N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher ...N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.展开更多
Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atm...Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atmospheric pollutant NO but also produces valuable ammonia(NH_(3)).Hence,through the synthesis and modification of Fe_(3)C nanocrystal cata-lysts,the as-obtained optimal sample of Fe_(3)C/C-900 was adopted as the NORR catalyst at ambient conditions.As a result,the Fe_(3)C/C-900 catalyst showed an NH_(3)Faraday efficiency of 76.5%and an NH_(3)yield rate of 177.5μmol·h^(-1)·cm^(-2)at the working potentials of-0.8 and-1.2 V versus reversible hydrogen electrode(vs.RHE),respectively.And it delivered a stable NORR activity during the electrolysis.Moreover,we attribute the high NORR properties of Fe_(3)C/C-900 to two aspects:one is the enhanced intrinsic activity of Fe_(3)C nanocrystals,including the lowering of the energy barrier of rate-limiting step(*NOH→*N)and the inhibition of hydrogen evolution;on the other hand,the favorable dispersion of active components,the effective adsorption of gaseous NO,and the release of liquid NH_(3)products facilitated by the porous carbon substrate.展开更多
Electrochemical nitrate reduction(eNO_(3)RR)and nitric oxide reduction(eNORR)to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production,particularly ...Electrochemical nitrate reduction(eNO_(3)RR)and nitric oxide reduction(eNORR)to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production,particularly within the recently proposed reverse artificial nitrogen cycle route:N_(2)→NO_(x)→NH_(3).Notably,experimental studies have demonstrated that eNORR exhibits superior performance over eNO_(3)RR on Cu6Sn5 catalysts.However,the fundamental mechanisms underlying this difference remain poorly understood.Herein,we performed systematic theoretical calculations to explore the reaction pathways,electronic structure effects,and potential-dependent Faradic efficiency associated with ammonia production via these two distinct electrochemical pathways(eNORR and eNO_(3)RR)on Cu6Sn5.By implementing an advanced‘adaptive electric field controlled constant potential(EFC-CP)’methodology combined with microkinetic modeling,we successfully reproduced the experimental observations and identified the key factors affecting ammonia production in both reaction pathways.It was found that eNORR outperforms eNO_(3)RR because it circumvents the ^(*)NO_(2) dissociation and ^(*)NO_(2) desorption steps,leading to distinct surface coverage of key intermediates between the two pathways.Furthermore,the reaction rates were found to exhibit a pronounced dependence on the surface coverage of ^(*)NO in eNORR and ^(*)NO_(2) in eNO_(3)RR.Specifically,the facile desorption of ^(*)NO_(2) on the Cu6Sn5 surface in eNO_(3)RR limits the attainable surface coverage of ^(*)NO,thereby impeding its performance.In contrast,the eNORR can maintain a high surface coverage of adsorbed ^(*)NO species,contributing to its enhanced ammonia production performance.These fundamental insights provide valuable guidance for the rational design of catalysts and the optimization of reaction routes,facilitating the development of more efficient,sustainable,and scalable techniques for ammonia production.展开更多
Super high molecular weight copolymers of AM/NaA/AMPS were prepared by oxidation–reduction[OR-P(AM/NaA/AMPS)]and controlled radical polymerization[CR-P(AM/NaA/AMPS)].The resulting copolymers were fully characterized,...Super high molecular weight copolymers of AM/NaA/AMPS were prepared by oxidation–reduction[OR-P(AM/NaA/AMPS)]and controlled radical polymerization[CR-P(AM/NaA/AMPS)].The resulting copolymers were fully characterized,and the reaction conditions for their preparation were optimized.OR-P(AM/NaA/AMPS),CR-P(AM/NaA/AMPS),and conventional partially hydrolyzed polyacrylamide(HPAM)in brine solution were comprehensively characterized by thermogravimetric analysis,scanning electron microscopy,atomic force microscopy,and dynamic light scattering.ORP(AM/NaA/AMPS)and CR-P(AM/NaA/AMPS)containing AMPS monomer showed better salt resistance,temperature tolerance,and viscosification property than the conventional HPAM polymer,making them more promising for enhanced oil recovery.Through comprehensive comparison and analysis,it was found that OR-P(AM/NaA/AMPS)was more conducive for high-temperature condition due to the existence of xanthone in OR-P(AM/NaA/AMPS).On the other hand,CR-P(AM/NaA/AMPS)was more suitable for high-mineral atmosphere,which could be attributed to its higher intrinsic viscosity.展开更多
Porous metal nanostructures exhibit excellent catalytic properties due to their high surface-to-volume ratios and abundant catalytic active sites. However, it is still challenging to control nanopores density and stru...Porous metal nanostructures exhibit excellent catalytic properties due to their high surface-to-volume ratios and abundant catalytic active sites. However, it is still challenging to control nanopores density and structural features in a facile route and the preparation of porous alloy nanorods for catalytic application has not been well explored. In this work, we demonstrate a synthetic strategy to fabricate highly porous Au–Ag alloy nanorods(P-Au Ag NRs) by critically dealloying Ag atoms from homogeneous solid Au–Ag alloy nanorods(Au Ag NRs). Combining the merits of the tunable plasmonic properties of noble metal nanorods, excellent stabilities of alloys, and superior catalytic activities of porous structures, we use the P-Au Ag NRs as a Raman probe for the in situ monitoring of the catalytic oxidation of 3,3',5,5' tetramethylbenzidine(TMB) and reduction of 4-nitrothiophenol(4-NTP). We also compare their compositiondependent catalytic activities. The results show that P-Au Ag NRs possess superior chemical stability and higher catalytic activity than those of core-shell structures due to synergistic structural and chemical mechanisms. This strategy provides a predictive design approach for the next-generation alloy catalysts with high-performance.展开更多
