CN108947529A - 一种非金属离子掺杂的钨酸镧型混合质子-电子导体透氢材料及其制备方法与应用 - Google Patents
一种非金属离子掺杂的钨酸镧型混合质子-电子导体透氢材料及其制备方法与应用 Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 75
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 75
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 57
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 29
- 239000002253 acid Substances 0.000 title claims abstract description 25
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002156 mixing Methods 0.000 title claims abstract description 25
- 239000011532 electronic conductor Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 8
- XPFAJCSMHOQBQB-UHFFFAOYSA-N 2-aminoacetic acid;nitric acid Chemical compound O[N+]([O-])=O.NCC(O)=O XPFAJCSMHOQBQB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 3
- 239000008246 gaseous mixture Substances 0.000 claims abstract description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 3
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract 2
- 239000000843 powder Substances 0.000 claims description 30
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 13
- 229910017677 NH4H2 Inorganic materials 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910001018 Cast iron Inorganic materials 0.000 claims description 6
- 239000004471 Glycine Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 4
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 4
- 238000009738 saturating Methods 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 10
- 230000035699 permeability Effects 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- 238000010926 purge Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 235000009508 confectionery Nutrition 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- -1 phosphonium ion Chemical class 0.000 description 4
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011533 mixed conductor Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
本发明公开了一种非金属离子掺杂的钨酸镧型混合质子‑电子导体透氢材料及其制备方法与应用。该材料的化学通式为LnaW1‑xMxO12‑δ，其中Ln是镧系元素La、Nd、Eu、Er中的一种；M是非金属元素P、S的一种；δ为非化学计量比；0≤δ≤1，5.3≤a≤5.7，0≤x≤0.5。本发明的材料可采用甘氨酸‑硝酸盐燃烧法制备。本发明的材料中，通过非金属离子的掺杂提高了膜材料的电导率，从而使得膜材料的透氢量得到提升。并且该材料在含氢气氛下具有很好的操作稳定性，可以用于从含氢混合气中分离氢气。
Description
技术领域
本发明属于氢气分离材料应用技术领域，具体涉及一种非金属离子掺杂的钨酸镧型混合质子-电子导体透氢材料及其制备方法与应用。
背景技术
混合质子-电子导体透氢材料是一种无机致密陶瓷材料，因其同时具有质子和电子导电性，在高温下对氢气的选择性高达100%。另外，将它用于一系列涉氢反应中能有效提高反应的效率和能量的利用率。因此，混合质子-电子导体透氢材料被广泛地研究。
自从1970年La2O3-WO3体系的相平衡被研究以来，钨酸镧型氧化物备受关注。Haugsrud等人研究了Ca掺杂的Ln6WO12 (Ln = La、Nd、Gd、Er)的导电性，发现La6WO12表现出最高的质子导电性3-5×10-3 S•cm-1，在潮湿的气氛下且操作温度低于1150 °C时，质子是主要的离子传导载体。Escolástico等人对Nd6WO12-Eu6WO12-Er6WO12的晶体结构、晶粒大小和导电性进行了研究，发现他们的晶体结构是立方萤石对称结构，并且Eu6WO12显示出最高的导电性能。他们还研究了Nd6WO12片状膜的透氢性能，510 μm的膜在1000 °C透氢量为0.023mL/（min•cm2）。Gil和Escolástico分别研究了非对称片状膜La28-xW4+xO54+3x/2和对称片状膜La5.5WO11.25-δ的透氢性能。总的来说，钨酸镧型混合导体透氢膜这类材料的透氢性能较低，在含氢气氛下长期操作稳定性不足。
发明内容
为了解决现有技术的缺点和不足之处，本发明的目的在于提供一种非金属离子掺杂的钨酸镧型混合质子-电子导体透氢材料及其制备方法。
本发明的另一目的在于提供上述一种非金属离子掺杂的钨酸镧型混合质子-电子导体透氢材料在氢气分离中的应用。
本发明的目的通过以下技术方案实现。
一种非金属离子掺杂的钨酸镧型混合质子-电子导体透氢材料，该材料的化学通式为LnaW1-xMxO12-δ，其中Ln是镧系元素La、Nd、Eu和Er中的一种；M是非金属元素P和S的一种；δ为非化学计量比；0 ≤δ≤ 1，5.3 ≤ a ≤ 5.7，0 ≤ x ≤ 0.5。
以上所述的一种非金属离子掺杂的钨酸镧型混合质子-电子导体透氢材料的制备方法，制备方法为甘氨酸-硝酸盐燃烧法，包括以下步骤：
（1）称量原料金属氧化物La2O3、Nd2O3、Eu2O3、Er2O3、WO3，非金属铵盐NH4H2PO4、NH4H2SO4；
（2）将步骤（1）中称取的La2O3、Nd2O3、Eu2O3或Er2O3溶于浓硝酸中，将WO3溶于氨水中，NH4H2PO4或NH4H2SO4溶于水中，三种溶液混合均匀，在所得的混合液中加入甘氨酸，加热搅拌混合液至凝胶状；
（3）将步骤（2）中获得的凝胶放入电炉中焙烧，得到粉体的前驱体；
（4）将步骤（3）中得到的粉体的前驱体放入马弗炉中，在800~1000℃下保温，得到成相粉体；
（5）将步骤（4）中获得的成相粉体放入铸铁模具中，在10MPa~20MPa压力下保压，获得生坯；
（6）将步骤（5）中得到的生坯放入高温马弗炉中，在1300~1600℃下保温，得到非金属离子掺杂的钨酸镧型混合质子-电子导体透氢材料。
优选的，步骤（2）中加入的甘氨酸的量为混合液中每1mol金属离子加入90~110g甘氨酸。
优选的，步骤（2）所述加热搅拌的温度为150~300℃，时间为24~36h。
优选的，步骤（3）中电炉焙烧的温度为150~450℃。
优选的，步骤（4）、步骤（6）所述保温的时间为5~10h。
优选的，步骤（4）中马弗炉热处理的升降速率为每分钟1~5℃。
优选的，步骤（5）所述保压的时间为5~20min。
优选的，步骤（6）中高温马弗炉热处理的升降速率为每分钟1~2℃。
以上所述的一种非金属离子掺杂的钨酸镧型混合质子-电子导体透氢材料应用于混合气中分离氢气的反应器。
与现有技术相比，本发明具有如下优点及有益效果：
（1）本发明通过甘氨酸-硝酸盐燃烧法获得的粉体颗粒直径小，粉体成相温度低，节约能耗；
