A cost-efficient and stable oxygen evolution electrocatalyst is essential for improving energy storage and conversion efficiencies. Herein, 2D nanosheets with randomly cross-linked CoNi layered double hydroxide （LDH...A cost-efficient and stable oxygen evolution electrocatalyst is essential for improving energy storage and conversion efficiencies. Herein, 2D nanosheets with randomly cross-linked CoNi layered double hydroxide （LDH） and small CoO nanocrystals were designed and synthesized via in situ reduction and interface- directed assembly in air. The formation of CoNi LDH/CoO nanosheets was attributed to the strong extrusion of hydrated metal-oxide clusters driven by the interfacial tension. The obtained loose and porous nanosheets exhibited low crystallinity due to the presence of numerous defects. Owing to the orbital hybridization between metal 3d and O 2p orbitals, and electron transfer between metal atoms through Ni-O-Co, a number of Co and Ni atoms in the CoNi LDH present a high ＋3 valency. These unique characteristics result in a high density of oxygen evolution reaction （OER） active sites, improving the affinity between OH- and catalyst, and resulting in a large accessible surface area and permeable channels for ion adsorption and transport. Therefore, the resulting nanosheets exhibited high catalytic activity towards the OER. The CoNi LDH/CoO featured a low onset potential of 1.48 V in alkaline medium, and required an overpotential of only 300 mV at a current density of 10 mA.cm-2, while displaying good stability in accelerated durability tests.展开更多
Inductively coupled plasma mass spectrometry （ICP-MS） is the most commonly used technique to deter- mine the abundances of trace elements in a wide range of geological materials. However, incomplete sample digestion...Inductively coupled plasma mass spectrometry （ICP-MS） is the most commonly used technique to deter- mine the abundances of trace elements in a wide range of geological materials. However, incomplete sample digestion, isobaric interferences and instrumental drift remain obvious problems that must be overcome in order to obtain precise and accurate results, For this reason, we have done many experi- ments and developed a set of simple, cost-effective and practical methods widely applicable for precise and rapid determination of trace element abundances in geological materials using ICP-MS. Commonly used high-pressure digestion technique is indeed effective in decomposing refractory phases, but this inevitably produces fluoride complexes that create new problems. We demonstrate that the fluoride complexes formed during high-pressure digestion can be readily re-dissolved using high-pressure vessel at 190 ℃ for only 2 h for 50 mg sample. In the case of isobaric interferences, although oxide （e.g., MO^＋/M^＋） and hydroxide （e.g., MO^＋/M^＋） productivity is variable between runs, the （MO^＋/M^＋）/（CeO^＋/Ce^＋） and （MOH^＋/M^＋）/（CeO^＋/Ce^＋） ratios remain constant, making isobaric interference correction for all other elements of interest straightforward, for which we provide an easy-to-use off-line procedure. We also show that mass-time-intensity drift curve is smooth as recognized previously, for which the correction can be readily done by analyzing a quality-control （QC） solution and using off-line Excel VBA procedure without internal standards. With these methods, we can produce data in reasonable agreement with rec- ommended values of international rock reference standards with a relative error of 〈8% and precision generally better than 5%. Importantly, compared to the widely used analytical practice, we can effectively save 〉60% of time （e.g., 〈24 h vs. 〉60 h）.展开更多
One of the major obstacles for the clinical use of biodegradable magnesium(Mg)-based materials is their high corrosion rate. Micro-arc oxidation(MAO) coatings on Mg alloys provide mild corrosion protection owing to th...One of the major obstacles for the clinical use of biodegradable magnesium(Mg)-based materials is their high corrosion rate. Micro-arc oxidation(MAO) coatings on Mg alloys provide mild corrosion protection owing to their porous structure. Hence, in this study a dense Mg(OH)2 film was fabricated on MAO-coated Mg alloy AZ31 in an alkaline electrolyte containing ethylenediamine tetraacetic acid disodium(EDTA-2 Na) to reinforce the protection. Surface morphology, chemical composition and growth process of the MAO/Mg(OH)2 hybrid coating were examined using field-emission scanning electron microscopy, energy dispersive X-ray spectrometer, X-ray diffraction, X-ray photoelectron spectroscopy and Fourier transform infrared spectrophotometer. Corrosion resistance of the coatings was evaluated via potentiodynamic polarization curves and hydrogen evolution tests. Results manifested that the Mg(OH)2 coating possesses a porous nano-sized structure and completely seals the micro-pores and micro-cracks of the MAO coating.The intermetallic compound of AlMn phase in the substrate plays a key role in the growth of Mg(OH)2 film. The current density of Mg(OH)2-MAO composite coating decreases three orders of magnitude in comparison with that of bare substrate, indicating excellent corrosion resistance. The Mg(OH)2-MAO composite coating is beneficial to the formation of calcium phosphate corrosion products on the surface of Mg alloy AZ31, demonstrating a great promise for orthopaedic applications.展开更多
