Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and on...Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and only a limited candidates have been reported so far.In this work,we found for the first time that a continuous solid solution,Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2)(0≤α≤1,could be obtained by mutual substitution of cations at center‐symmetric Na3 and Na4 sites while keeping the crystal building blocks of anionic P_(2)O_(7) unchanged.In particular,a novel off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)is thus proposed,and its structure,energy storage mechanism,and electrochemical performance are extensively investigated to unveil the structure–function relationship.The as‐prepared off‐stoichiometric electrode delivers appealing performance with a reversible discharge capacity of 83 mAh g^(−1),a working voltage of 2.9 V(vs.Na^(+)/Na),the retention of 89.2%of the initial capacity after 500 cycles,and enhanced rate capability of 51 mAh g^(−1)at a current density of 1600 mA g^(−1).This research shows that sodium ferric pyrophosphate could form extended solid solution composition and promising phase is concealed in the range of Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2),offering more chances for exploration of new cathode materials for the construction of high‐performance SIBs.展开更多
The microwave radiation method was introduced to prepare the Fe_2O_3/SO solid superacid.Its structure and properties were investigated by means of X-ray diffraction and infrared spectrum analyses as well as measuremen...The microwave radiation method was introduced to prepare the Fe_2O_3/SO solid superacid.Its structure and properties were investigated by means of X-ray diffraction and infrared spectrum analyses as well as measurement of magnetic susceptibility and rate of esterification. The structure of the superacids prepared in microwave field can be crystalline or non-crystalline, the latter has not been reported yet in literatures. Comparing with the traditional superacid, the non-crystalline Fe2O3/SO superacid prepared in microwave field has the highest magnetic susceptibility and catalytic activity. The di-coordination of Fe2O3 and SO and the S=O bi-bond were reinforced by microwave radiation, which is favorable for increasing the acid intensity of the Fe2O3/SO catalyst展开更多
Tungstated zirconia(WO_(3)/ZrO_(2))solid acid catalysts with different WO_(3) contents were prepared by a hydrothermal method and then used in the catalytic aquathermolysis of heavy oil from Xinjiang.The WO_(3)/ZrO_(2...Tungstated zirconia(WO_(3)/ZrO_(2))solid acid catalysts with different WO_(3) contents were prepared by a hydrothermal method and then used in the catalytic aquathermolysis of heavy oil from Xinjiang.The WO_(3)/ZrO_(2) solid acid catalyst was characterized by a range of characterization methods,including X-ray diffraction,NH3-temperature programmed desorption,and pyridine infrared spectroscopy.The WO_(3) content of the WO_(3)/ZrO_(2) catalysts had an important impact on the structure and property of the catalysts.When the WO_(3) mass fraction was 20%,it facilitated the formation of tetragonal zirconia,thereby enhancing the creation of robust acidic sites.Acidity is considered to have a strong impact on the catalytic performance of the aquathermolysis of heavy oil.When the catalyst containing 20%WO_(3) was used to catalyze the aquathermolysis of heavy oil under conditions of 14.5 MPa,340℃,and 24 h,the viscosity of heavy oil decreased from 47266 to 5398 mPa·s and the viscosity reduction rate reached 88.6%.The physicochemical properties of heavy oil before and after the aquathermolysis were analyzed using a saturates,aromatics,resins,and asphaltenes analysis,gas chromatography,elemental analysis,densimeter etc.After the aquathermolysis,the saturate and aromatic contents significantly increased from 43.3%to 48.35%and 19.47%to 21.88%,respectively,with large reductions in the content of resin and asphaltene from 28.22%to 25.06%and 5.36%to 2.03%,respectively.The sulfur and nitrogen contents,and the density of the oil were significantly decreased.These factors were likely the main reasons for promoting the viscosity reduction of heavy oil during the aquathermolysis over the WO_(3)/ZrO_(2) solid acid catalysts.展开更多