（2）本发明的非金属离子掺杂的混合质子-电子导体透氢材料透氢量相比未掺杂的有所提升；
（3）本发明选择非金属离子掺杂的混合质子-电子导体透氢材料在含氢氛围下能长期稳定操作。
附图说明
图1为实施例1制备一种非金属离子掺杂的钨酸镧型混合质子-电子导体透氢材料的过程示意图。
图2为所得粉体LWP25、NWS10、LWO的相结构表征图。
图3为实施例1所得粉体LWP25的扫描电镜图。
图4a、图4b分别为实施例1所得LWP25透氢材料的表面和截面扫描电镜图。
图5是实施例1制备得到的的LWP25和LWO透氢材料在透氢性能测试中的氢气渗透量曲线图。
图6是LWP25透氢材料在900℃下进行50h的透氢测试的性能图。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
本实施例的一种磷离子掺杂的钨酸镧基混合质子-电子导体透氢材料La5.5W0.75P0.25O12-δ (δ = 0.5)（LWP25）和未掺杂的钨酸镧基混合质子-电子导体材料La5.5WO12-δ (δ = 0.4) (LWO)，如图1所示，制备方法包括以下步骤：
（1）称取LWP25原料:12.334g La2O3溶于质量分数为65%的浓硝酸，2.553g WO3溶于质量分数为18%的氨水，0.317g NH4H2PO4 溶于去离子水，三者混合均匀，在混合液中加入8.56g甘氨酸；
（2）称取LWO原料:11.916g La2O3溶于质量分数为65%的浓硝酸，3.083g WO3溶于质量分数为18%的氨水，二者混合均匀，在混合液中加入8.65g甘氨酸；
（3）分别将步骤（1）和（2）中获得的硝酸盐混合液加热到150℃搅拌36h，至溶液呈现凝胶状，随后将凝胶放入电炉中，加热至300℃焙烧，获得粉体的前驱体；将粉体置于马弗炉中，以升降温速率每分钟1℃至800℃保温10h，获得粉体LWP25和LWO。
（3）分别称取1g成相粉体LWP25和LWO放入铸铁模具中，在10MPa压力下保持20min，得到生坯；将生坯放入高温马弗炉中以升降温速率每分钟2℃至1300℃保温10h，即可获得致密的LWP25和LWO透氢材料。
（4）将制备得到的膜材料分别使用220目、400目、800目、2000目砂纸进行打磨和抛光，直至膜片厚度为0.5mm。随后将膜放入乙醇介质中进行超声清洗并烘干。使用陶瓷密封胶进行将膜材料密封在刚玉管上，刚玉管外侧套以一石英管作为进料侧。室温下静置12h后，升温至950℃开始进行透氢性能测试，测试温度范围为850至950℃。透氢性能测试的条件为：进料侧通入40mL/min氢气和40mL/min氦气混合气，吹扫侧通入30mL/min氩气，吹扫侧尾气通入气相色谱中进行氢气含量的检测和稳定性测试，尾气流速使用皂泡流量计校准。
将步骤（2）中获得的粉体LWP25进行相结构表征，如图2所示，表明磷离子掺杂的钨酸镧型材料保持了原有的钨酸镧的相结构；还进行了扫描电镜表征，图3中显示制得的粉体的颗粒直径分布在0.5至1.0μm。
将步骤（3）中获得的膜材料进行扫描电镜表征，图4是烧结致密的LWP25透氢材料表面和截面电镜图片，在表面图中晶界清晰分明，各个晶胞紧密相连，截面图中显示材料内部并无明显的缺陷或通孔，证明制备得到的透氢材料是致密的。
图5是制备得到的LWP25和LWO透氢材料在透氢性能测试中的透氢量，LWP25在850至950℃范围内的透氢量高于LWO在该温度范围的透氢量，证明磷离子掺杂能提高钨酸镧基透氢材料的性能。
图6是在900℃下，LWP25透氢材料进行50h的透氢测试的性能图，LWP25透氢材料在50h测试中透氢量无明显下降，表明LWP25透氢材料具有良好的性能稳定性。
实施例2
本实施例的一种硫离子掺杂的钨酸镧基混合质子-电子导体透氢材料Nd5.3W0.9S0.1O12-δ(δ = 1)（NWS10）制备方法包括以下步骤：
（1）称取NWP10原料:8.01g Nd2O3溶于质量分数为65%的浓硝酸，1.87g WO3溶于质量分数为18%的氨水，0.103g NH4H2SO4 溶于去离子水，三者混合均匀，在混合液中加入5.56g甘氨酸；
（2）将步骤（1）中获得的硝酸盐混合液加热到300℃搅拌24h，至溶液呈现凝胶状，随后将凝胶放入电炉中，加热至150℃焙烧，获得粉体的前驱体；将粉体置于马弗炉中，以升降温速率每分钟3℃至1000℃保温5h，获得粉体NWS10。