Mining activities have created great wealth, but they have also discharged large quantities of tailings. As an important source of heavy metal contamination, sulfide tailings are usually disposed of in open-air impoun...Mining activities have created great wealth, but they have also discharged large quantities of tailings. As an important source of heavy metal contamination, sulfide tailings are usually disposed of in open-air impoundments and thus are exposed to microbial oxidation. Microbial activities greatly enhance sulfide oxidation and result in the release of heavy metals and the precipitation of iron (oxy) hydroxides and sulfates. These secondary minerals in turn influence the mobility of dissolved metals and play important roles in the natural attenuation of heavy metals. Elucidating the microbe–mineral interactions in tailings will improve our understanding of the environmental consequence of mining activities.展开更多
The congruent tri-doped Mg:Mn:Fe:LiNbO 3 crystal has been grown by Czochralski method. Some crystal samples are reduced in Li 2CO 3 powder at 500 ℃ for 24 hours or oxidized for 10 hours at 1100 ℃ in Nb 2O 5 powder. ...The congruent tri-doped Mg:Mn:Fe:LiNbO 3 crystal has been grown by Czochralski method. Some crystal samples are reduced in Li 2CO 3 powder at 500 ℃ for 24 hours or oxidized for 10 hours at 1100 ℃ in Nb 2O 5 powder. Compared with As-grown Mg:Mn:Fe:LiNbO 3, the absorption edge in UV-Vis. absorption spectrum of the oxidized sample and the reduced shifts to the violet and the red, respectively. Reduction increases the absorption of crystals in visible light region. In two-wave coupling experiments, the writing time, maximum diffraction efficiency and the erasure time of crystal samples in the same conditions are determined. The results indicate that oxidation and reduction disposing has great effect on the holographic recording properties of these crystals. The reduced crystal exhibits the fastest response time of 160 s among the crystal series. The mechanism of post-disposing effect on the holographic recording properties of Mg:Mn:Fe:LiNbO 3 crystals are investigated.展开更多
TiO2/γ-Al2O3 supported In/Ag catalysts were prepared by impregnation method,and investigated for NO reduction with CO as the reducing agent under lean burn conditions.The microscopic structure and surface properties ...TiO2/γ-Al2O3 supported In/Ag catalysts were prepared by impregnation method,and investigated for NO reduction with CO as the reducing agent under lean burn conditions.The microscopic structure and surface properties of the catalysts were studied by N2 adsorption-desorption,X-ray diffraction,transmission electron microscopy,X-ray photoelectron spectroscopy,ultraviolet-visible spectroscopy,H2 temperature-programmed reduction and Fourier transform infrared spectroscopy.TiO2/γ-Al2O3 supported In/Ag is a good catalyst for the reduction of NO to N2.It displayed high dispersion,large amounts of surface active components and high NO adsorption capacity,which gave good catalytic performance and stability for the reduction of NO with CO under lean burn conditions.The silver species stabilized and improved the dispersion of the indium species.The introduction of TiO2 into the γ-Al2O3 support promoted NO adsorption and improved the dispersion of the indium species and silver species.展开更多
This feature article illustrates the potential of polarization modulation infrared reflection absorption spectroscopy(PM IRRAS)to provide molecular-level information about the structure,orientation and conformation of...This feature article illustrates the potential of polarization modulation infrared reflection absorption spectroscopy(PM IRRAS)to provide molecular-level information about the structure,orientation and conformation of constituents of thin films at electrode surfaces.PM IRRAS relies on the surface selection rules stating that the p-polarized IR beam is enhanced,while the s-polarized beam is attenuated at the metal surface.The difference between p-and s-polarized beams eliminates the background of the solvent and provides IR spectra at a single electrode potential.In contrast,two other popular in situ IR spectroscopic techniques,namely,subtractively normalized interfacial Fourier transform infrared spectroscopy(SNIFTIRS)and surface-enhanced infrared reflection absorption spectroscopy(SEIRAS),provide potential difference spectra to remove the signal from the bulk solution.In this feature article,we provide a brief tutorial on how to run the PM IRRAS experiment and describe the methods used for background elimination first.The application of the PM IRRAS in the biomimetic research is then illustrated by three examples:construction of a tethered bilayer,reconstitution of colicin into a phospholipid bilayer and determination of the orientation of nucleolipids in a monolayer assembled at a gold electrode surface.Finally,the structural changes of graphene oxide during its electrochemical reduction are described to highlight the promising application of PM IRRAS in materials science.展开更多
A laboratory incubation experiment was conducted to investigate nitrous oxide(N 2O) emission and reduction in a paddy soil(Stagnic Anthrosol) response to the pretreatment of water regime. The paddy soil was maintaine...A laboratory incubation experiment was conducted to investigate nitrous oxide(N 2O) emission and reduction in a paddy soil(Stagnic Anthrosol) response to the pretreatment of water regime. The paddy soil was maintained under either air dried(sample D) or submerged(sample F) conditions for 110 d before the soil was adjusted into soil moisture of 20%, 40%, 60%, 80% and 100% water holding capacity(WHC) respectively, and then incubated with or without 10%(v/v) acetylene for 138 h at 25℃. At lower soil water content (≤60% WHC), N 2O emission from the sample F was 2 29 times higher than that from the sample D( P <0 01). While, N 2O emission from the sample F was only 29 and 14 percent of that from the sample D at the soil moisture of 80% and 100% WHC, respectively( P <0 01). The maximal N 2O emissions observed at soil moisture of 80% WHC were about 24 and 186 times higher than the minima obtained at the soil moisture of 20% WHC for the sample F and D, respectively. But at the soil moisture of 80% and 100% WHC, N 2O emission from the sample F with acetylene(F+ACE) was comparable to that of the sample D with acetylene (D+ACE). The results showed that the F sample produced N 2O ability in denitrification was similar to the sample D, however, the sample F was in the better reduction of N 2O to N 2 than the sample D even after the soil moisture was adjusted into the same level of 80% or 100% WHC. Therefore, the pretreatment of water regime influenced the strength and product composition of denitrification and N 2O emission from the paddy soil.展开更多
