CN112851322A - Pd单原子BiFeO3压电多孔陶瓷、其制法及高效制氢 - Google Patents
Pd单原子BiFeO3压电多孔陶瓷、其制法及高效制氢 Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 90
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 68
- 239000001257 hydrogen Substances 0.000 title claims abstract description 68
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910002902 BiFeO3 Inorganic materials 0.000 claims abstract description 74
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 239000008187 granular material Substances 0.000 claims description 20
- 229920002472 Starch Polymers 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 235000019698 starch Nutrition 0.000 claims description 17
- 239000008107 starch Substances 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 14
- 238000003825 pressing Methods 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 230000010287 polarization Effects 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 150000001621 bismuth Chemical class 0.000 claims description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 10
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 10
- 239000007789 gas Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 5
- 239000002574 poison Substances 0.000 abstract description 5
- 231100000614 poison Toxicity 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000007789 sealing Methods 0.000 description 11
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- 239000000463 material Substances 0.000 description 7
- 229910000085 borane Inorganic materials 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 description 3
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- 239000007772 electrode material Substances 0.000 description 3
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- 239000003208 petroleum Substances 0.000 description 2
- 229910003203 NH3BH3 Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 238000003797 solvolysis reaction Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种Pd单原子BiFeO3压电多孔陶瓷、其制法与自供能高效制氢中的应用。该压电多孔陶瓷包括BiFeO3压电多孔陶瓷基体以及均匀分散于压电多孔陶瓷基体表面及孔道内的Pd单原子,所述Pd单原子的质量分数为0.01wt%‑0.1wt%。本发明提供的一种Pd单原子BiFeO3压电多孔陶瓷材料中Pd的含量低,同时具有较高的催化活性,降低了贵金属的使用,从而大大降低了生产成本。该Pd单原子BiFeO3压电多孔陶瓷材料可用为氢燃料电池提供氢源,制氢效率高、纯度高,不含一氧化碳、硫化氢、磷化氢、氯离子等使燃料电池中毒的气体,且制备方法简单易行、绿色环保,不排放对环境有害物质。
Description
技术领域
本发明涉及一种Pd单原子BiFeO3压电多孔陶瓷,特别涉及一种Pd单原子BiFeO3压电多孔陶瓷的制备方法以及其于自供能高效制氢中的应用,属于能源材料领域。
背景技术
随着我国经济社会的发展,我国能源消耗越来越大,目前我国的石油进口量占总原油消耗量的70%左右。这一方面消耗了石油资源,另一方面使用原油排放的温室气体也污染了环境。为此,我国政府出台政策,鼓励发展新能源汽车。尤其是,以氢燃料电池为驱动力的新能源汽车是优先鼓励的发展方向。
但是,氢燃料电池的电极材料容易被混合在氢气中的一氧化碳、硫化氢、磷化氢、氯离子等杂质中毒,从而影响氢燃料电池的使用寿命。因此,制备高纯氢对发展氢燃料电池和新能源汽车产业,具有重要的应用价值。另外,尽管贵金属作为催化剂可以制氢,但是贵金属价格高,资源有限,从而限制了贵金属的广泛应用。因此,如何使用质量较少的贵金属同时具有较高的催化活性的材料制备高纯氢是一个亟待解决的问题。
发明内容
现有的氢源大多来源于化工制氢,其中含有容易使燃料电池电极材料中毒的一氧化碳、硫化氢、磷化氢、氯离子等气态物质。本发明的目的在于提供一种Pd单原子BiFeO3压电多孔陶瓷、其制备方法以及于车载自供能高效制氢中的应用,以克服现有制氢技术中的不足,还克服了现有技术中的贵金属Pd利用率低、催化活性低导致的成本较高的不足。
为实现前述发明目的,本发明采用的技术方案包括:所述一种Pd单原子BiFeO3压电多孔陶瓷,包括BiFeO3压电多孔陶瓷基体以及均匀分散于压电多孔陶瓷表面的Pd单原子;
其中,所述Pd单原子的质量分数为0.01wt%-0.1wt%;
所述BiFeO3压电多孔陶瓷基体的孔径为0.1mm~1.0mm。
优选地,所述Pd单原子的质量分数上限选自0.02wt%、0.03wt%、0.04wt%、0.05wt%、0.06wt%、0.07wt%、0.08wt%、0.09wt%、0.10wt%;所述Pd单原子的质量分数下限选自0.01wt%、0.02wt%、0.03wt%、0.04wt%、0.05wt%、0.06wt%、0.07wt%、0.08wt%、0.09wt%。
优选地,所述BiFeO3压电多孔陶瓷的孔径上限选自0.2mm、0.3mm、0.4mm、0.5mm、0.6mm、0.7mm、0.8mm、0.9mm、1.0mm;所述BiFeO3压电多孔陶瓷的孔径下限选自0.01mm、0.02mm、0.03mm、0.04mm、0.05mm、0.06mm、0.07mm、0.08mm、0.09mm。
可选地,所述Pd单原子还分散于所述BiFeO3压电多孔陶瓷孔道表面。
所述一种Pd单原子BiFeO3压电多孔陶瓷的制备方法,包括以下步骤:
(1)制备BiFeO3颗粒:将铋盐、铁盐与碱反应,生成BiFeO3颗粒;
(2)造粒:向步骤(1)制得的BiFeO3颗粒中分别加入0.1-5.0wt%的淀粉和5-8wt%的聚乙烯醇溶液球磨造粒;
(3)制备陶坯:将步骤(2)制得的BiFeO3颗粒加入到20mm×20mm尺寸的模具中,用压膜机在10MPa压力下压制成陶坯;
(4)造孔与脱胶:将陶坯加热至350-450℃,恒温1-2h;继续升温进行脱胶处理;
(5)成型:脱胶后在温度为850℃条件下处理2h,冷却后制得BiFeO3多孔陶瓷;
(6)极化处理:将BiFeO3多孔陶瓷片在3KV/mm电压下极化25min,放置24h后制得BiFeO3压电多孔陶瓷;
(7)Pd单原子BiFeO3压电多孔陶瓷的制备:将BiFeO3压电多孔陶瓷置于PdCl2溶液中进行超声处理,即制得所述Pd单原BiFeO3压电多孔陶瓷。
可选地,所述造孔温度为450℃。
可选地,所述脱胶处理的温度为550℃。
可选地,所述铋盐选自氯化铋、硝酸铋中的至少一种。
可选地,所述铁盐选自硝酸铁、氯化铁中的至少一种。
可选地,所述碱选自氢氧化钠、氢氧化钾和氨水中的至少一种。
可选地,所述BiFeO3颗粒由氯化铋、硝酸铁和氢氧化钾反应制得。
