钒基催化剂中V价态的电化学方法测定
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摘要
在电解液pH=1.0、扫描电压-0.6～0.9 V、灵敏度1 mA、扫描速率0.05 V/s的条件下,用循环伏安法测得V_2O_5、VO_2及V_2O_3的CV曲线,以出现的还原电位作为标准参数,对比钒基催化剂在CV曲线中的还原电位。测试结果表明:MgV_2O_4和V-Mg/β催化剂中的V以V~(3+)存在,丙烷-氧处理后的V-Mg/β催化剂中V~(3+)活性减弱,出现了V~(5+)的还原峰,表明丙烷-氧处理过程中部分V~(3+)转化为V~(5+)。
The cyclic voltammetry(CV) curves of vanadium oxides, V_2O_3, VO_2 and V_2O_5 were measured with scanning voltage of-0.6～0.9 V, sensitivity of 1 mA and scanning rate of 0.05 V/s under electrolyte pH=1.0. The reduction potentials recorded for these vanadium oxides in CV curves were used as standard parameters in the study of the valance state of vanadium in vanadium-based catalysts. The reduction potentials of the vanadium-based catalysts in the CV curves indicate that the vanadium is presented as V~(3+) both in the MgV_2O_4 and V-Mg/β catalysts. After treating with propane-oxygen, the activity of V~(3+) in V-Mg/β catalyst decreases meanwhile a reduction peak of V~(5+) appears, indicating that part of the V~(3+) is converted into the V~(5+) during the propane-oxygen treatment.
The cyclic voltammetry(CV) curves of vanadium oxides, V_2O_3, VO_2 and V_2O_5 were measured with scanning voltage of-0.6～0.9 V, sensitivity of 1 mA and scanning rate of 0.05 V/s under electrolyte pH=1.0. The reduction potentials recorded for these vanadium oxides in CV curves were used as standard parameters in the study of the valance state of vanadium in vanadium-based catalysts. The reduction potentials of the vanadium-based catalysts in the CV curves indicate that the vanadium is presented as V~(3+) both in the MgV_2O_4 and V-Mg/β catalysts. After treating with propane-oxygen, the activity of V~(3+) in V-Mg/β catalyst decreases meanwhile a reduction peak of V~(5+) appears, indicating that part of the V~(3+) is converted into the V~(5+) during the propane-oxygen treatment.
引文
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[14] 段钱花,王森林,王丽品.电沉积多孔复合Ni-P/LaNi5电极及其析氢电催化性能[J].物理化学学报,2013,29(1):123-130.DUAN Q H,WANG S L,WANG L P.Electro-deposition of the porous composite Ni-P/LaNi5 electrode and its electro-Catalytic performance toward hydrogen evolution reaction[J].Acta Physico-Chimica Sinica,2013,29(1):123-130.
[15] 谢中,刘业翔.铽氧化物电极表面的XPS和电化学循环伏安分析[J].中国稀土学报,2000(3):216-219.XIE Z,LIU Y X.XPS and cyclic voltammetric surface characterization of Tb Oxide electrocatalysts[J].Journal of the Chinese Society of Rare Earths,2000(3):216-219.
[16] 徐松.提高钒渣制取五氧化二钒浸出率的实验及机理研究[D].重庆:重庆大学,2014.XUE S.The experimental and mechanism reseach of improving the leaching ratio of vanadium[D].Chongqing:Chongqing University,2014.
[2] 照日格图,李文钊,于春英,等.丙烷选择氧化制丙烯醛研究进展[J].天然气化工,2000(3):50-54.ZHAORI G T,LI W Z,YU C Y,et al.The progress in research of selective oxidation of propane to acrolein[J].Natural Gas Chemical Industry,2000(3):50-54.
[3] 方智敏,翁维正,万惠霖,等.丙烷氧化脱氢VMgO催化剂活性位的研究[J].厦门大学学报(自然科学版),1998(4):61-67.FANG Z M,WENG W Z,WAN H L,et al.Study on active sites of VMgO catalysts for oxidative dehydrogenation of propane[J].Journal of Xiamen University(Natural Science),1998(4):61-67.