A great amount of red mud generated from alumina production by Bayer process was considered as a low-grade iron ore with a grade of 5wt% to 30wt% iron.We adopted the reduction roastingmagnetic separation process to re...A great amount of red mud generated from alumina production by Bayer process was considered as a low-grade iron ore with a grade of 5wt% to 30wt% iron.We adopted the reduction roastingmagnetic separation process to recover ferric oxide from red mud.The red mud samples were processed by reduction roasting,grinding and magnetic separating respectively.The effects of different parameters on the recovery rate of iron were studied in detail.The optimum techqicalparameters were proposed with 700 ℃roasting for 20 min,as 50wt% carbon and 4wt% additive were added.The experimentalresults indicated that the iron recovery and the grade of totaliron were 91% and 60%,respectively.A novelprocess is applicable to recover ferric oxide from the red mud waste fines.展开更多
The catalytic activity of Pd catalysts supported on Ce0.73Tb0.27Ox/SiO2, Ce0.6Zr0.4Ox/Si O2,Ce0.73Tb0.27Ox/La2O3–Al2O3and Ce0.6Zr0.4Ox/La2O3–Al2O3was studied using the reduction of NO by CO. The catalysts were chara...The catalytic activity of Pd catalysts supported on Ce0.73Tb0.27Ox/SiO2, Ce0.6Zr0.4Ox/Si O2,Ce0.73Tb0.27Ox/La2O3–Al2O3and Ce0.6Zr0.4Ox/La2O3–Al2O3was studied using the reduction of NO by CO. The catalysts were characterized by X-ray fluorescence, surface area, X-ray diffraction, temperature-programmed reduction, CO chemisorption and oxygen storage capacity. Temperature-programmed reduction results indicated that Tb or Zr incorporation improves the reducibility and oxygen storage capacity. CO chemisorption data suggested the presence of large Pd O particles due to the low CO/Pd ratio. No significant differences were obtained in light off temperatures（T Light off） for all Pd catalysts and the most active was1.5%Pd/Ce0.6Zr0.4Ox/SiO2.展开更多
As the emission control regulations get stricter,the NO;reduction in the sintering process becomes an important environmental concern owing to its role in the formation of photochemical smog and acid rain.The NOxemiss...As the emission control regulations get stricter,the NO;reduction in the sintering process becomes an important environmental concern owing to its role in the formation of photochemical smog and acid rain.The NOxemissions from the sintering machine account for 48% of total amount from the iron and steel industry.Thus,it is essential to reduce NO;emissions from the sintering machine,for the achievement of clean production of sinter.Ca-Fe oxides,serving as the main binding phase in the sinter,are therefore used as additives into the sintering mixture to reduce NOxemissions.The results show that the NO;reduction ratio achieves 27.76% with 8% Ca-Fe oxides additives since the Ca-Fe oxides can advance the ignition and inhibit the nitrogen oxidation compared with the conventional condition.Meanwhile,the existence of Ca-Fe oxides was beneficial to the sinter quality since they were typical low melting point compounds.The optimal mass fraction of Ca-Fe oxides additives should be less than 8%since the permeability of sintering bed was significantly decreased with a further increase of the Ca-Fe oxides fines,inhibiting the mineralization reaction of sintering mixture.Additionally,the appropriate particle size can be obtained when mixing an equal amount of Ca-Fe oxides additives of-0.5 mm and 0.5-3.0 mm in size.展开更多
The hydrogen reduction of tungsten oxides WO_(2.90),W_(20)O_(58) and WO_3 were directly studied using high temperature X-ray diffraction analysis.The differences between tetragonal WO_(2.90) and monoclinic W_(20)O_(58...The hydrogen reduction of tungsten oxides WO_(2.90),W_(20)O_(58) and WO_3 were directly studied using high temperature X-ray diffraction analysis.The differences between tetragonal WO_(2.90) and monoclinic W_(20)O_(58) were discussed.Pure β-W was obtained from oxide WO_(2.90),while there appears small amount of WO_2 during the reduction of W_(20)O_(58) to β-W.展开更多
Niobium oxide nanowire-deposited carbon fiber（CF） samples were prepared using a hydrothermal method with amorphous Nb2O5·nH2O as precursor. The physical properties of the samples were characterized by means of ...Niobium oxide nanowire-deposited carbon fiber（CF） samples were prepared using a hydrothermal method with amorphous Nb2O5·nH2O as precursor. The physical properties of the samples were characterized by means of numerous techniques, including X-ray diffraction（XRD）, energy-dispersive spectroscopy（EDS）, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, selected-area electron diffraction（SAED）, UV–visible spectroscopy（UV–vis）, N2 adsorption–desorption, Fourier transform infrared spectroscopy（FT-IR）, and X-ray photoelectron spectroscopy. The efficiency for the removal of Cr（VI） was determined.Parameters such as pH value and initial Cr（VI） concentration could influence the Cr（VI） removal efficiency or adsorption capacity of the Nb2O5/carbon fiber sample obtained after hydrothermal treatment at 160°C for 14 hr. The maximal Cr（VI） adsorption capacity of the Nb2O5 nanowire/CF sample was 115 mg/g. This Nb2O5/CF sample also showed excellent photocatalytic activity and stability for the reduction of Cr（Ⅵ） under UV-light irradiation： the Cr（VI） removal efficiency reached 99.9% after UV-light irradiation for 1 hr and there was no significant decrease in photocatalytic performance after the use of the sample for 10 repeated cycles. Such excellent Cr（VI） adsorption capacity and photocatalytic performance was related to its high surface area,abundant surface hydroxyl groups, and good UV-light absorption ability.展开更多
