单、双层钙钛矿型催化剂的制备及化学与物理性能比较
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摘要
采用以柠檬酸和葡萄糖为络合剂的溶胶-凝胶法制备了钙钛矿型复合氧化物LaSrBMnO_6(B=Fe、Co)、LaSrCoFeO_6；La_(0．5)Sr_(0．5)BO_3(B=Fe、Co、Mn)；La-B-Ti-O(B=Mg、Ca、Sr、Co)和La-Co-V-O、La_2CoMnO_6、La_2MnVO_6等四个系列的催化剂，运用XRD、TPR、FT-IR、BET、TEM、电导率和磁性等对其性质进行了表征，并考察了在甲烷燃烧反应中的催化性能。
实验结果表明，在5H_2％／95％N_2气氛氛围中1100℃焙烧3h后，催化剂LaSrBMnO_6(B=Fe，Co)和LaSrCoFeO_6均生成了单相物相。其中，LaSrCoFeO_6对甲烷催化燃烧的起燃温度最低为460℃，完全转化温度为673℃；反应温度在500-650℃之间催化剂LaSrFeMnO_6对甲烷催化燃烧活性最好；催化剂LaSrCoMnO_6对甲烷燃烧催化活性最差。在室温下电导测试发现LaSrFeMnO_6的导电性最好，催化剂LaSrCoFeO_6的导电性最差。
对几种单、双钙钛矿进行了化学与物理性能的比较，在三种催化剂LaSrCoFeO_6、La_(0．5)Sr_(0．5)CoO_3和La_(0．5)Sr_(0．5)FeO_3中，LaSrCoFeO_6对甲烷燃烧的催化活性最好，在测试温度范围内，LaSrCoFeO_6的导电性最差；在三种催化剂LaSrCoMnO_6、La_(0．5)Sr_(0．5)MnO_3和La_(0．5)Sr_(0．5)CoO_3中，La_(0．5)Sr_(0．5)MnO_3对甲烷燃烧的催化活性最好，在测试温度范围内其导电性也最好；在三种催化剂LaSrFeMnO_6、La_(0．5)Sr_(0．5)MnO_3和La_(0．5)Sr_(0．5)FeO_3中，La_(0．5)Sr_(0．5)MnO_3对甲烷燃烧的催化活性最好，在测试温度范围内，催化剂LaSrFeMnO_6的导电性最好。
采用柠檬酸作络合剂的溶胶-凝胶法制备的三种催化剂La_2CoMnO_6、La_2MnVO_6和La-Co-V-O，在5H_2％／95％N_2气氛氛围中1100℃焙烧3h后制备单相双钙钛矿型催化剂La_2CoMnO_6和La_2MnVO_6，而体系La-Co-V-O没有得到单相物相。同时，对比两种催化剂LaSrCoMnO_6和La_2CoMnO_6对甲烷催化燃烧的活性及其磁性。
以葡萄糖作络合剂的溶胶-凝胶法制备催化剂La-B-Ti-O(B=Mg、Ca、Sr、Co)，在空气中1100℃焙烧3h后制备出单相双钙钛矿型催化剂La_2MgTiO_6，其它三种催化剂La-B-Ti-O(B=Ca、Sr、Co)没有得到单相物相。对催化剂La_2MgTiO_6进行不同焙烧温度的结构和性能比较，发现在500℃焙烧3h后即制得单相催化剂La_2MgTiO_6；而在800℃焙烧3h后，催化剂La_2MgTiO_6对甲烷催化燃烧活性最好。
The perovskite-type composite oxide LaSrBMnO_6(B=Fe、Co) ,LaSrCoFeO_6;La_(0.5)Sr_(0.5)BO_3(B=Fe、Co、Mn); La-B-Ti-O(B=Mg、Ca、Sr、Co) and La-Co-V-O、La_2CoMnO_6、La_2MnVO_6 were synthesized by the sol-gel method and characterized by means of XRD、TPR、BET、FT-IR、TEM、the catalytic activity evaluation、conductivity and magnetic properties.