To further enhance the corrosion resistance of the porous micro-arc oxidation(MAO) ceramic layers on AZ31 magnesium alloy, superhydrophobic Mg-Al layered double hydroxide(LDH) coating was fabricated on MAO-coated AZ31...To further enhance the corrosion resistance of the porous micro-arc oxidation(MAO) ceramic layers on AZ31 magnesium alloy, superhydrophobic Mg-Al layered double hydroxide(LDH) coating was fabricated on MAO-coated AZ31 alloy by using in-situ growth method followed by surface modification with stearic acid. The characteristics of different coatings were investigated by XRD, SEM and EDS. The effect of the hydrothermal treatment time on the formation of the LDH coatings was studied. The results demonstrated that the micro-pores and cracks of MAO coating were gradually sealed via in-situ growing LDH with prolonging hydrothermal treating time. Electrochemical measurement displayed that the lowest corrosion current density, the most positive corrosion potential and the highest impedance modulus were observed for superhydrophobic LDH/MAO coating compared with those of MAO coating and LDH/MAO coating. Immersion experiment proved that the superhydrophobic LDH/MAO coating with the active anti-corrosion capability significantly enhanced the long-term corrosion protection for MAO coated alloy.展开更多
Polyvinyl alcohol is a refractory compound widely used in industry. Here we report supercritical water oxidation of polyvinyl alcohol solution and desizing wastewater with and without sodium hydroxide addition. Howeve...Polyvinyl alcohol is a refractory compound widely used in industry. Here we report supercritical water oxidation of polyvinyl alcohol solution and desizing wastewater with and without sodium hydroxide addition. However, it is difficult to implement complete degradation of organics even though polyvinyl alcohol can readily crack under supercritical water treatment. Sodium hydroxide had a significant catalytic effect during the supercritical water oxidation of polyvinyl alcohol. It appears that the OH ion participated in the C-C bond cleavage of polyvinyl alcohol molecules, the CO2-capture reaction and the neutralization of intermediate organic acids, promoting the overall reactions moving in the forward direction. Acetaldehyde was a typical intermediate product during reaction. For supercritical water oxidation of desizing wastewater, a high destruction rate （98.25%） based on total organic carbon was achieved. In addition, cases where initial wastewater was alkaline were favorable for supercritical water oxidation treatment, but salt precipitation and blockage issues arising during the process need to be taken into account seriously.展开更多
Layered double hydroxide(LDH) has been widely developed in the field of corrosion and protection in recent years based on its unique characteristics including anion capacity, anion exchange ability, structure memory e...Layered double hydroxide(LDH) has been widely developed in the field of corrosion and protection in recent years based on its unique characteristics including anion capacity, anion exchange ability, structure memory effect, and barrier resistance. This paper comprehensively reviews recent work on the preparations, properties of LDH in the forms of powder and film and their applications in different environments in corrosion and protection. Some novel perspectives are also proposed at the end of the review for future research in corrosion and protection field.展开更多
The objective of the present study is to characterize the production of hydrogen with a sorptionenhanced steam-methane reaction process using Ca(OH)2 as the CO2 adsorbent. Theoretical equilibrium compositions at diffe...The objective of the present study is to characterize the production of hydrogen with a sorptionenhanced steam-methane reaction process using Ca(OH)2 as the CO2 adsorbent. Theoretical equilibrium compositions at different operation conditions were calculated using an iterative method. It was found that with Ca(OH)2 as the CO2 sorbent, the concentration of CO2 adsorption was reduced in the product stream, that gave rise to higher methane conversion and higher H2 concentration. An experimental setup was built to test the theoretical calculation. The effects of sorbents and the particle size of Ca(OH)2 on the concentration of CO2 and H2 were investigated in detail. Results showed that the reactor packed with catalyst and Ca(OH)2 particles produced H2 concentration of 94%. It was nearly 96% of the theoretical equilibrium limit, much higher than H2 equilibrium concentration of 67.5% without CO2 sorption under the same conditions of 500℃, 0.2 MPa pressure and a steam-to-methane ratio 6. In addition, the residual mole fraction of CO2 was less than 0.001.展开更多
Photocatalytic CO2 reduction holds promise as a future technology for the manufacture of fuels and commodity chemicals.However,factors controlling product selectivity remain poorly understood.Herein,we compared the pe...Photocatalytic CO2 reduction holds promise as a future technology for the manufacture of fuels and commodity chemicals.However,factors controlling product selectivity remain poorly understood.Herein,we compared the performance of a homologous series of Zn-based layered double hydroxide(ZnM-LDH)photocatalysts for CO2 reduction.By varying the trivalent or tetravalent metal cations in the ZnM-LDH photocatalysts(M=Ti4+,Fe3+,Co3+,Ga3+,Al3+),the product selectivity of the reaction could be precisely controlled.ZnTi-LDH afforded CH4 as the main reduction product;ZnFe-LDH and ZnCo-LDH yielded H2 exclusively from water splitting;whilst ZnGa-LDH and ZnAl-LDH generated CO.In-situ diffuse reflectance infrared