The hydrogen reduction of tungsten oxides WO_(272)and WO_2 were studied directly using high-temperature X-ray diffraction analysis,The pure β-W was obtained from the reduction of WO_(272)The transformation of β-W to...The hydrogen reduction of tungsten oxides WO_(272)and WO_2 were studied directly using high-temperature X-ray diffraction analysis,The pure β-W was obtained from the reduction of WO_(272)The transformation of β-W to x-W was also studied in both hydrogen and nitrogen.The forming condition of β-W from WO_2 was discussed.Finally.a complete schematic diagram of reduction of tungsten oxides was given in this paper.展开更多
Activity of three-way palladium catalyst was examined by means of a pulse-flam-microreactor. The effects of cerium on the catalytic properties of gamma-alumina-supported palladium for the reduction of nitric oxide wer...Activity of three-way palladium catalyst was examined by means of a pulse-flam-microreactor. The effects of cerium on the catalytic properties of gamma-alumina-supported palladium for the reduction of nitric oxide were studied with X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR). The reduction of nitric oxide on palladium catalysts is inhibited significantly by hydrocarbon. However, the reduction of nitric oxide was improved by the addition of cerium to the catalysts. The XPS and TPR studies showed that the presence of cerium provided, palladium oxide in a hard-reduced state and suppressed the chemisorption of hydrocarbons on the palladium oxide. Additionally,cerium could increase surface specific oxygen storage capacity and decrease the apparent activation energy for the rea;ltion CO+NO-->CO2-+-1/2 N-2. So a high conversion of NOx reduction could shift to higher A/F ratio.展开更多
The functionalization of multi-walled carbon nanotubes （MWCNTs） by ozone treatment has been sys- tematically investigated by using Raman spectroscopy, transmission electron microscopy （TEM）, Fourier transform inha...The functionalization of multi-walled carbon nanotubes （MWCNTs） by ozone treatment has been sys- tematically investigated by using Raman spectroscopy, transmission electron microscopy （TEM）, Fourier transform inhared spectroscopy （FTIR）, X-ray photoelectron spectroscopy （XPS）, organic elemental anal- ysis （OEA） and Boehm titration. The results showed that the functionalization process occurred at defective sites （opened mouths, tube caps, debris, etc.） before opening caps and truncating walls, and finally the graphitic structure was deteriorated. The surface oxygen content first increased with the treatment time but kept at around 8.0 wt% after 5 h. The analysis of the distribution of oxygen-containing groups re- vealed that phenolic hydroxyl was gradually converted to carboxyl and lactone, The carboxyl was found to play a pivotal role to reduce the over-potentials when we used the functionalized MWCNTs as the cat- alyst for oxygen reduction reaction （ORR）.展开更多
The （COCl）2/Hantzsch ester is found to be an effective system for the metal-free reduction of tertiary phosphine oxides. The reaction proceeds under mild conditions, and is applicable to triarylphosphine oxides and ...The （COCl）2/Hantzsch ester is found to be an effective system for the metal-free reduction of tertiary phosphine oxides. The reaction proceeds under mild conditions, and is applicable to triarylphosphine oxides and alkyldiarylphosphine oxides to produce the corresponding tertiary phosphines in good to excellent yields. This new finding provides a practical, convenient and metal-free method for the reduction of tertiary phosphine oxides to tertiary phosphines, and shows potential application in organic synthesis.展开更多
The monomolecular surface layer of acceptor doped CeO_(2) may become neutral and metallic or charged and semiconducting.This is revealed in the theoretical analysis of the oxygen pressure dependence of the surface def...The monomolecular surface layer of acceptor doped CeO_(2) may become neutral and metallic or charged and semiconducting.This is revealed in the theoretical analysis of the oxygen pressure dependence of the surface defects concentration in acceptor doped ceria with two different dopant types and operated under different oxygen pressures.Recently published experimental data for highly reduced Sm0.2Ce0.8O1.9-x(SDC)containing a fixed valence dopant Sm3+are very different from those published for Pr0.1Ce0.9O_(2)-x(PCO) with the variable valence dopant Pr4+/Pr3+being reduced under milder conditions.The theoretical analysis of these experimental results fits very well the experimental results of SDC and PCO.It leads to the following predictions:the highly reduced surface of SDC is metallic and neutral,the metallic surface electron density of state is gs=0.9×10^(38)J-1·m^(-2)(1.4×1015eV^(-1)·cm^(-2)),the electron effective mass is meff,s=3.3me,and the phase diagram of the reduced surface has theα(fcc)structure as in the bulk.In PCO a double layer is predicted to be formed between the surface and the bulk with the surface being negatively charged and semiconducting.The surface of PCO maintains high Pr^(3+) defect concentration as well as relative high oxygen vacancy concentration at oxygen pressures higher than in the bulk.The reasons for the difference between a metallic and semiconducting surface layer of acceptor doped CeO_(2) are reviewed,as well as the key theoretical considerations applied in coping with this problem.For that we make use of the experimental data and theoretical analysis available for acceptor doped ceria.展开更多
基金We acknowledge the National Natural Science Foundation of China(No.22275134)for fi nancial support.