We find that the single-phase perovskite-type oxides LaSrBMnO_6(B=Fe,Co), LaSrCoFeO_6 and La_(0.5)Sr_(0.5)BO_3(B=Fe,Co,Mn) were synthesized by the sol-gel using citric acid as complex agent. It is shown that LaSrFeMnO_6 showed a higher conductivity than LaSrCoMnO_6 and LaSrCoFeO_6 after 1100℃calcinations for 3h in 5H_2%/95%N_2. LaSrCoFeO_6 showed a better catalytic activity for methane combustion than LaSrBMnO_6(B=Fe,Co), which T_(10)(methane conversion of 10%) and T_(90)(methane conversion of 90 % ) were 460℃and 673℃respectively, and LaSrFeMnO_6 showed the best catalytic activity between 500-650℃.
The chemical and physical properties of several of the single, double perovskite-type oxides were compared under the same condition. In the first group, LaSrCoFeO_6, La_(0.5)Sr_(0.5)CoO_3and La_(0.5_Sr_(0.5)FeO_3, LaSrCoFeO_6 had the best catalytic activity for methane combustion but the worst conductivity. In the second group, LaSrCoMnO_6, La_(0.5)Sr_(0.5)MnO_3 and La_(0.5)Sr_(0.5)CoO_3, La_(0.5)Sr_(0.5)MnO_3 had the best catalytic activity and conductivity. In the third group, LaSrFeMnO_6,La_(0.5)Sr_(0.5)MnO_3 and La_(0.5)Sr_(0.5)FeO_3, La_(0.5)Sr_(0.5)MnO_3 had the best catalytic activity and LaSrFeMnO_6 had the best conductivity.
The La_2CoMnO_6, La_2MnVO_6 and La-Co-V-O were prepared by the sol-gel using citric acid as complex agent. The studies showed that single-phase perovskite-type oxides La_2CoMnO_6 and La_2MnVO_6 were synthesidzed after 1100℃calcinations for 3h in 5H_2%/95%N_2, but the system of La-Co-V-O was not synthesized single-phase. Meanwhile, we also compared catalytic activity for methane combustion and magnetic activity of LaSrCoMnO_6 and La_2CoMnO_6.
Four systems of perovskite-type composite oxides La-B-Ti-O(B=Mg,Ca,Sr,Co) were prepared by sol-gel using glucose as complex agent. Experimental results show that La-B-Ti-O(B=Ca、Sr、Co) were not synthesized single-phase perovskite-type oxides and the La_2MgTiO_6 was synthesized after 500℃calcinations for 3h in the air. The catalytic activity of La_2MgTiO_6 was the best after 800℃calcinations for 3h in the air.
实验结果表明，在5H_2％／95％N_2气氛氛围中1100℃焙烧3h后，催化剂LaSrBMnO_6(B=Fe，Co)和LaSrCoFeO_6均生成了单相物相。其中，LaSrCoFeO_6对甲烷催化燃烧的起燃温度最低为460℃，完全转化温度为673℃；反应温度在500-650℃之间催化剂LaSrFeMnO_6对甲烷催化燃烧活性最好；催化剂LaSrCoMnO_6对甲烷燃烧催化活性最差。在室温下电导测试发现LaSrFeMnO_6的导电性最好，催化剂LaSrCoFeO_6的导电性最差。
对几种单、双钙钛矿进行了化学与物理性能的比较，在三种催化剂LaSrCoFeO_6、La_(0．5)Sr_(0．5)CoO_3和La_(0．5)Sr_(0．5)FeO_3中，LaSrCoFeO_6对甲烷燃烧的催化活性最好，在测试温度范围内，LaSrCoFeO_6的导电性最差；在三种催化剂LaSrCoMnO_6、La_(0．5)Sr_(0．5)MnO_3和La_(0．5)Sr_(0．5)CoO_3中，La_(0．5)Sr_(0．5)MnO_3对甲烷燃烧的催化活性最好，在测试温度范围内其导电性也最好；在三种催化剂LaSrFeMnO_6、La_(0．5)Sr_(0．5)MnO_3和La_(0．5)Sr_(0．5)FeO_3中，La_(0．5)Sr_(0．5)MnO_3对甲烷燃烧的催化活性最好，在测试温度范围内，催化剂LaSrFeMnO_6的导电性最好。