measurements,valence band XPS and density function theory calculations were applied to rationalize the CO2 reduction selectivities of the different ZnM-LDH photocatalysts.The analyses revealed that the d-band center(ed)position of the M3+or M4+cations controlled the adsorption strength of CO2 and thus the selectivity to carbon-containing products or H2.Cations with d-band centers relatively close to the Fermi level(Ti4+,Ga3+and Al3+)adsorbed CO2 strongly yielding CH4 or CO,whereas metal cations with d-band centers further from the Fermi level(Fe3+and Co3+)adsorbed CO2 poorly,thereby yielding H2 only(from water splitting).Our findings clarify the role of trivalent and tetravalent metal cations in LDH photocatalysts for the selective CO2 reduction,paving new ways for the development of improved LDH photocatalyst with high selectivities to specific products.展开更多
Basically,Mg–Al layered double hydroxide(LDH)coatings are prepared on the surface of micro-arc oxidation(MAO)coated magnesium(Mg)alloys at a high temperature or a low pH value.This scenario leads to the growth rate o...Basically,Mg–Al layered double hydroxide(LDH)coatings are prepared on the surface of micro-arc oxidation(MAO)coated magnesium(Mg)alloys at a high temperature or a low pH value.This scenario leads to the growth rate of LDH coating inferior to the dissolution rate of the MAO coating.This in turn results in limited corrosion resistance of the composite coating.In this study,a Mg–Al LDH coating on MAO-coated Mg alloy AZ31 is prepared through a water bath with a higher pH(13.76)at a lower temperature(60℃).FE-SEM,EDS,XRD,XPS,and FT-IR are applied to analyze the surface morphology,chemical compositions,and growth process.Electrochemical polarization,electrochemical impedance spectroscopy(EIS)and hydrogen evolution tests are employed to evaluate the corrosion resistance of the samples.The results disclose that the MAO coating is completely covered by the nanosheet-structured LDH coating with a thickness of approximately 3.8μm.The corrosion current density of the MAO-LDH composite coating is decreased four orders of magnitude in comparison to its substrate;the presence of a wide passivation region in anodic polarization branch demonstrates its strong self-healing ability,indicating the hybrid coating possesses excellent corrosion resistance.The formation mechanism of the LDH coating on the MAO-coated Mg alloy is proposed.Furthermore,the cytocompatibility is assessed via an indirect extraction test for MC3T3-E1 pre-osteoblasts,which indicates an acceptable cytocompatibility of osteoblasts for the composite coating.展开更多
Seawater electrolysis is an extremely attractive approach for harvesting clean hydrogen energy,but detrimental chlorine species(i.e.,chloride and hypochlorite)cause severe corrosion at the anode.Here,we report our rec...Seawater electrolysis is an extremely attractive approach for harvesting clean hydrogen energy,but detrimental chlorine species(i.e.,chloride and hypochlorite)cause severe corrosion at the anode.Here,we report our recent finding that benzoate anions-intercalated NiFe-layered double hydroxide nanosheet on carbon cloth(BZ-NiFe-LDH/CC)behaves as a highly efficient and durable monolithic catalyst for alkaline seawater oxidation,affords enlarged interlayer spacing of LDH,inhibits chlorine(electro)chemistry,and alleviates local pH drop of the electrode.It only needs an overpotential of 320 mV to reach a current density of 500 mA·cm^(−2)in 1 M KOH.In contrast to the fast activity decay of NiFe-LDH/CC counterpart during long-term electrolysis,BZ-NiFe-LDH/CC achieves stable 100-h electrolysis at an industrial-level current density of 500 mA·cm^(−2)in alkaline seawater.Operando Raman spectroscopy studies further identify structural changes of disorderedδ(NiIII-O)during the seawater oxidation process.展开更多
Rational design and controlled fabrication of efficient and cost-effective electrodes for the oxygen evolution reaction （OER） are critical for addressing the unpre- cedented energy crisis. Nickel-iron layered double...Rational design and controlled fabrication of efficient and cost-effective electrodes for the oxygen evolution reaction （OER） are critical for addressing the unpre- cedented energy crisis. Nickel-iron layered double hydroxides （NiFe-LDHs） with specific interlayer anions （i.e. phosphate, phosphite, and hypophosphite） were fabricated by a co-predpitation method and investigated as oxygen evolution electrocatalysts. Intercalation of the phosphorus oxoanion enhanced the OER activity in an alkaline solution; the optimal performance （i.e., a low onset potential of 215 mV, a small Tafel slope of 37.7 mV/dec, and stable electrochemical behavior） was achieved with the hypophosphite-intercalated NiFe-LDH catalyst, demonstrating dramatic enhancement over the traditional carbonate-intercalated NiFe-LDH in terms of activity and durability. This enhanced performance is attributed to the interaction between the intercalated phosphorous oxoanions and the edge-sharing MO6 （M = Ni, Fe） layers, which modifies the surface electronic structure of the Ni sites. This concept should be inspiring for the design of more effective LDH-based oxygen evolution electrocatalvsts.展开更多