文摘N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.
基金supported by the Guangxi Natural Science Fund for Distinguished Young Scholars(2024GXNSFFA010008)Shenzhen Science and Technology Program(JCYJ20230807112503008).
文摘Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atmospheric pollutant NO but also produces valuable ammonia(NH_(3)).Hence,through the synthesis and modification of Fe_(3)C nanocrystal cata-lysts,the as-obtained optimal sample of Fe_(3)C/C-900 was adopted as the NORR catalyst at ambient conditions.As a result,the Fe_(3)C/C-900 catalyst showed an NH_(3)Faraday efficiency of 76.5%and an NH_(3)yield rate of 177.5μmol·h^(-1)·cm^(-2)at the working potentials of-0.8 and-1.2 V versus reversible hydrogen electrode(vs.RHE),respectively.And it delivered a stable NORR activity during the electrolysis.Moreover,we attribute the high NORR properties of Fe_(3)C/C-900 to two aspects:one is the enhanced intrinsic activity of Fe_(3)C nanocrystals,including the lowering of the energy barrier of rate-limiting step(*NOH→*N)and the inhibition of hydrogen evolution;on the other hand,the favorable dispersion of active components,the effective adsorption of gaseous NO,and the release of liquid NH_(3)products facilitated by the porous carbon substrate.
文摘Electrochemical nitrate reduction(eNO_(3)RR)and nitric oxide reduction(eNORR)to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production,particularly within the recently proposed reverse artificial nitrogen cycle route:N_(2)→NO_(x)→NH_(3).Notably,experimental studies have demonstrated that eNORR exhibits superior performance over eNO_(3)RR on Cu6Sn5 catalysts.However,the fundamental mechanisms underlying this difference remain poorly understood.Herein,we performed systematic theoretical calculations to explore the reaction pathways,electronic structure effects,and potential-dependent Faradic efficiency associated with ammonia production via these two distinct electrochemical pathways(eNORR and eNO_(3)RR)on Cu6Sn5.By implementing an advanced‘adaptive electric field controlled constant potential(EFC-CP)’methodology combined with microkinetic modeling,we successfully reproduced the experimental observations and identified the key factors affecting ammonia production in both reaction pathways.It was found that eNORR outperforms eNO_(3)RR because it circumvents the ^(*)NO_(2) dissociation and ^(*)NO_(2) desorption steps,leading to distinct surface coverage of key intermediates between the two pathways.Furthermore,the reaction rates were found to exhibit a pronounced dependence on the surface coverage of ^(*)NO in eNORR and ^(*)NO_(2) in eNO_(3)RR.Specifically,the facile desorption of ^(*)NO_(2) on the Cu6Sn5 surface in eNO_(3)RR limits the attainable surface coverage of ^(*)NO,thereby impeding its performance.In contrast,the eNORR can maintain a high surface coverage of adsorbed ^(*)NO species,contributing to its enhanced ammonia production performance.These fundamental insights provide valuable guidance for the rational design of catalysts and the optimization of reaction routes,facilitating the development of more efficient,sustainable,and scalable techniques for ammonia production.
基金supported by the National Science and Technology Major Project(No.2016ZX05011-003)The Certificate of China Postdoctoral Science Foundation(No.2016M592241).
文摘Super high molecular weight copolymers of AM/NaA/AMPS were prepared by oxidation–reduction[OR-P(AM/NaA/AMPS)]and controlled radical polymerization[CR-P(AM/NaA/AMPS)].The resulting copolymers were fully characterized,and the reaction conditions for their preparation were optimized.OR-P(AM/NaA/AMPS),CR-P(AM/NaA/AMPS),and conventional partially hydrolyzed polyacrylamide(HPAM)in brine solution were comprehensively characterized by thermogravimetric analysis,scanning electron microscopy,atomic force microscopy,and dynamic light scattering.ORP(AM/NaA/AMPS)and CR-P(AM/NaA/AMPS)containing AMPS monomer showed better salt resistance,temperature tolerance,and viscosification property than the conventional HPAM polymer,making them more promising for enhanced oil recovery.Through comprehensive comparison and analysis,it was found that OR-P(AM/NaA/AMPS)was more conducive for high-temperature condition due to the existence of xanthone in OR-P(AM/NaA/AMPS).On the other hand,CR-P(AM/NaA/AMPS)was more suitable for high-mineral atmosphere,which could be attributed to its higher intrinsic viscosity.