采用柠檬酸作络合剂的溶胶-凝胶法制备的三种催化剂La_2CoMnO_6、La_2MnVO_6和La-Co-V-O，在5H_2％／95％N_2气氛氛围中1100℃焙烧3h后制备单相双钙钛矿型催化剂La_2CoMnO_6和La_2MnVO_6，而体系La-Co-V-O没有得到单相物相。同时，对比两种催化剂LaSrCoMnO_6和La_2CoMnO_6对甲烷催化燃烧的活性及其磁性。
以葡萄糖作络合剂的溶胶-凝胶法制备催化剂La-B-Ti-O(B=Mg、Ca、Sr、Co)，在空气中1100℃焙烧3h后制备出单相双钙钛矿型催化剂La_2MgTiO_6，其它三种催化剂La-B-Ti-O(B=Ca、Sr、Co)没有得到单相物相。对催化剂La_2MgTiO_6进行不同焙烧温度的结构和性能比较，发现在500℃焙烧3h后即制得单相催化剂La_2MgTiO_6；而在800℃焙烧3h后，催化剂La_2MgTiO_6对甲烷催化燃烧活性最好。
The perovskite-type composite oxide LaSrBMnO_6(B=Fe、Co) ,LaSrCoFeO_6;La_(0.5)Sr_(0.5)BO_3(B=Fe、Co、Mn); La-B-Ti-O(B=Mg、Ca、Sr、Co) and La-Co-V-O、La_2CoMnO_6、La_2MnVO_6 were synthesized by the sol-gel method and characterized by means of XRD、TPR、BET、FT-IR、TEM、the catalytic activity evaluation、conductivity and magnetic properties.
We find that the single-phase perovskite-type oxides LaSrBMnO_6(B=Fe,Co), LaSrCoFeO_6 and La_(0.5)Sr_(0.5)BO_3(B=Fe,Co,Mn) were synthesized by the sol-gel using citric acid as complex agent. It is shown that LaSrFeMnO_6 showed a higher conductivity than LaSrCoMnO_6 and LaSrCoFeO_6 after 1100℃calcinations for 3h in 5H_2%/95%N_2. LaSrCoFeO_6 showed a better catalytic activity for methane combustion than LaSrBMnO_6(B=Fe,Co), which T_(10)(methane conversion of 10%) and T_(90)(methane conversion of 90 % ) were 460℃and 673℃respectively, and LaSrFeMnO_6 showed the best catalytic activity between 500-650℃.
The chemical and physical properties of several of the single, double perovskite-type oxides were compared under the same condition. In the first group, LaSrCoFeO_6, La_(0.5)Sr_(0.5)CoO_3and La_(0.5_Sr_(0.5)FeO_3, LaSrCoFeO_6 had the best catalytic activity for methane combustion but the worst conductivity. In the second group, LaSrCoMnO_6, La_(0.5)Sr_(0.5)MnO_3 and La_(0.5)Sr_(0.5)CoO_3, La_(0.5)Sr_(0.5)MnO_3 had the best catalytic activity and conductivity. In the third group, LaSrFeMnO_6,La_(0.5)Sr_(0.5)MnO_3 and La_(0.5)Sr_(0.5)FeO_3, La_(0.5)Sr_(0.5)MnO_3 had the best catalytic activity and LaSrFeMnO_6 had the best conductivity.
The La_2CoMnO_6, La_2MnVO_6 and La-Co-V-O were prepared by the sol-gel using citric acid as complex agent. The studies showed that single-phase perovskite-type oxides La_2CoMnO_6 and La_2MnVO_6 were synthesidzed after 1100℃calcinations for 3h in 5H_2%/95%N_2, but the system of La-Co-V-O was not synthesized single-phase. Meanwhile, we also compared catalytic activity for methane combustion and magnetic activity of LaSrCoMnO_6 and La_2CoMnO_6.
Four systems of perovskite-type composite oxides La-B-Ti-O(B=Mg,Ca,Sr,Co) were prepared by sol-gel using glucose as complex agent. Experimental results show that La-B-Ti-O(B=Ca、Sr、Co) were not synthesized single-phase perovskite-type oxides and the La_2MgTiO_6 was synthesized after 500℃calcinations for 3h in the air. The catalytic activity of La_2MgTiO_6 was the best after 800℃calcinations for 3h in the air.
引文
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