The effect of the amount of precipitant ammonia on the Cu0/Cu＋ratio of Cu/Si O2 prepared by the deposition–precipitation method is investigated. Species at different preparation stages, resulted from the amount of a...The effect of the amount of precipitant ammonia on the Cu0/Cu＋ratio of Cu/Si O2 prepared by the deposition–precipitation method is investigated. Species at different preparation stages, resulted from the amount of ammonia used, are identified by the XRD and FTIR techniques. Chrysocolla together with either copper nitrate hydroxide or copper hydroxide coexist in the uncalcined catalysts. Upon calcination, the latter two species are converted to Cu O particles while chrysocolla remains. Following reduction, Cu O is transformed to metallic Cu and chrysocolla is converted to Cu2 O. The value of Cu0/Cu＋ratio can be evaluated using the peak areas in their TPR profiles. Hydrogenation of dimethyl oxalate（DMO） to ethylene glycol（EG） shows that the selectivity of EG depends on the Cu0/Cu＋ratio. Catalyst prepared with the addition of ammonia solution at n（NH3）/n（Cu2＋） = 0.9 for precipitation–deposition gains a more suitable Cu0/Cu＋ratio upon reduction and thus has a higher selectivity for EG.展开更多
Bioreduction as a novel nanoparticle synthesizing technology attracts increasing attention. Dried cells of the bacterium Aeromonas sp. SH10 rapidly reduced [Ag（NH3）2]^＋ to Ago in the solution into which some amount...Bioreduction as a novel nanoparticle synthesizing technology attracts increasing attention. Dried cells of the bacterium Aeromonas sp. SH10 rapidly reduced [Ag（NH3）2]^＋ to Ago in the solution into which some amount of OH^- was introduced. The surface plasmon resonance centered at 425 nm on the UV-vis spectra and five broad Bragg reflections on the XRD pattern showed that stable silver nanoparticles were formed during the bioreduction process. TEM and SEM observations suggested that the silver nanoparticles were uniform in size and well dispersed on the cells and in the solution. Therefore, silver nanoparticles could be prepared rapidly by this bioreduction technology.展开更多
Composite solid base catalysts derived from Ca‐M‐Al(M=Mg,La,Ce,Y)layered double hydroxides(LDH)were synthesized,characterized and applied to the transesterification of methanol with propylene carbonate.X‐ray diffra...Composite solid base catalysts derived from Ca‐M‐Al(M=Mg,La,Ce,Y)layered double hydroxides(LDH)were synthesized,characterized and applied to the transesterification of methanol with propylene carbonate.X‐ray diffraction analyses of the catalysts show that all of the catalysts were in the form of composite oxides.Compared with the Ca‐Al LDH catalyst,the specific surface areas and pore volumes of the catalysts were increased with the introduction of Mg,La or Ce.The catalytic performance of these catalysts increases in the order of Ca‐Y‐Al<Ca‐Al<Ca‐Ce‐Al<Ca‐La‐Al<Ca‐Mg‐Al,which is consistent with the total surface basic amounts of these materials and the formation of especially strong basic sites following modification with Mg and La.The Ca‐Mg‐Al catalyst shows the highest(Ca+Mg):Al atomic ratio,indicating that it likely contains more unsaturated O2?ions,providing it with the highest concentration of very strong basic sites.The recyclability of these catalysts is improved following the addition of Mg,La,Ce or Y,with the Ca‐Mg‐Al maintaining a high level of activity after ten recycling trials.X‐ray diffraction analyses of fresh and used Ca‐Mg‐Al demonstrate that this catalyst is exceptionally stable,which could be of value in practical applications related to heterogeneous catalysis.展开更多
A series of activated carbons from Taixi anthracite were prepared by steam activation in the presence of KOH and then they were modified by different methods. The regulation of porosity and the modification of surface...A series of activated carbons from Taixi anthracite were prepared by steam activation in the presence of KOH and then they were modified by different methods. The regulation of porosity and the modification of surface chemistry were carried out with the aim to improve the benzene adsorption capacity of activated carbon. The influences of KOH and activation process parameters including activation temperature, activation time and steam flow rate on porosity of activated carbon were evaluated, and the effect of modification methods on surface chemistry was investigated. Also, the relationship between benzene adsorption capacity and porosity and surface chemistry was analyzed. Results show that activation temperature is the dominant factor in the activation process; the introduction of KOH into the raw material can enhance the reactivity of char in activation process, meanwhile it shows a negative effect on the porosity development, especially on the mesopore development. Results of FTIR analysis indicate that anthracite-based activated carbon with condensed aromatics and chemically inert oxygen does not present the nature to be surface modified. Besides, benzene adsorption capacity has an approximate linear relationship with surface area and in our preparation, benzene adsorption capacity and surface area of activated carbon are up to 1210 m 2 /g and 423 mg/g, respectively.展开更多
基金We gratefully acknowledge the support of this research by the Key Program Projects of the National Natural Science Foundation of China （No. 21031001）, the National Natural Science Foundation of China （Nos. 21371053 and 21573062）, the Cultivation Fund of the Key Scientific and Technical Innovation Project, Program for Innovative Research Team in University （No. IRT-1237）, Application Technology Research and Development Projects in Harbin （No. 2013AE4BW051）, International Science ＆ Technology Cooperation Program of China （No. 2014DFR41110）, and the Foundation of Heilongjiang Province of China （No. QC2013C009）.