Alumina supports modified by lanthanum （La） and barium （Ba） were prepared by peptization. Catalysts with different KOH contents supported on modified alumina were prepared by impregnation method. Various technique...Alumina supports modified by lanthanum （La） and barium （Ba） were prepared by peptization. Catalysts with different KOH contents supported on modified alumina were prepared by impregnation method. Various techniques, including N2 adsorption-desorption （Brunauer-Emmet-Teller method, BET）, X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and fourier transform infrared absorption spectroscopy （FT-IR）. Catalytic activity for microalgae oil conversion to methyl ester via transesterification was evaluated and analyzed by GC-MS and GC. BET results showed that the support possessed high specific surface area, suitable pore volume and pore size distribution. Activity results indicated that the catalyst with 25 wt% KOH showed the best activity for microalgae oil conversion. XRD and SEM results revealed that Al-O-K compound was the active phase for microalgae oil conversion. The agglomeration and changing of pore structure should be the main reasons for the catalyst deactivation when KOH content was higher than 30 wt%.展开更多
Waste selective catalytic reduction(SCR)catalysts are potential environmental hazards.In this study,the recovery of vanadium and tungsten from waste SCR catalysts by K_(2)CO_(3)roasting and water leaching was investig...Waste selective catalytic reduction(SCR)catalysts are potential environmental hazards.In this study,the recovery of vanadium and tungsten from waste SCR catalysts by K_(2)CO_(3)roasting and water leaching was investigated.The roasting and leaching conditions were optimized:the leaching efficiencies of vanadium and tungsten were 91.19%and 85.36%,respectively,when 18 equivalents of K_(2)CO_(3)were added to perform the roasting at 900℃ for 2 h,followed by leaching at 90°C for 1 h.Notably,in the described conditions,the leaching rate of silicon was only 28.55%.Titanates,including K_(2)Ti_(6)O_(13)and KTi8017,were also produced.Si removal was achieved in 85%efficiency adjusting the pH to 9.5,and the Si impurity thus isolated was composed of amorphous Si.Tungsten and vanadium were precipitated using CaCl_(2).At pH 10 and following the addition of 0.10 mol of H_(2)O_(2)and 16 equivalents of CaCl_(2),the precipitating efficiencies of tungsten and vanadium were 96.89%and 99.65%,respectively.The overall yield of tungsten and vanadium was 82.71%and 90.87%,respectively.展开更多
A β”/β-Al_2O_3 solid electrolyte was prepared and used in a Na conentration galvanic cell: (-)O_2(in Ar),SnO_2,Na_2SnO_3|β"/β-Al_2O_3]NaCrO_2,Cr_2O_3,O_2(in Ar)(+).The emf measurements were carried out in te...A β”/β-Al_2O_3 solid electrolyte was prepared and used in a Na conentration galvanic cell: (-)O_2(in Ar),SnO_2,Na_2SnO_3|β"/β-Al_2O_3]NaCrO_2,Cr_2O_3,O_2(in Ar)(+).The emf measurements were carried out in temperature range of 912—1223 K:E=652.1— 0.2092 T+2.3(mV).Using this equation and cited free energies of formation of NaCrO_2, Cr_2O_3 and SnO_2,the molar free energy of formation of Na_2 SnO_3 may be calculated by ΔG°=-1050+0.2544 T±5.4(kJ mol^(-1)).展开更多
Stable and high‐efficiency bifunctional catalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desired for the practical application of Li‐O_(2)batteries with excellent rate performanc...Stable and high‐efficiency bifunctional catalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desired for the practical application of Li‐O_(2)batteries with excellent rate performance and cycle stability.Herein,a novel hybrid bifunctional catalyst with carbon nanofibers inlaid with hollow Co_(3)O_(4)nanoparticles and separate active sites for ORR and OER were prepared and applied in Li‐O_(2)batteries.Benefiting from the synergistic effect of unique porous structural features and high electrocatalytic activity of hollow Co3O4 intimately bound to N‐doped carbon nanofibers,the assembled Li‐O_(2)batteries with novel catalyst exhibited high specific capacity,excellent rate capability,and cycle stability up to 150 cycles under a capacity limitation of 500 mAh g^(–1)at a current density of 100 mA g^(–1).The facile synthesis and preliminary results in this work show the as‐prepared catalyst as a promising bifunctional electrocatalyst for applications in metal‐air batteries,fuel cells,and electrocatalysis.展开更多
基金National Natural Science Foundation of China,Grant/Award Numbers:21972108,U20A20249,U22A20438Changzhou Science and Technology Bureau,Grant/Award Number:CM20223017Innovation and Technology Commission(ITC)of Hong Kong,The Innovation&Technology Fund(ITF)with Project No.ITS/126/21。