[4] ALBONETTI S,CAVANI F,TRIFIRO F,et al.Key aspects of catalyst design for the selective oxidation of paraffins[J].Catalysis Review,1996,38(4):413-438
[5] 徐秀峰,张蓬洲.用XPS表征氧、氮、硫元素的存在形态[J].煤炭转化,1996(1):72-77.XU X F,ZHANG P Z.The XPS study of forms of oxygen,nitrogen and sulphur elements in gas coal[J].Coal Conversion,1996(1):72-77.
[6] 章连香,符斌.X-射线荧光光谱分析技术的发展[J].中国无机分析化学,2013,3(3):1-7.ZHANG L X,FU B.Advances in X-ray fluorescence spectrometry[J].Chinese Journal of Inorganic Analytical Chemistry,2013,3(3):1-7.
[7] 屈凌波,郁有祝,郭玉华.金的电化学价态分析和定量测定研究[J].黄金,2009,30(5):43-45.QU L B,YU Y Z,GUO Y H.Valence analysis and quantitative determination of gold by electrochemical method[J].Gold,2009,30(5):43-45.
[8] 陆晓华,蔡乾涛,余红兵,等.尿液中不同价态硒的吸附溶出伏安法测定[J].环境科学,1993(3):65-68,94-95.LU X H,CAI Q T,YU H B,et al.Speciation of selenium in Urine by adsorptive stripping voltammetric method[J].Environmental Science,1993(3):65-68,94-95.
[9] 王雪飞,赵思晴,杨丹,等.循环伏安法在新型电化学传感器中的应用[J].云南化工,2018,45(1):137-138.WANG X F,ZHAO S Q,YANG D,et al.Application of cyclic voltammetry in novel electrochemical sensors[J].Yunnan Chemical Technology,2018,45(1):137-138.
[10] 齐济.钒氧化物及其复合玻璃的制备与性质研究[D].大连:大连理工大学,2008.QI J.Preparation and Properties of vanadium oxides and their composite glasses[D].Dalian University of Technology,2008.
[11] 高晓霞.电化学分析导论[M].北京:北京科学出版社,2010.GAO X X,et al.Introduction to Electroanalytical Chemistry[M].Beijing Science Press,2010.
[12] ANDREW T.Gunman,Maple Heights et al.Preparation of vanadium III oxidic compounds,and dehydrogenation of paraffins.United States Patent [19],Patent Number:4,737,355.Apr.12,1988.
[13] 郑朋,唐艳辉,余玲,等.V/β-分子筛和V/γ-Al2O3催化剂上丙烷氧化脱氢制丙烯[J].北京服装学院学报(自然科学版),2016,36(4):77-84.ZHENG P,TANG Y H,YU L,et al.Oxidative dehydrogenation of propane to propene on V/β and V/γ-Al2O3[J].Journal of Beijing Institute of Clothing Technology(Natural Science Edition),2016,36(4):77-84.
[14] 段钱花,王森林,王丽品.电沉积多孔复合Ni-P/LaNi5电极及其析氢电催化性能[J].物理化学学报,2013,29(1):123-130.DUAN Q H,WANG S L,WANG L P.Electro-deposition of the porous composite Ni-P/LaNi5 electrode and its electro-Catalytic performance toward hydrogen evolution reaction[J].Acta Physico-Chimica Sinica,2013,29(1):123-130.
[15] 谢中,刘业翔.铽氧化物电极表面的XPS和电化学循环伏安分析[J].中国稀土学报,2000(3):216-219.XIE Z,LIU Y X.XPS and cyclic voltammetric surface characterization of Tb Oxide electrocatalysts[J].Journal of the Chinese Society of Rare Earths,2000(3):216-219.
[16] 徐松.提高钒渣制取五氧化二钒浸出率的实验及机理研究[D].重庆:重庆大学,2014.XUE S.The experimental and mechanism reseach of improving the leaching ratio of vanadium[D].Chongqing:Chongqing University,2014.