文摘A cost-efficient and stable oxygen evolution electrocatalyst is essential for improving energy storage and conversion efficiencies. Herein, 2D nanosheets with randomly cross-linked CoNi layered double hydroxide （LDH） and small CoO nanocrystals were designed and synthesized via in situ reduction and interface- directed assembly in air. The formation of CoNi LDH/CoO nanosheets was attributed to the strong extrusion of hydrated metal-oxide clusters driven by the interfacial tension. The obtained loose and porous nanosheets exhibited low crystallinity due to the presence of numerous defects. Owing to the orbital hybridization between metal 3d and O 2p orbitals, and electron transfer between metal atoms through Ni-O-Co, a number of Co and Ni atoms in the CoNi LDH present a high ＋3 valency. These unique characteristics result in a high density of oxygen evolution reaction （OER） active sites, improving the affinity between OH- and catalyst, and resulting in a large accessible surface area and permeable channels for ion adsorption and transport. Therefore, the resulting nanosheets exhibited high catalytic activity towards the OER. The CoNi LDH/CoO featured a low onset potential of 1.48 V in alkaline medium, and required an overpotential of only 300 mV at a current density of 10 mA.cm-2, while displaying good stability in accelerated durability tests.
基金supported by National Natural Science Foundation of China(41130314 and 41630968)Chinese Academy of Sciences Innovation Grant(Y42217101L)+1 种基金Qingdao National Laboratory for Marine Science and Technology(2015ASKJ03)Marine Geological Process and Environment(U1606401)
文摘Inductively coupled plasma mass spectrometry （ICP-MS） is the most commonly used technique to deter- mine the abundances of trace elements in a wide range of geological materials. However, incomplete sample digestion, isobaric interferences and instrumental drift remain obvious problems that must be overcome in order to obtain precise and accurate results, For this reason, we have done many experi- ments and developed a set of simple, cost-effective and practical methods widely applicable for precise and rapid determination of trace element abundances in geological materials using ICP-MS. Commonly used high-pressure digestion technique is indeed effective in decomposing refractory phases, but this inevitably produces fluoride complexes that create new problems. We demonstrate that the fluoride complexes formed during high-pressure digestion can be readily re-dissolved using high-pressure vessel at 190 ℃ for only 2 h for 50 mg sample. In the case of isobaric interferences, although oxide （e.g., MO^＋/M^＋） and hydroxide （e.g., MO^＋/M^＋） productivity is variable between runs, the （MO^＋/M^＋）/（CeO^＋/Ce^＋） and （MOH^＋/M^＋）/（CeO^＋/Ce^＋） ratios remain constant, making isobaric interference correction for all other elements of interest straightforward, for which we provide an easy-to-use off-line procedure. We also show that mass-time-intensity drift curve is smooth as recognized previously, for which the correction can be readily done by analyzing a quality-control （QC） solution and using off-line Excel VBA procedure without internal standards. With these methods, we can produce data in reasonable agreement with rec- ommended values of international rock reference standards with a relative error of 〈8% and precision generally better than 5%. Importantly, compared to the widely used analytical practice, we can effectively save 〉60% of time （e.g., 〈24 h vs. 〉60 h）.
基金supported by the National Natural Science Foundation of China(Nos.51571134 and 51601108)the SDUST Research Fund(No.2014TDJH104)
文摘One of the major obstacles for the clinical use of biodegradable magnesium(Mg)-based materials is their high corrosion rate. Micro-arc oxidation(MAO) coatings on Mg alloys provide mild corrosion protection owing to their porous structure. Hence, in this study a dense Mg(OH)2 film was fabricated on MAO-coated Mg alloy AZ31 in an alkaline electrolyte containing ethylenediamine tetraacetic acid disodium(EDTA-2 Na) to reinforce the protection. Surface morphology, chemical composition and growth process of the MAO/Mg(OH)2 hybrid coating were examined using field-emission scanning electron microscopy, energy dispersive X-ray spectrometer, X-ray diffraction, X-ray photoelectron spectroscopy and Fourier transform infrared spectrophotometer. Corrosion resistance of the coatings was evaluated via potentiodynamic polarization curves and hydrogen evolution tests. Results manifested that the Mg(OH)2 coating possesses a porous nano-sized structure and completely seals the micro-pores and micro-cracks of the MAO coating.The intermetallic compound of AlMn phase in the substrate plays a key role in the growth of Mg(OH)2 film. The current density of Mg(OH)2-MAO composite coating decreases three orders of magnitude in comparison with that of bare substrate, indicating excellent corrosion resistance. The Mg(OH)2-MAO composite coating is beneficial to the formation of calcium phosphate corrosion products on the surface of Mg alloy AZ31, demonstrating a great promise for orthopaedic applications.
