in situ pulsed laser irradiation in liquids(PLIL)for the bifunctional electrocatalysis of oxygen evolution reaction(OER)and furfural oxidation reaction(FOR),respectively.Simultaneous oxidation of NF surface to NiO and deposition of CoO and/or Cu_(2)O on NF during PLIL offer distinct advantages for enhancing both the OER and FOR.CoO/NiO/NF electrocatalyst provides a consistently low overpotential of~359 m V(OER)at 10 m A/cm^(2),achieving the maximum FA yield(~16.37 m M)with 61.5%selectivity,79.5%carbon balance,and a remarkable Faradaic efficiency of~90.1%during 2 h of FOR at 1.43 V(vs.reversible hydrogen electrode).Mechanistic pathway via in situ electrochemical-Raman spectroscopy on CoO/NiO/NF reveals the involvement of phase transition intermediates(NiOOH and CoOOH)as surface-active centers during electrochemical oxidation.The carbonyl carbon in FF is attacked by hydroxyl groups to form unstable hydrates that subsequently undergo further oxidation to yield FA products.This method holds promise for large-scale applications,enabling simultaneous production of renewable building materials and fuel.
基金supported by the National Natural Science Foundation of China(22078251)Hubei Province Key Research and Development Program(2023DJC167)the research project of Hubei Provincial Department of Education(D20191504).
文摘The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene(NMST)to 2-nitro-4-methylsulfonyl benzoic acid(NMSBA)with atmospheric air or molecular oxygen in alkaline medium presents a significant challenge for the chemical industry.Here,we report the synthesis of FeOOH/Fe_(3)O_(4)/metal-organic framework(MOF)polygonal mesopores microflower templated from a MIL-88B(Fe)at room temperature,which exposes polygonal mesopores with atomistic edge steps and lattice defects.The obtained FeOOH/Fe_(3)O_(4)/MOF catalyst was adsorbed onto glass beads and then introduced into the microchannel reactor.In the alkaline environment,oxygen was used as oxidant to catalyze the oxidation of NMST to NMSBA,showing impressive performance.This sustainable system utilizes oxygen as a clean oxidant in an inexpensive and environmentally friendly NaOH/methanol mixture.The position and type of substituent critically affect the products.Additionally,this sustainable protocol enabled gram-scale preparation of carboxylic acid and benzyl alcohol derivatives with high chemoselectivities.Finally,the reactions can be conducted in a pressure reactor,which can conserve oxygen and prevent solvent loss.Moreover,compared with the traditional batch reactor,the self-built microchannel reactor can accelerate the reaction rate,shorten the reaction time,and enhance the selectivity of catalytic oxidation reactions.This approach contributes to environmental protection and holds potential for industrial applications.
基金supported by the Postdoctoral Fellowship Program(Grade A)of China Postdoctoral Science Foundation(No.BX20240429)the National Science and Technology Major Project of the Ministry of Science and Technology of China(No.2024ZD1004007)+3 种基金the National Key R&D Program of China(Nos.2022YFC2904502 and 2022YFC2904501)the National Natural Science Foundation of China(No.52204298)the Major Science and Technology Projects in Yunnan Province(No.202202AB080012)the High Performance Computing Center of Central South University。
文摘Herein,a first-principles investigation was innovatively conducted to research the surface oxidation of ZnS-like sphalerite in the absence and presence of H_(2)O .The findings showed that single O_(2) was preferred to be dissociated adsorption on sphalerite surface by generating SAO and Zn AO bonds,and the S atom on the surface was the most energy-supported site for O_(2) adsorption,on which a≡Zn-O-S-O-Zn≡structure will be formed.However,dissociated adsorption of single H_(2)O will not happen.It was preferred to be adsorbed on the top Zn atom on sphalerite surface in molecular form through Zn-O bond.Besides,sphalerite oxidation can occur as if O_(2) was present regardless of the presence of H_(2)O ,and when H_(2)O and O_(2) coexisted,the formation of sulfur oxide(SO_(2) )needed a lower energy barrier and it was easier to form on sphalerite surface than that only O_(2) existed.In the absence of H_(2)O ,when SO_(2) was generated,further oxidation of which would form neutral zinc sulfate.In the presence of H_(2)O ,the formation of SO_(2) on sphalerite surface was easier and the rate of further oxidation to form sulfate was also greater.Consequently,the occurrence of sphalerite oxidation was accelerated.
文摘The problem of water and sulfur poisoning in flue gas atmosphere remains a significant obstacle for low-temperature deNO_(x) catalysts.This study investigated the sulfation mechanism of the CoMn_(2)O_(4)/CeTiO_(x)(CMCT)catalyst during the selective catalytic reduction of NO_(x) with NH3 under conditions containing H2O and SO_(2) at 150℃.Employing a comprehensive suite of time-resolved analysis and characterization techniques,the evolution of sulfate species was systematically categorized into three stages:initial rapid surface sulfate accumulation,the transformation of surface sulfates to bulk metal sulfates,and partial sulfates decomposition after the removal of H2O and SO_(2).These findings indicate that bulk metal sulfates irreversibly deactivate the catalyst by distorting active component lattices and consuming oxygen vacancies,whereas surface sulfates(including ammonium sulfates and surface-coordinated metal sulfates)cause reversible performance loss through decomposition.Furthermore,the competitive adsorption of H2O and SO_(2) significantly influences the catalytic efficiency,with H2O suppressing SO_(2) adsorption while simultaneously enhancing the formation of Brönsted acid sites.This research underscores the critical role of sulfate dynamics on catalyst performance,revealing the enhanced SO_(2) resistance of the Eley-Rideal mechanism facilitated by the Ce-Ti support relative to the Langmuir-Hinshelwood pathway.Collectively,the study unravels the complex interplay of sulfate dynamics influencing catalyst performance and provides potential approaches to mitigate deactivation in demanding atmospheric conditions.
基金supported by the National Natural Science Foundation of China (22169002)the Chongzuo Key Research and Development Program of China (20220603)the Counterpart Aid Project for Discipline Construction from Guangxi University(2023M02)
文摘P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.