基金financially supported by the National Natural Science Foundation of China (Nos. 11774171, 21805137 and11874220)the Fundamental Research Funds for the Central Universities (No. NT2020019)+1 种基金the Open Fund of Key Laboratory for Intelligent Nano Materials and Devices of the Ministry of Education(No. INMD-2020M03)the Priority Academic Program Development of Jiangsu Higher Education Institutions (No. KYZZ16-0165)。
文摘Porous metal nanostructures exhibit excellent catalytic properties due to their high surface-to-volume ratios and abundant catalytic active sites. However, it is still challenging to control nanopores density and structural features in a facile route and the preparation of porous alloy nanorods for catalytic application has not been well explored. In this work, we demonstrate a synthetic strategy to fabricate highly porous Au–Ag alloy nanorods(P-Au Ag NRs) by critically dealloying Ag atoms from homogeneous solid Au–Ag alloy nanorods(Au Ag NRs). Combining the merits of the tunable plasmonic properties of noble metal nanorods, excellent stabilities of alloys, and superior catalytic activities of porous structures, we use the P-Au Ag NRs as a Raman probe for the in situ monitoring of the catalytic oxidation of 3,3',5,5' tetramethylbenzidine(TMB) and reduction of 4-nitrothiophenol(4-NTP). We also compare their compositiondependent catalytic activities. The results show that P-Au Ag NRs possess superior chemical stability and higher catalytic activity than those of core-shell structures due to synergistic structural and chemical mechanisms. This strategy provides a predictive design approach for the next-generation alloy catalysts with high-performance.
文摘Mining activities have created great wealth, but they have also discharged large quantities of tailings. As an important source of heavy metal contamination, sulfide tailings are usually disposed of in open-air impoundments and thus are exposed to microbial oxidation. Microbial activities greatly enhance sulfide oxidation and result in the release of heavy metals and the precipitation of iron (oxy) hydroxides and sulfates. These secondary minerals in turn influence the mobility of dissolved metals and play important roles in the natural attenuation of heavy metals. Elucidating the microbe–mineral interactions in tailings will improve our understanding of the environmental consequence of mining activities.
基金The subject has been supported by Chinese National Advanced Technology 863 Project(Grant No.8632001AA31304)Chinese National 973 Project(Grant No.G19990330).
文摘The congruent tri-doped Mg:Mn:Fe:LiNbO 3 crystal has been grown by Czochralski method. Some crystal samples are reduced in Li 2CO 3 powder at 500 ℃ for 24 hours or oxidized for 10 hours at 1100 ℃ in Nb 2O 5 powder. Compared with As-grown Mg:Mn:Fe:LiNbO 3, the absorption edge in UV-Vis. absorption spectrum of the oxidized sample and the reduced shifts to the violet and the red, respectively. Reduction increases the absorption of crystals in visible light region. In two-wave coupling experiments, the writing time, maximum diffraction efficiency and the erasure time of crystal samples in the same conditions are determined. The results indicate that oxidation and reduction disposing has great effect on the holographic recording properties of these crystals. The reduced crystal exhibits the fastest response time of 160 s among the crystal series. The mechanism of post-disposing effect on the holographic recording properties of Mg:Mn:Fe:LiNbO 3 crystals are investigated.
基金supported by the National Science & Technology Pillar Program(2012BAF03B02)National Natural Science Foundation of China(21101085,U1162203)+3 种基金Natural Science Foundation of Liaoning Province(2015020196)Doctoral Fund of Shandong Province(BS2015HZ003)Fushun Science & Technology Program(FSKJHT 201423)Liaoning Excellent Talents Program in University(LJQ2012031)~~
文摘TiO2/γ-Al2O3 supported In/Ag catalysts were prepared by impregnation method,and investigated for NO reduction with CO as the reducing agent under lean burn conditions.The microscopic structure and surface properties of the catalysts were studied by N2 adsorption-desorption,X-ray diffraction,transmission electron microscopy,X-ray photoelectron spectroscopy,ultraviolet-visible spectroscopy,H2 temperature-programmed reduction and Fourier transform infrared spectroscopy.TiO2/γ-Al2O3 supported In/Ag is a good catalyst for the reduction of NO to N2.It displayed high dispersion,large amounts of surface active components and high NO adsorption capacity,which gave good catalytic performance and stability for the reduction of NO with CO under lean burn conditions.The silver species stabilized and improved the dispersion of the indium species.The introduction of TiO2 into the γ-Al2O3 support promoted NO adsorption and improved the dispersion of the indium species and silver species.
基金This research was funded by Discovery Grants from the Natural Sciences and Engineering Research Council of Canada(JL:RGPIN-2022-03958AC:RGPIN-2022-04238).
文摘This feature article illustrates the potential of polarization modulation infrared reflection absorption spectroscopy(PM IRRAS)to provide molecular-level information about the structure,orientation and conformation of constituents of thin films at electrode surfaces.PM IRRAS relies on the surface selection rules stating that the p-polarized IR beam is enhanced,while the s-polarized beam is attenuated at the metal surface.The difference between p-and s-polarized beams eliminates the background of the solvent and provides IR spectra at a single electrode potential.In contrast,two other popular in situ IR spectroscopic techniques,namely,subtractively normalized interfacial Fourier transform infrared spectroscopy(SNIFTIRS)and surface-enhanced infrared reflection absorption spectroscopy(SEIRAS),provide potential difference spectra to remove the signal from the bulk solution.In this feature article,we provide a brief tutorial on how to run the PM IRRAS experiment and describe the methods used for background elimination first.The application of the PM IRRAS in the biomimetic research is then illustrated by three examples:construction of a tethered bilayer,reconstitution of colicin into a phospholipid bilayer and determination of the orientation of nucleolipids in a monolayer assembled at a gold electrode surface.Finally,the structural changes of graphene oxide during its electrochemical reduction are described to highlight the promising application of PM IRRAS in materials science.