基金Project(17JS083) supported by the Key Laboratory Program of Shaanxi Education Department,ChinaProject(2016JZ018) supported by the Key Program of Natural Science Research of Shaanxi Province,ChinaProject(51701162) supported by the National Natural Science Foundation of China
文摘To further enhance the corrosion resistance of the porous micro-arc oxidation(MAO) ceramic layers on AZ31 magnesium alloy, superhydrophobic Mg-Al layered double hydroxide(LDH) coating was fabricated on MAO-coated AZ31 alloy by using in-situ growth method followed by surface modification with stearic acid. The characteristics of different coatings were investigated by XRD, SEM and EDS. The effect of the hydrothermal treatment time on the formation of the LDH coatings was studied. The results demonstrated that the micro-pores and cracks of MAO coating were gradually sealed via in-situ growing LDH with prolonging hydrothermal treating time. Electrochemical measurement displayed that the lowest corrosion current density, the most positive corrosion potential and the highest impedance modulus were observed for superhydrophobic LDH/MAO coating compared with those of MAO coating and LDH/MAO coating. Immersion experiment proved that the superhydrophobic LDH/MAO coating with the active anti-corrosion capability significantly enhanced the long-term corrosion protection for MAO coated alloy.
基金supported by the National High Technology Research and Development Program of China (No.2006AA06Z313)the Program for New Century Excellent Talents in University of Chinese Education Ministry (No.NCET-07-0678)the Opened Fund of Jiangsu Key Lab for Clean Energy and Power Machinery Engineering (No.QK08003)
文摘Polyvinyl alcohol is a refractory compound widely used in industry. Here we report supercritical water oxidation of polyvinyl alcohol solution and desizing wastewater with and without sodium hydroxide addition. However, it is difficult to implement complete degradation of organics even though polyvinyl alcohol can readily crack under supercritical water treatment. Sodium hydroxide had a significant catalytic effect during the supercritical water oxidation of polyvinyl alcohol. It appears that the OH ion participated in the C-C bond cleavage of polyvinyl alcohol molecules, the CO2-capture reaction and the neutralization of intermediate organic acids, promoting the overall reactions moving in the forward direction. Acetaldehyde was a typical intermediate product during reaction. For supercritical water oxidation of desizing wastewater, a high destruction rate （98.25%） based on total organic carbon was achieved. In addition, cases where initial wastewater was alkaline were favorable for supercritical water oxidation treatment, but salt precipitation and blockage issues arising during the process need to be taken into account seriously.
基金financially supported by the State Key Project of Research and Development (No. 2016YFC1100300)the National Natural Science Foundation of China (No. 21203158, 21773199, and 21621091)。
文摘Layered double hydroxide(LDH) has been widely developed in the field of corrosion and protection in recent years based on its unique characteristics including anion capacity, anion exchange ability, structure memory effect, and barrier resistance. This paper comprehensively reviews recent work on the preparations, properties of LDH in the forms of powder and film and their applications in different environments in corrosion and protection. Some novel perspectives are also proposed at the end of the review for future research in corrosion and protection field.
文摘The objective of the present study is to characterize the production of hydrogen with a sorptionenhanced steam-methane reaction process using Ca(OH)2 as the CO2 adsorbent. Theoretical equilibrium compositions at different operation conditions were calculated using an iterative method. It was found that with Ca(OH)2 as the CO2 sorbent, the concentration of CO2 adsorption was reduced in the product stream, that gave rise to higher methane conversion and higher H2 concentration. An experimental setup was built to test the theoretical calculation. The effects of sorbents and the particle size of Ca(OH)2 on the concentration of CO2 and H2 were investigated in detail. Results showed that the reactor packed with catalyst and Ca(OH)2 particles produced H2 concentration of 94%. It was nearly 96% of the theoretical equilibrium limit, much higher than H2 equilibrium concentration of 67.5% without CO2 sorption under the same conditions of 500℃, 0.2 MPa pressure and a steam-to-methane ratio 6. In addition, the residual mole fraction of CO2 was less than 0.001.