文摘Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and only a limited candidates have been reported so far.In this work,we found for the first time that a continuous solid solution,Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2)(0≤α≤1,could be obtained by mutual substitution of cations at center‐symmetric Na3 and Na4 sites while keeping the crystal building blocks of anionic P_(2)O_(7) unchanged.In particular,a novel off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)is thus proposed,and its structure,energy storage mechanism,and electrochemical performance are extensively investigated to unveil the structure–function relationship.The as‐prepared off‐stoichiometric electrode delivers appealing performance with a reversible discharge capacity of 83 mAh g^(−1),a working voltage of 2.9 V(vs.Na^(+)/Na),the retention of 89.2%of the initial capacity after 500 cycles,and enhanced rate capability of 51 mAh g^(−1)at a current density of 1600 mA g^(−1).This research shows that sodium ferric pyrophosphate could form extended solid solution composition and promising phase is concealed in the range of Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2),offering more chances for exploration of new cathode materials for the construction of high‐performance SIBs.
文摘The microwave radiation method was introduced to prepare the Fe_2O_3/SO solid superacid.Its structure and properties were investigated by means of X-ray diffraction and infrared spectrum analyses as well as measurement of magnetic susceptibility and rate of esterification. The structure of the superacids prepared in microwave field can be crystalline or non-crystalline, the latter has not been reported yet in literatures. Comparing with the traditional superacid, the non-crystalline Fe2O3/SO superacid prepared in microwave field has the highest magnetic susceptibility and catalytic activity. The di-coordination of Fe2O3 and SO and the S=O bi-bond were reinforced by microwave radiation, which is favorable for increasing the acid intensity of the Fe2O3/SO catalyst
基金the financial support from the Open Fund Project of the National Oil Shale Exploitation Research and Development Center,China(No.33550000-22-ZC0613-0255)the Graduate Student Innovation and Practical Ability Training Program of Xi’an Shiyou University(No.YCS23213098)+3 种基金the National Natural Science Foundation of China(No.52274039)the Natural Science Basic Research Plan in Shaanxi Province of China(Program No.2024JC-YBMS-085)the CNPC Innovation Found(No.2022DQ02-0402)The authors also thank the Modern Analysis and Test Center of Xi’an Shiyou University for their help with the characterization of catalysts and analysis of products.
文摘Tungstated zirconia(WO_(3)/ZrO_(2))solid acid catalysts with different WO_(3) contents were prepared by a hydrothermal method and then used in the catalytic aquathermolysis of heavy oil from Xinjiang.The WO_(3)/ZrO_(2) solid acid catalyst was characterized by a range of characterization methods,including X-ray diffraction,NH3-temperature programmed desorption,and pyridine infrared spectroscopy.The WO_(3) content of the WO_(3)/ZrO_(2) catalysts had an important impact on the structure and property of the catalysts.When the WO_(3) mass fraction was 20%,it facilitated the formation of tetragonal zirconia,thereby enhancing the creation of robust acidic sites.Acidity is considered to have a strong impact on the catalytic performance of the aquathermolysis of heavy oil.When the catalyst containing 20%WO_(3) was used to catalyze the aquathermolysis of heavy oil under conditions of 14.5 MPa,340℃,and 24 h,the viscosity of heavy oil decreased from 47266 to 5398 mPa·s and the viscosity reduction rate reached 88.6%.The physicochemical properties of heavy oil before and after the aquathermolysis were analyzed using a saturates,aromatics,resins,and asphaltenes analysis,gas chromatography,elemental analysis,densimeter etc.After the aquathermolysis,the saturate and aromatic contents significantly increased from 43.3%to 48.35%and 19.47%to 21.88%,respectively,with large reductions in the content of resin and asphaltene from 28.22%to 25.06%and 5.36%to 2.03%,respectively.The sulfur and nitrogen contents,and the density of the oil were significantly decreased.These factors were likely the main reasons for promoting the viscosity reduction of heavy oil during the aquathermolysis over the WO_(3)/ZrO_(2) solid acid catalysts.