文摘A laboratory incubation experiment was conducted to investigate nitrous oxide(N 2O) emission and reduction in a paddy soil(Stagnic Anthrosol) response to the pretreatment of water regime. The paddy soil was maintained under either air dried(sample D) or submerged(sample F) conditions for 110 d before the soil was adjusted into soil moisture of 20%, 40%, 60%, 80% and 100% water holding capacity(WHC) respectively, and then incubated with or without 10%(v/v) acetylene for 138 h at 25℃. At lower soil water content (≤60% WHC), N 2O emission from the sample F was 2 29 times higher than that from the sample D( P <0 01). While, N 2O emission from the sample F was only 29 and 14 percent of that from the sample D at the soil moisture of 80% and 100% WHC, respectively( P <0 01). The maximal N 2O emissions observed at soil moisture of 80% WHC were about 24 and 186 times higher than the minima obtained at the soil moisture of 20% WHC for the sample F and D, respectively. But at the soil moisture of 80% and 100% WHC, N 2O emission from the sample F with acetylene(F+ACE) was comparable to that of the sample D with acetylene (D+ACE). The results showed that the F sample produced N 2O ability in denitrification was similar to the sample D, however, the sample F was in the better reduction of N 2O to N 2 than the sample D even after the soil moisture was adjusted into the same level of 80% or 100% WHC. Therefore, the pretreatment of water regime influenced the strength and product composition of denitrification and N 2O emission from the paddy soil.
基金Funded by the Fundamental Research Funds for the Central Universities(No.310827151063)the Provincial Training Program of Innovation and Entrepreneurship for Undergraduates(No.201510710134)
文摘A great amount of red mud generated from alumina production by Bayer process was considered as a low-grade iron ore with a grade of 5wt% to 30wt% iron.We adopted the reduction roastingmagnetic separation process to recover ferric oxide from red mud.The red mud samples were processed by reduction roasting,grinding and magnetic separating respectively.The effects of different parameters on the recovery rate of iron were studied in detail.The optimum techqicalparameters were proposed with 700 ℃roasting for 20 min,as 50wt% carbon and 4wt% additive were added.The experimentalresults indicated that the iron recovery and the grade of totaliron were 91% and 60%,respectively.A novelprocess is applicable to recover ferric oxide from the red mud waste fines.
基金supported by the Consejo de Desarrollo Científico y Humanístico of La Universidad del Zulia (CONDES-LUZ CC-0090-12)Fondo Nacional de Ciencia, Tecnología e Innovación (FONACIT N° 2011001345)
文摘The catalytic activity of Pd catalysts supported on Ce0.73Tb0.27Ox/SiO2, Ce0.6Zr0.4Ox/Si O2,Ce0.73Tb0.27Ox/La2O3–Al2O3and Ce0.6Zr0.4Ox/La2O3–Al2O3was studied using the reduction of NO by CO. The catalysts were characterized by X-ray fluorescence, surface area, X-ray diffraction, temperature-programmed reduction, CO chemisorption and oxygen storage capacity. Temperature-programmed reduction results indicated that Tb or Zr incorporation improves the reducibility and oxygen storage capacity. CO chemisorption data suggested the presence of large Pd O particles due to the low CO/Pd ratio. No significant differences were obtained in light off temperatures（T Light off） for all Pd catalysts and the most active was1.5%Pd/Ce0.6Zr0.4Ox/SiO2.
文摘As the emission control regulations get stricter,the NO;reduction in the sintering process becomes an important environmental concern owing to its role in the formation of photochemical smog and acid rain.The NOxemissions from the sintering machine account for 48% of total amount from the iron and steel industry.Thus,it is essential to reduce NO;emissions from the sintering machine,for the achievement of clean production of sinter.Ca-Fe oxides,serving as the main binding phase in the sinter,are therefore used as additives into the sintering mixture to reduce NOxemissions.The results show that the NO;reduction ratio achieves 27.76% with 8% Ca-Fe oxides additives since the Ca-Fe oxides can advance the ignition and inhibit the nitrogen oxidation compared with the conventional condition.Meanwhile,the existence of Ca-Fe oxides was beneficial to the sinter quality since they were typical low melting point compounds.The optimal mass fraction of Ca-Fe oxides additives should be less than 8%since the permeability of sintering bed was significantly decreased with a further increase of the Ca-Fe oxides fines,inhibiting the mineralization reaction of sintering mixture.Additionally,the appropriate particle size can be obtained when mixing an equal amount of Ca-Fe oxides additives of-0.5 mm and 0.5-3.0 mm in size.
文摘The hydrogen reduction of tungsten oxides WO_(2.90),W_(20)O_(58) and WO_3 were directly studied using high temperature X-ray diffraction analysis.The differences between tetragonal WO_(2.90) and monoclinic W_(20)O_(58) were discussed.Pure β-W was obtained from oxide WO_(2.90),while there appears small amount of WO_2 during the reduction of W_(20)O_(58) to β-W.