基金financial support from the National Key Projects for Fundamental Research and Development of China (2016YFB0600901, 2017YFA0206904, 2017YFA0206900, 2018YFB1502002)the National Natural Science Foundation of China (51825205, 51772305, 51572270, U1662118, 21871279, 21802154, 21902168)+10 种基金the Beijing Natural Science Foundation (2191002, 2182078, 2194089)the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17000000)the Royal Society-Newton Advanced Fellowship (NA170422)the International Partnership Program of Chinese Academy of Sciences (GJHZ1819, GJHZ201974)the Beijing Municipal Science and Technology Project (Z181100005118007)the K. C. Wong Education Foundationthe Young Elite Scientist Sponsorship Program by CAST (YESS)the Youth Innovation Promotion Association of the CASthe Energy Education Trust of New Zealandthe Mac Diarmid Institute for Advanced Materials and Nanotechnologythe Dodd Walls Centre for Photonic and Quantum Technologies。
文摘Photocatalytic CO2 reduction holds promise as a future technology for the manufacture of fuels and commodity chemicals.However,factors controlling product selectivity remain poorly understood.Herein,we compared the performance of a homologous series of Zn-based layered double hydroxide(ZnM-LDH)photocatalysts for CO2 reduction.By varying the trivalent or tetravalent metal cations in the ZnM-LDH photocatalysts(M=Ti4+,Fe3+,Co3+,Ga3+,Al3+),the product selectivity of the reaction could be precisely controlled.ZnTi-LDH afforded CH4 as the main reduction product;ZnFe-LDH and ZnCo-LDH yielded H2 exclusively from water splitting;whilst ZnGa-LDH and ZnAl-LDH generated CO.In-situ diffuse reflectance infrared measurements,valence band XPS and density function theory calculations were applied to rationalize the CO2 reduction selectivities of the different ZnM-LDH photocatalysts.The analyses revealed that the d-band center(ed)position of the M3+or M4+cations controlled the adsorption strength of CO2 and thus the selectivity to carbon-containing products or H2.Cations with d-band centers relatively close to the Fermi level(Ti4+,Ga3+and Al3+)adsorbed CO2 strongly yielding CH4 or CO,whereas metal cations with d-band centers further from the Fermi level(Fe3+and Co3+)adsorbed CO2 poorly,thereby yielding H2 only(from water splitting).Our findings clarify the role of trivalent and tetravalent metal cations in LDH photocatalysts for the selective CO2 reduction,paving new ways for the development of improved LDH photocatalyst with high selectivities to specific products.
基金supported by the National Natural Science Foundation of China(No.51571134)the SDUST Research Fund(No.2014TDJH104).
文摘Basically,Mg–Al layered double hydroxide(LDH)coatings are prepared on the surface of micro-arc oxidation(MAO)coated magnesium(Mg)alloys at a high temperature or a low pH value.This scenario leads to the growth rate of LDH coating inferior to the dissolution rate of the MAO coating.This in turn results in limited corrosion resistance of the composite coating.In this study,a Mg–Al LDH coating on MAO-coated Mg alloy AZ31 is prepared through a water bath with a higher pH(13.76)at a lower temperature(60℃).FE-SEM,EDS,XRD,XPS,and FT-IR are applied to analyze the surface morphology,chemical compositions,and growth process.Electrochemical polarization,electrochemical impedance spectroscopy(EIS)and hydrogen evolution tests are employed to evaluate the corrosion resistance of the samples.The results disclose that the MAO coating is completely covered by the nanosheet-structured LDH coating with a thickness of approximately 3.8μm.The corrosion current density of the MAO-LDH composite coating is decreased four orders of magnitude in comparison to its substrate;the presence of a wide passivation region in anodic polarization branch demonstrates its strong self-healing ability,indicating the hybrid coating possesses excellent corrosion resistance.The formation mechanism of the LDH coating on the MAO-coated Mg alloy is proposed.Furthermore,the cytocompatibility is assessed via an indirect extraction test for MC3T3-E1 pre-osteoblasts,which indicates an acceptable cytocompatibility of osteoblasts for the composite coating.
基金supported by the National Natural Science Foundation of China(No.21575137).
文摘Seawater electrolysis is an extremely attractive approach for harvesting clean hydrogen energy,but detrimental chlorine species(i.e.,chloride and hypochlorite)cause severe corrosion at the anode.Here,we report our recent finding that benzoate anions-intercalated NiFe-layered double hydroxide nanosheet on carbon cloth(BZ-NiFe-LDH/CC)behaves as a highly efficient and durable monolithic catalyst for alkaline seawater oxidation,affords enlarged interlayer spacing of LDH,inhibits chlorine(electro)chemistry,and alleviates local pH drop of the electrode.It only needs an overpotential of 320 mV to reach a current density of 500 mA·cm^(−2)in 1 M KOH.In contrast to the fast activity decay of NiFe-LDH/CC counterpart during long-term electrolysis,BZ-NiFe-LDH/CC achieves stable 100-h electrolysis at an industrial-level current density of 500 mA·cm^(−2)in alkaline seawater.Operando Raman spectroscopy studies further identify structural changes of disorderedδ(NiIII-O)during the seawater oxidation process.
文摘Rational design and controlled fabrication of efficient and cost-effective electrodes for the oxygen evolution reaction （OER） are critical for addressing the unpre- cedented energy crisis. Nickel-iron layered double hydroxides （NiFe-LDHs） with specific interlayer anions （i.e. phosphate, phosphite, and hypophosphite） were fabricated by a co-predpitation method and investigated as oxygen evolution electrocatalysts. Intercalation of the phosphorus oxoanion enhanced the OER activity in an alkaline solution; the optimal performance （i.e., a low onset potential of 215 mV, a small Tafel slope of 37.7 mV/dec, and stable electrochemical behavior） was achieved with the hypophosphite-intercalated NiFe-LDH catalyst, demonstrating dramatic enhancement over the traditional carbonate-intercalated NiFe-LDH in terms of activity and durability. This enhanced performance is attributed to the interaction between the intercalated phosphorous oxoanions and the edge-sharing MO6 （M = Ni, Fe） layers, which modifies the surface electronic structure of the Ni sites. This concept should be inspiring for the design of more effective LDH-based oxygen evolution electrocatalvsts.