基金supported by the Institute of Chemical Materials Foundation of CAEP(No.626010937)
文摘Alumina supports modified by lanthanum （La） and barium （Ba） were prepared by peptization. Catalysts with different KOH contents supported on modified alumina were prepared by impregnation method. Various techniques, including N2 adsorption-desorption （Brunauer-Emmet-Teller method, BET）, X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and fourier transform infrared absorption spectroscopy （FT-IR）. Catalytic activity for microalgae oil conversion to methyl ester via transesterification was evaluated and analyzed by GC-MS and GC. BET results showed that the support possessed high specific surface area, suitable pore volume and pore size distribution. Activity results indicated that the catalyst with 25 wt% KOH showed the best activity for microalgae oil conversion. XRD and SEM results revealed that Al-O-K compound was the active phase for microalgae oil conversion. The agglomeration and changing of pore structure should be the main reasons for the catalyst deactivation when KOH content was higher than 30 wt%.
基金from the Fundamental Research Funds for the Central Universities(2010YH14).
文摘Waste selective catalytic reduction(SCR)catalysts are potential environmental hazards.In this study,the recovery of vanadium and tungsten from waste SCR catalysts by K_(2)CO_(3)roasting and water leaching was investigated.The roasting and leaching conditions were optimized:the leaching efficiencies of vanadium and tungsten were 91.19%and 85.36%,respectively,when 18 equivalents of K_(2)CO_(3)were added to perform the roasting at 900℃ for 2 h,followed by leaching at 90°C for 1 h.Notably,in the described conditions,the leaching rate of silicon was only 28.55%.Titanates,including K_(2)Ti_(6)O_(13)and KTi8017,were also produced.Si removal was achieved in 85%efficiency adjusting the pH to 9.5,and the Si impurity thus isolated was composed of amorphous Si.Tungsten and vanadium were precipitated using CaCl_(2).At pH 10 and following the addition of 0.10 mol of H_(2)O_(2)and 16 equivalents of CaCl_(2),the precipitating efficiencies of tungsten and vanadium were 96.89%and 99.65%,respectively.The overall yield of tungsten and vanadium was 82.71%and 90.87%,respectively.
文摘A β”/β-Al_2O_3 solid electrolyte was prepared and used in a Na conentration galvanic cell: (-)O_2(in Ar),SnO_2,Na_2SnO_3|β"/β-Al_2O_3]NaCrO_2,Cr_2O_3,O_2(in Ar)(+).The emf measurements were carried out in temperature range of 912—1223 K:E=652.1— 0.2092 T+2.3(mV).Using this equation and cited free energies of formation of NaCrO_2, Cr_2O_3 and SnO_2,the molar free energy of formation of Na_2 SnO_3 may be calculated by ΔG°=-1050+0.2544 T±5.4(kJ mol^(-1)).
文摘Stable and high‐efficiency bifunctional catalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desired for the practical application of Li‐O_(2)batteries with excellent rate performance and cycle stability.Herein,a novel hybrid bifunctional catalyst with carbon nanofibers inlaid with hollow Co_(3)O_(4)nanoparticles and separate active sites for ORR and OER were prepared and applied in Li‐O_(2)batteries.Benefiting from the synergistic effect of unique porous structural features and high electrocatalytic activity of hollow Co3O4 intimately bound to N‐doped carbon nanofibers,the assembled Li‐O_(2)batteries with novel catalyst exhibited high specific capacity,excellent rate capability,and cycle stability up to 150 cycles under a capacity limitation of 500 mAh g^(–1)at a current density of 100 mA g^(–1).The facile synthesis and preliminary results in this work show the as‐prepared catalyst as a promising bifunctional electrocatalyst for applications in metal‐air batteries,fuel cells,and electrocatalysis.