基金financially supported by the major Project of the national science and technology of China (No. SQ2017YFGX010248)the Beijing Natural Science Foundation (No. 2172011)
文摘Niobium oxide nanowire-deposited carbon fiber（CF） samples were prepared using a hydrothermal method with amorphous Nb2O5·nH2O as precursor. The physical properties of the samples were characterized by means of numerous techniques, including X-ray diffraction（XRD）, energy-dispersive spectroscopy（EDS）, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, selected-area electron diffraction（SAED）, UV–visible spectroscopy（UV–vis）, N2 adsorption–desorption, Fourier transform infrared spectroscopy（FT-IR）, and X-ray photoelectron spectroscopy. The efficiency for the removal of Cr（VI） was determined.Parameters such as pH value and initial Cr（VI） concentration could influence the Cr（VI） removal efficiency or adsorption capacity of the Nb2O5/carbon fiber sample obtained after hydrothermal treatment at 160°C for 14 hr. The maximal Cr（VI） adsorption capacity of the Nb2O5 nanowire/CF sample was 115 mg/g. This Nb2O5/CF sample also showed excellent photocatalytic activity and stability for the reduction of Cr（Ⅵ） under UV-light irradiation： the Cr（VI） removal efficiency reached 99.9% after UV-light irradiation for 1 hr and there was no significant decrease in photocatalytic performance after the use of the sample for 10 repeated cycles. Such excellent Cr（VI） adsorption capacity and photocatalytic performance was related to its high surface area,abundant surface hydroxyl groups, and good UV-light absorption ability.
文摘The hydrogen reduction of tungsten oxides WO_(272)and WO_2 were studied directly using high-temperature X-ray diffraction analysis,The pure β-W was obtained from the reduction of WO_(272)The transformation of β-W to x-W was also studied in both hydrogen and nitrogen.The forming condition of β-W from WO_2 was discussed.Finally.a complete schematic diagram of reduction of tungsten oxides was given in this paper.
文摘Activity of three-way palladium catalyst was examined by means of a pulse-flam-microreactor. The effects of cerium on the catalytic properties of gamma-alumina-supported palladium for the reduction of nitric oxide were studied with X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR). The reduction of nitric oxide on palladium catalysts is inhibited significantly by hydrocarbon. However, the reduction of nitric oxide was improved by the addition of cerium to the catalysts. The XPS and TPR studies showed that the presence of cerium provided, palladium oxide in a hard-reduced state and suppressed the chemisorption of hydrocarbons on the palladium oxide. Additionally,cerium could increase surface specific oxygen storage capacity and decrease the apparent activation energy for the rea;ltion CO+NO-->CO2-+-1/2 N-2. So a high conversion of NOx reduction could shift to higher A/F ratio.
基金financially supported by the National Natural Science Foundation of China(Nos.21307142 and 21403261)Ningbo Science and Technology Bureau(No.2014D10004)
文摘The functionalization of multi-walled carbon nanotubes （MWCNTs） by ozone treatment has been sys- tematically investigated by using Raman spectroscopy, transmission electron microscopy （TEM）, Fourier transform inhared spectroscopy （FTIR）, X-ray photoelectron spectroscopy （XPS）, organic elemental anal- ysis （OEA） and Boehm titration. The results showed that the functionalization process occurred at defective sites （opened mouths, tube caps, debris, etc.） before opening caps and truncating walls, and finally the graphitic structure was deteriorated. The surface oxygen content first increased with the treatment time but kept at around 8.0 wt% after 5 h. The analysis of the distribution of oxygen-containing groups re- vealed that phenolic hydroxyl was gradually converted to carboxyl and lactone, The carboxyl was found to play a pivotal role to reduce the over-potentials when we used the functionalized MWCNTs as the cat- alyst for oxygen reduction reaction （ORR）.
基金the Natural Science Foundation of China(Nos.21021001,21072134 and J1103315/J0104)for financial support
文摘The （COCl）2/Hantzsch ester is found to be an effective system for the metal-free reduction of tertiary phosphine oxides. The reaction proceeds under mild conditions, and is applicable to triarylphosphine oxides and alkyldiarylphosphine oxides to produce the corresponding tertiary phosphines in good to excellent yields. This new finding provides a practical, convenient and metal-free method for the reduction of tertiary phosphine oxides to tertiary phosphines, and shows potential application in organic synthesis.
基金financially supported by the Technion V.P.for Research Fund(No.2023320)。
文摘The monomolecular surface layer of acceptor doped CeO_(2) may become neutral and metallic or charged and semiconducting.This is revealed in the theoretical analysis of the oxygen pressure dependence of the surface defects concentration in acceptor doped ceria with two different dopant types and operated under different oxygen pressures.Recently published experimental data for highly reduced Sm0.2Ce0.8O1.9-x(SDC)containing a fixed valence dopant Sm3+are very different from those published for Pr0.1Ce0.9O_(2)-x(PCO) with the variable valence dopant Pr4+/Pr3+being reduced under milder conditions.The theoretical analysis of these experimental results fits very well the experimental results of SDC and PCO.It leads to the following predictions:the highly reduced surface of SDC is metallic and neutral,the metallic surface electron density of state is gs=0.9×10^(38)J-1·m^(-2)(1.4×1015eV^(-1)·cm^(-2)),the electron effective mass is meff,s=3.3me,and the phase diagram of the reduced surface has theα(fcc)structure as in the bulk.In PCO a double layer is predicted to be formed between the surface and the bulk with the surface being negatively charged and semiconducting.The surface of PCO maintains high Pr^(3+) defect concentration as well as relative high oxygen vacancy concentration at oxygen pressures higher than in the bulk.The reasons for the difference between a metallic and semiconducting surface layer of acceptor doped CeO_(2) are reviewed,as well as the key theoretical considerations applied in coping with this problem.For that we make use of the experimental data and theoretical analysis available for acceptor doped ceria.
