含铈硫酸氧盐储氧材料的制备及储/释氧性能研究  

The Preparation and Oxygen Storage / Release Properties of Oxysulfates Containing Cerium as Oxygen Storage Material

作　　者：王男[1] 崔咪芬[1] 陈献[1] 汤吉海[1] 乔旭[1,2] 

机构地区：[1]南京工业大学化学化工学院,江苏省工业节水减排重点实验室,江苏南京210009 [2]南京工业大学材料化学工程国家重点实验室,江苏南京210009

出　　处：《化学反应工程与工艺》2011年第3期262-268,共7页Chemical Reaction Engineering and Technology

基　　金：国家“863”计划(2009AA03Z504);江苏省高校自然科学研究重大项目(09KJA530004)

摘　　要：采用表面活性剂辅助法分别制备了铈、镧及其复合物的硫酸氧盐和掺加铜元素的硫酸氧铈,利用X射线衍射(XRD)、傅里叶红外光谱变换法(FT-IR)、BET比表面积测试法(BET)、程序升温还原法(TPR)、程序升温氧化(TPO)和氧脉冲吸附等技术手段对这些储氧材料进行了表征。结果表明,Ce_2O_2SO_4、LaCeO_2SO_4的氧化还原温度较La_2O_2SO_4显著降低,Ce_2O_2SO_4和LaCeO_2SO_4程序升温发生释氧(还原,耗氢)的温度分别为550～780℃和600～760℃,主要发生在650～780℃和650～750℃,总耗氢量分别达46和44molH_2/mol;而La_2O_2SO_4发生释氧的温度为770～930℃。Ce_2O_2S程序升温发生储氧(氧化,耗氧)的温度为100～600℃,主要发生在300～500℃,400℃时储氧速率最大。LaCeO_2S储氧的温度比Ce_2O_2S约低20℃,且主要发生在220～500℃,380℃时储氧速率最大。Ce_2O_2S与LaCeO_2S的储氧量分别达到1 57和1 58 molO_2/mol,是理论储氧量(2 molO_2/mol)的78 5%和79%,La_2O_2S程序升温氧化在400℃开始,至1000℃还没有氧化完全。采用400℃恒温O_2脉冲测得硫酸氧铈的储氧能力为0 60 molO_2/mol,占总储氧量的38%。掺入过渡金属Cu进行改性后,其氧化还原的起始温度有所降低。（La1-xCex）2O2SO4 （x=0, 0.5, 1） and CuCeOxSO4 were synthesized by a template-assisted route and characterized by means of XRD, FT-IR, BET, TPR, TPO and O2-pulse. The results showed that the reduction temperature of Ce2O2SO4 and LaCeO2SO4 were significantly lower than that of La2O2SO4 in TPR. The reduction temperature range of Ce2O2SO4, LaCeO2SO4 and La2O2SO4 occurred in 550-780 ℃（mainly in 650-780 ℃）, 600-760 ℃（mainly in 650-750 ℃）and 770-930 ℃, respectively. The hydrogen consumption of Ce202SO4 and LaCeO2SO4 reached 4.6 molHz/mol and 4.4 molH2/moh respectively. The oxidation temperature range of Ce2O2S and LaCeO2S occurred in 100-600 ℃ and 100-550 ℃, mainly occurred in 300-500 ℃ and 220-500 ℃, with the maximum oxidation rate at 400 and 380 ℃, respectively. The OSC of the two above was 1.58 molO2/mol and 1,57 molO2/mol, respectively. La2O2S re-oxidation started at 400 ℃ to 1000 ℃ and it had not completed. The OSC of Ce2O2S that tested by the O2-pulse at 400 ℃ was 0.60 molO2/mol, 38% of the total OSC. After incorporating of transition metal Cu, the start temperature of TPR/TPO for CuCeOxSO4/CuCeOxS had decreased.

关 键 词：储氧材料 硫酸氧盐/硫化物 储/释氧性能 程序升温还原/氧化 氧脉冲 储氧量 

分 类 号：TQ133.3[化学工程—无机化工]