（3）称取2g 成相粉体NWS10放入铸铁模具中，在20MPa压力下保持5min，得到生坯；将生坯放入高温马弗炉中以升降温速率每分钟1℃至1400℃保温8h，即可获得致密的NWS10透氢材料。
（4）将获得的NWS10透氢材料进行性能表征。测试温度范围为850至950℃。透氢性能测试的条件为：进料侧通入40 mL/min氢气和40 mL/min氦气混合气，吹扫侧通入30 mL/min氩气。NWS10在950 oC下的透氢量为0.03 mL/（min cm2）。
实施例3
本实施例的一种磷离子掺杂的钨酸镧基混合质子-电子导体透氢材料Eu5.7W0.5P0.5O12-δ(δ = 0)（EuWP50）制备方法包括以下步骤：
（1）称取EWP50原料:10.43g Eu2O3溶于质量分数为65%的浓硝酸，1.21g WO3溶于质量分数为18%的氨水，0.59g NH4H2PO4 溶于去离子水，三者混合均匀，在混合液中加入6.45g甘氨酸；
（2）将步骤（1）中获得的硝酸盐混合液加热到220℃搅拌28h，至溶液呈现凝胶状，随后将凝胶放入电炉中，加热至250℃焙烧，获得粉体的前驱体；将粉体置于马弗炉中，以升降温速率每分钟1.5℃至900℃保温7.5h，获得粉体EuWP50。
（3）称取1.8g成相粉体EuWP50放入铸铁模具中，在16MPa压力下保持9min，得到生坯；将生坯放入高温马弗炉中以升降温速率每分钟1.5℃至1500℃保温10h，即可获得致密的EWP50透氢材料。
（4）将获得的EWP50透氢材料进行性能表征。测试温度范围为850至950℃。透氢性能测试的条件为：进料侧通入40 mL/min氢气和40 mL/min氦气混合气，吹扫侧通入30 mL/min氩气。EWP50在850 oC下的透氢量为0.009 mL/（min cm2）。
实施例4
本实施例的一种硫离子掺杂的钨酸镧基混合质子-电子导体透氢材料Er5.6W0.7S0.3O12-δ(δ = 0.75)（ErWS30）制备方法包括以下步骤：
（1）称取ErWS30原料:11.09g Er2O3溶于质量分数为65%的浓硝酸，1.68g WO3溶于质量分数为18%的氨水，0.36g NH4H2SO4 溶于去离子水，三者混合均匀，在混合液中加入6.53g甘氨酸；
（2）将步骤（1）中获得的硝酸盐混合液加热到190℃搅拌32h，至溶液呈现凝胶状，随后将凝胶放入电炉中，加热至450℃焙烧，获得粉体的前驱体；将粉体置于马弗炉中，以升降温速率每分钟5℃至950℃保温6h，获得粉体ErWS30。
（3）称取1.3g成相粉体ErWS30放入铸铁模具中，在13MPa压力下保持10min，得到生坯；将生坯放入高温马弗炉中以升降温速率每分钟2℃至1600℃保温5h，即可获得致密的ErWS10透氢材料。
（4）将获得的ErWS10透氢材料进行性能表征。测试温度范围为850至950℃。透氢性能测试的条件为：进料侧通入40 mL/min氢气和40 mL/min氦气混合气，吹扫侧通入30 mL/min氩气。ErWS10在900 oC下的透氢量为0.011 mL/（min cm2）。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (10)
1.一种非金属离子掺杂的钨酸镧型混合质子-电子导体透氢材料，其特征在于，该材料的化学通式为LnaW1-xMxO12-δ，其中Ln是镧系元素La、Nd、Eu和Er中的一种；M是非金属元素P和S的一种；δ为非化学计量比；0 ≤δ≤ 1，5.3 ≤ a ≤ 5.7，0 ≤ x ≤ 0.5。
2.制备权利要求1所述的一种非金属离子掺杂的钨酸镧型混合质子-电子导体透氢材料的方法，其特征在于，制备方法为甘氨酸-硝酸盐燃烧法，包括以下步骤：
（1）称量原料金属氧化物La2O3、Nd2O3、Eu2O3、Er2O3、WO3，非金属铵盐NH4H2PO4、NH4H2SO4；
（2）将步骤（1）中称取的La2O3、Nd2O3、Eu2O3或Er2O3溶于浓硝酸中，将WO3溶于氨水中，NH4H2PO4或NH4H2SO4溶于水中，三种溶液混合均匀，在所得的混合液中加入甘氨酸，加热搅拌混合液至凝胶状；
（3）将步骤（2）中获得的凝胶放入电炉中焙烧，得到粉体的前驱体；
（4）将步骤（3）中得到的粉体的前驱体放入马弗炉中，在800~1000℃下保温，得到成相粉体；
（5）将步骤（4）中获得的成相粉体放入铸铁模具中，在10MPa~20MPa压力下保压，获得生坯；
（6）将步骤（5）中得到的生坯放入高温马弗炉中，在1300~1600℃下保温，得到非金属离子掺杂的钨酸镧型混合质子-电子导体透氢材料。
