B位镨掺杂BaPr_(x)Fe_(1-x)O_(3-δ)透氧膜的制备及性能研究  

Preparation and properties of B-site praseodymium doped mixed conductor oxygen permeable membranes

作　　者：梁碧麟 余倩 贾思琦 李芳[1] 李其明[1] LIANG Bilin;YU Qian;JIA Siqi;LI Fang;LI Qiming(School of petrochemical Engineering,Liaoning Petrochemical University,Fushun 113001,China)

机构地区：[1]辽宁石油化工大学石油化工学院,抚顺113001

出　　处：《膜科学与技术》2025年第1期101-107,共7页Membrane Science and Technology

基　　金：国家自然科学基金项目(21201096,21703091);辽宁省教育厅资助项目(LJKMZ20220724,JYTMS20231442);辽宁科技厅计划指导项目(2019-ZD-0058)。

摘　　要：通过联合络合法合成了B位镨掺杂BaPr_(x)Fe_(1-x)O_(3-δ)系列钙钛矿透氧膜材料,有效优化了BaFeO_(3-δ)母体材料的晶相结构,该系列材料展示了良好的氧渗透性能.研究结果表明,通过B位镨掺杂可促使BaFeO_(3-δ)母体材料由六方晶型结构转变为立方钙钛矿结构,且BaPr_(x)Fe_(1-x)O_(3-δ)材料晶胞体积随着镨含量的增加而增大.系统对比了BaFeO_(3-δ)材料和BaPr_(x)Fe_(1-x)O_(3-δ)系列钙钛矿透氧膜材料在晶相结构、微观形貌、氧渗透通量和速率控制步骤等方面的差异.研究发现六方相BaFeO_(3-δ)母体膜片在中低温区间氧渗透性能极低,随着温度升高至950℃,其透氧量迅速增加至约0.4 mL/(cm^(2)·min),而BaPr_(0.05)Fe_(0.95)O_(3-δ)膜片的中低温透氧性能明显改善,850℃时其透氧量为0.42 mL/(cm^(2)·min),950℃时透氧量高达0.60 mL/(cm^(2)·min).PrxFe_(1-x)O_(3-δ)系列材料的透氧量随Pr掺杂量的增加呈现先增加后减少的趋势,在掺杂量为x=0.1时达到最大值.通过Wagner方程系统分析了BaPr_(0.05)Fe_(0.95)O_(3-δ)膜片(厚度为1.0 mm)的氧渗透动力学过程,发现其为体相扩散控制.该研究提供了一种基于镨微量掺杂调变BaFeO_(3-δ)的晶相结构和氧渗透性能的有效方法.A series of BaPr_(x)Fe_(1-x)O_(3-δ) perovskite oxygen-permeable membranes with Pr doping into B-site were synthesized using a combined complexation method,which effectively optimizes the crystal structure of BaFeO_(3-δ)parent material and demonstrates the enhanced oxygen permeability.Experimental results indicate that BaFeO_(3-δ)a parent material can transition from a hexagonal crystal structure to a cubic perovskite structure with minimal praseodymium doping,and the crystal cell volume of BaFeO_(3-δ) series increases progressively with higher Pr doping content.The crystal structure,surface morphologies,oxygen permeability,and the rate-determining step of BaPr_(x)Fe_(1-x)O_(3-δ) were systematically compared.It can be observed that the oxygen flux of BaFeO_(3-δ) membrane is very low at medium-low temperature,and its oxygen flux could increase rapidly to about 0.4 mL/(cm^(2).min)only at 950℃,In contrast,the medium-low oxygen permeation flux of BaPr_(0.05)Fe_(0.95)O_(3-δ) can be significantly improved.For instance,its oxygen permeation flux is 0.42 mL/(cm^(2)·min)at 850 C,and reach as high as 0.60 mL/(cm^(2)·min)at 95o C.The oxygen permeability of PrxFe_(1-x)O_(3-δ) series exhibits a trend of increasing first and then decreasing with increasing Pr content,reaching its maximum value atα=0.1.The oxygen permeation kinetics of BaPr_(0.05)Fe_(0.95)O_(3-δ)membrane(thickness of 1.0 mm)was systematically analyzed by Wagner equation,and it was found that it is controlled by bulk phase diffusion.This study provides an effective method for tuning the crystal structure and oxygen permeation performance of BaFeO_(3-δ) by doping Pr ions.

关 键 词：透氧膜 镨掺杂 钙钛矿 透氧量 晶相结构 

分 类 号：TQ028.8[化学工程]