基金Funding for the present study from the National Basic Research Program of China(973 Program,No.2011CB710800)the Opening Foundation(2014)of Zhejiang Zanyu Technology Co.,Ltd
文摘The effect of the amount of precipitant ammonia on the Cu0/Cu＋ratio of Cu/Si O2 prepared by the deposition–precipitation method is investigated. Species at different preparation stages, resulted from the amount of ammonia used, are identified by the XRD and FTIR techniques. Chrysocolla together with either copper nitrate hydroxide or copper hydroxide coexist in the uncalcined catalysts. Upon calcination, the latter two species are converted to Cu O particles while chrysocolla remains. Following reduction, Cu O is transformed to metallic Cu and chrysocolla is converted to Cu2 O. The value of Cu0/Cu＋ratio can be evaluated using the peak areas in their TPR profiles. Hydrogenation of dimethyl oxalate（DMO） to ethylene glycol（EG） shows that the selectivity of EG depends on the Cu0/Cu＋ratio. Catalyst prepared with the addition of ammonia solution at n（NH3）/n（Cu2＋） = 0.9 for precipitation–deposition gains a more suitable Cu0/Cu＋ratio upon reduction and thus has a higher selectivity for EG.
基金Supported by the National Natural Science Foundation of China (No.20376076).
文摘Bioreduction as a novel nanoparticle synthesizing technology attracts increasing attention. Dried cells of the bacterium Aeromonas sp. SH10 rapidly reduced [Ag（NH3）2]^＋ to Ago in the solution into which some amount of OH^- was introduced. The surface plasmon resonance centered at 425 nm on the UV-vis spectra and five broad Bragg reflections on the XRD pattern showed that stable silver nanoparticles were formed during the bioreduction process. TEM and SEM observations suggested that the silver nanoparticles were uniform in size and well dispersed on the cells and in the solution. Therefore, silver nanoparticles could be prepared rapidly by this bioreduction technology.
基金supported by the Natural Science Foundation of Shanxi Province(201601D102006)the Key Science and Technology Program of Shanxi Province,China(MD2014-09,MD2014-10)~~
文摘Composite solid base catalysts derived from Ca‐M‐Al(M=Mg,La,Ce,Y)layered double hydroxides(LDH)were synthesized,characterized and applied to the transesterification of methanol with propylene carbonate.X‐ray diffraction analyses of the catalysts show that all of the catalysts were in the form of composite oxides.Compared with the Ca‐Al LDH catalyst,the specific surface areas and pore volumes of the catalysts were increased with the introduction of Mg,La or Ce.The catalytic performance of these catalysts increases in the order of Ca‐Y‐Al<Ca‐Al<Ca‐Ce‐Al<Ca‐La‐Al<Ca‐Mg‐Al,which is consistent with the total surface basic amounts of these materials and the formation of especially strong basic sites following modification with Mg and La.The Ca‐Mg‐Al catalyst shows the highest(Ca+Mg):Al atomic ratio,indicating that it likely contains more unsaturated O2?ions,providing it with the highest concentration of very strong basic sites.The recyclability of these catalysts is improved following the addition of Mg,La,Ce or Y,with the Ca‐Mg‐Al maintaining a high level of activity after ten recycling trials.X‐ray diffraction analyses of fresh and used Ca‐Mg‐Al demonstrate that this catalyst is exceptionally stable,which could be of value in practical applications related to heterogeneous catalysis.
基金the financial support by the Special Fund for Basic Scientific Research of Central Colleges (No.2009KH10)the Beijing Postdoctoral Fund (No. B148)the Green Shoots Plan of Beijing Academy of Science and Technology of China (No. B142)
文摘A series of activated carbons from Taixi anthracite were prepared by steam activation in the presence of KOH and then they were modified by different methods. The regulation of porosity and the modification of surface chemistry were carried out with the aim to improve the benzene adsorption capacity of activated carbon. The influences of KOH and activation process parameters including activation temperature, activation time and steam flow rate on porosity of activated carbon were evaluated, and the effect of modification methods on surface chemistry was investigated. Also, the relationship between benzene adsorption capacity and porosity and surface chemistry was analyzed. Results show that activation temperature is the dominant factor in the activation process; the introduction of KOH into the raw material can enhance the reactivity of char in activation process, meanwhile it shows a negative effect on the porosity development, especially on the mesopore development. Results of FTIR analysis indicate that anthracite-based activated carbon with condensed aromatics and chemically inert oxygen does not present the nature to be surface modified. Besides, benzene adsorption capacity has an approximate linear relationship with surface area and in our preparation, benzene adsorption capacity and surface area of activated carbon are up to 1210 m 2 /g and 423 mg/g, respectively.