3.根据权利要求2所述的制备方法，其特征在于，步骤（2）中加入的甘氨酸的量为混合液中每1mol金属离子加入90~110g甘氨酸。
4.根据权利要求2所述的制备方法，其特征在于，步骤（2）所述加热搅拌的温度为150~300℃，时间为24~36h。
5.根据权利要求2所述的制备方法，其特征在于，步骤（3）中电炉焙烧的温度为150~450℃。
6.根据权利要求2所述的制备方法，其特征在于，步骤（4）、步骤（6）所述保温的时间为5~10h。
7.根据权利要求2所述的制备方法，其特征在于，步骤（4）中马弗炉热处理的升降速率为每分钟1~5℃。
8.根据权利要求2所述的制备方法，其特征在于，步骤（5）所述保压的时间为5~20min。
9.根据权利要求2所述的制备方法，其特征在于，步骤（6）中高温马弗炉热处理的升降速率为每分钟1~2℃。
10.权利要求1所述的一种非金属离子掺杂的钨酸镧型混合质子-电子导体透氢材料应用于混合气中分离氢气的反应器。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1934033A (zh) * | 2004-04-21 | 2007-03-21 | Lg化学株式会社 | 具有新型晶体结构的金属复合氧化物及其作为离子型导体的用途 |
| WO2009065180A1 (en) * | 2007-11-23 | 2009-05-28 | The University Of Queensland | Non-metal doped metal oxide nanosheets and method of production thereof |
| CN102812587A (zh) * | 2010-02-12 | 2012-12-05 | 普罗迪亚股份有限公司 | 质子传导膜 |
| CN105330290A (zh) * | 2015-10-19 | 2016-02-17 | 华南理工大学 | 一种用于h2s分解的混合导体陶瓷膜的制备及测试方法 |
| CN106943888A (zh) * | 2017-03-31 | 2017-07-14 | 华南理工大学 | 一种阴离子掺杂的萤石型钨酸基混合导体透氢膜材料及其制备方法与应用 |
-
2018
- 2018-06-25 CN CN201810663232.3A patent/CN108947529B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1934033A (zh) * | 2004-04-21 | 2007-03-21 | Lg化学株式会社 | 具有新型晶体结构的金属复合氧化物及其作为离子型导体的用途 |
| WO2009065180A1 (en) * | 2007-11-23 | 2009-05-28 | The University Of Queensland | Non-metal doped metal oxide nanosheets and method of production thereof |
| CN102812587A (zh) * | 2010-02-12 | 2012-12-05 | 普罗迪亚股份有限公司 | 质子传导膜 |
| CN105330290A (zh) * | 2015-10-19 | 2016-02-17 | 华南理工大学 | 一种用于h2s分解的混合导体陶瓷膜的制备及测试方法 |
| CN106943888A (zh) * | 2017-03-31 | 2017-07-14 | 华南理工大学 | 一种阴离子掺杂的萤石型钨酸基混合导体透氢膜材料及其制备方法与应用 |
Non-Patent Citations (1)
| Title |
|---|
| LI.MR ETAL.: ""SrCo0.85Fe0.1P0.05O3-δperovskite as a cathode for intermediate-temperature solid oxide fuel cells", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114870648A (zh) * | 2022-05-17 | 2022-08-09 | 华南理工大学 | 一种混合导体透氢膜材料及其制备方法和应用 |
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