可选地,所述氢氧化钾的浓度为0.1mol/L-1.0mol/L。
可选地,所述BiFeO3颗粒由硝酸铋、氯化铁和氨水反应制得。
可选地,所述氨水的浓度为0.1mol/L-1.0mol/L。
可选地,所述淀粉的质量为0.5-8wt%。
可选地,所述淀粉的质量为0.5wt%。
可选地,所述淀粉的质量为1.0wt%。
可选地,所述淀粉的质量为2.0wt%。
可选地,所述淀粉的质量为3.0wt%。
可选地,所述淀粉的质量为4.0wt%。
可选地,所述淀粉的质量为5.0wt%。
可选地,所述淀粉的质量为6.0wt%。
可选地,所述淀粉的质量为7.0wt%。
可选地,所述淀粉的质量为8.0wt%。
可选地,所述聚乙烯醇(PVA)溶液的质量浓度为5.0~8.0wt%。
可选地,所述聚乙烯醇(PVA)溶液的质量浓度为6.0wt%。
可选地,所述聚乙烯醇(PVA)溶液的质量浓度为7.0wt%。
可选地,所述造孔处理的温度为350℃、380℃、400℃、450℃;
可选地,所述脱胶处理的温度为450℃、500℃、550℃、600℃;
可选地,所述超声处理时间为30~80min,所述超声处理频率为20-60KHz。
可选地,所述超声处理时间上限为40min、50min、60min、70min、80min;所述超声处理时间下限为30min、40min、50min、60min、70min。
所述的Pd单原子BiFeO3压电多孔陶瓷于自供能高效制氢中的应用。
优选地,所述超声波的频率为10-60KHz。
优选地,所述超声波的频率上限为20KHz、30KHz、40KHz、50KHz、60KHz;所述超声波的频率下限为10KHz、20KHz、30KHz、40KHz、50KHz。
优选地,所述Pd单原子BiFeO3压电多孔陶瓷于车载自供能制氢中的应用。
优选地,在温度为1-95℃的条件下,对Pd单原子BiFeO3压电多孔陶瓷材料和氨硼烷水溶液形成的制氢反应体系施加机械振动或超声波振动实现氢气的制备。
优选地,一种自供能压电催化制氢方法,其包括以下步骤:
(1)将氨硼烷水溶液置于催化制氢反应器中,再向该氨硼烷水溶液中加入Pd单原子BiFeO3压电多孔陶瓷材料,形成制氢反应体系,之后密封所述反应器;
(2)将所述反应器的温度调节至1-95℃后将系统抽至真空,待所述反应器内达到真空状态后再将所述反应器内的温度调至20-30℃;
(3)对所述反应器内的制氢反应体系施加超声波,使所述制氢反应体系内发生反应,并产生氢气。
本发明中压电材料能将机械能转化为电能,其作用原理是利用材料在结构上的不对称性,在外力作用下原来电中性的材料产生了正负电荷中心不重合,从而导致材料的二端或二面带有不同的电荷。机械振动或超生振动实现机械能与电能的转变。
本发明提供的压电催化制氢的反应机理为:在合适的催化剂存在下,NH3BH3可以通过溶剂分解或热分解释放氢,如下式(I)所示:
NH3BH3(aq)+2H2O(l)=NH4 +(aq)+BO2 -(aq)+3H2(g)式(I)
在本发明中,Pd单原子BiFeO3压电多孔陶瓷材料是一种具有压电效应的催化剂。该催化剂在超声波振荡中产生压电效应,材料内部形成自建电场,使电子定向移动,产生的电子与水中质子H+发生反应产生氢气,产生的空穴与氢负离子H-结合产生氢气。
本发明制得的氢气为高纯氢气,不含一氧化碳、硫化氢等使燃料电池电极材料中毒的污染物。
在一具体实施例中,将本发明制得的Pd单原子BiFeO3压电多孔陶瓷材料制氢体系应用于行驶的汽车中,将汽车行驶过程中的振动能转化为电能,再经压电催化反应制得氢气,作为汽车燃料,实现自供能制氢。
在一具体实施例中,将本发明制得的Pd单原子BiFeO3压电多孔陶瓷材料制氢体系应用于噪声较大的生产车间,将车间生产时产生的声波转化为电能,实现自供能制氢。
与现有技术相比,本发明的优点包括:
(1)本发明提供的一种Pd单原子BiFeO3压电多孔陶瓷材料中Pd的含量较低同时具有较高的催化活性,降低了贵金属的使用,从而大大降低了生产成本。
(2)本发明提供的一种Pd单原子BiFeO3压电多孔陶瓷材料的制备方法简单易行、绿色环保,不排放对环境有害物质。
(3)本发明提供的一种Pd单原子BiFeO3压电多孔陶瓷材料可为氢燃料电池提供高纯氢,其中不含有一氧化碳、硫化氢、磷化氢、氯离子等使燃料电池中毒的气体。
具体实施方式
鉴于现有技术中的不足,本案发明人经长期研究和大量实践,得以提出本发明的技术方案。如下将对该技术方案、其实施过程及原理等作进一步的解释说明。
以下结合若干实施例对本发明的技术方案作进一步的解释说明。
本申请实施例中所用药品均为市售。
实施例1
所述一种Pd单原子BiFeO3压电多孔陶瓷的制备方法,包括以下步骤:
(1)制备BiFeO3颗粒:将氯化铋、氯化铁与氨水反应,生成BiFeO3颗粒;
(2)造粒:向步骤(1)制得的BiFeO3颗粒中分别加入0.5wt%的淀粉和一定量的聚乙烯醇溶液球磨造粒;
(3)制备陶坯:将步骤(2)制得的BiFeO3颗粒加入到20mm×20mm尺寸的模具中,用压膜机在10MPa压力下压制成陶坯;
(4)造孔与脱胶:将陶坯加热至400℃,恒温2h;继续升温至500℃条件下进行脱胶处理;
(5)成型:脱胶后在温度为860℃条件下处理0.5h,冷却后制得BiFeO3多孔陶瓷;
(6)极化处理:将BiFeO3多孔陶瓷片在3KV/mm电压下极化20min,放置24h后制得BiFeO3压电多孔陶瓷;
(7)Pd单原子BiFeO3压电多孔陶瓷的制备:将BiFeO3压电多孔陶瓷置于0.1mol/LPdCl2溶液中进行超声处理,即制得所述Pd单原BiFeO3压电多孔陶瓷。
制氢反应如下:
步骤一:提供浓度为0.05mol/L的100mL的NH3BH3溶液中,并置于反应器中,再向溶液中加入上述自供能压电多孔陶瓷,盖上石英玻璃板并密封反应器;
步骤二:将步骤一中的制氢系统和低温恒温槽连接好后密封处理,控制低温恒温槽温度为1℃后将系统内抽至真空,待系统内到达真空状态后再通过低温恒温槽将控制系统温度为25℃;
步骤三:将反应器置于28KHz超声波清洗器中,打开超声,将制氢系统调整至系统循环状态后进行实验,每隔一个小时通过气相色谱仪检测每个小时的氢气产量。
实施例2
所述一种Pd单原子BiFeO3压电多孔陶瓷的制备方法,包括以下步骤:
(1)制备BiFeO3颗粒:将氯化铋、硝酸铁与氢氧化钾反应,生成BiFeO3颗粒;
(2)造粒:向步骤(1)制得的BiFeO3颗粒中分别加入1.0wt%的淀粉和一定量的聚乙烯醇溶液球磨造粒;
(3)制备陶坯:将步骤(2)制得的BiFeO3颗粒加入到20mm×20mm尺寸的模具中,用压膜机在15MPa压力下压制成陶坯;
(4)造孔与脱胶:将陶坯加热至350℃,恒温1h;继续升温在温度为550℃下进行脱胶处理;
(5)成型:脱胶后在温度为880℃条件下处理0.1h,冷却后制得BiFeO3多孔陶瓷;
(6)极化处理:将BiFeO3多孔陶瓷片在4KV/mm电压下极化30min,放置24h后制得BiFeO3压电多孔陶瓷;
(7)Pd单原子BiFeO3压电多孔陶瓷的制备:将BiFeO3压电多孔陶瓷置于0.5mol/LPdCl2溶液中进行超声处理,即制得所述Pd单原BiFeO3压电多孔陶瓷。
制氢反应如下:
步骤一:提供浓度为0.05mol/L的100mL的NH3BH3溶液中,并置于反应器中,再向溶液中加入上述自供能压电多孔陶瓷,盖上石英玻璃板并密封反应器;
步骤二:将步骤一中的制氢系统和低温恒温槽连接好后密封处理,控制低温恒温槽温度为1℃后将系统内抽至真空,待系统内到达真空状态后再通过低温恒温槽将控制系统温度为25℃;
步骤三:将反应器置于28KHz超声波清洗器中,打开超声,将制氢系统调整至系统循环状态后进行实验,每隔一个小时通过气相色谱仪检测每个小时的氢气产量。
实施例3
所述一种Pd单原子BiFeO3压电多孔陶瓷的制备方法,包括以下步骤:
(1)制备BiFeO3颗粒:将硝酸铁、硝酸铋与氢氧化钠反应,生成BiFeO3颗粒;
(2)造粒:向步骤(1)制得的BiFeO3颗粒中分别加入2.0wt%的淀粉和一定量的聚乙烯醇溶液球磨造粒;
(3)制备陶坯:将步骤(2)制得的BiFeO3颗粒加入到20mm×20mm尺寸的模具中,用压膜机在20MPa压力下压制成陶坯;
(4)造孔与脱胶:将陶坯加热至450℃,恒温2h;继续升温至600℃下进行脱胶处理;
(5)成型:脱胶后在温度为900℃条件下处理0.5h,冷却后制得BiFeO3多孔陶瓷;
(6)极化处理:将BiFeO3多孔陶瓷片在4KV/mm电压下极化40min,放置24h后制得BiFeO3压电多孔陶瓷;
(7)Pd单原子BiFeO3压电多孔陶瓷的制备:将BiFeO3压电多孔陶瓷置于0.8mol/LPdCl2溶液中进行超声处理,即制得所述Pd单原BiFeO3压电多孔陶瓷。
制氢反应如下:
步骤一:提供浓度为0.05mol/L的100mL的NH3BH3溶液中,并置于反应器中,再向溶液中加入上述自供能压电多孔陶瓷,盖上石英玻璃板并密封反应器;
步骤二:将步骤一中的制氢系统和低温恒温槽连接好后密封处理,控制低温恒温槽温度为1℃后将系统内抽至真空,待系统内到达真空状态后再通过低温恒温槽将控制系统温度为25℃;
步骤三:将反应器置于28KHz超声波清洗器中,打开超声,将制氢系统调整至系统循环状态后进行实验,每隔一个小时通过气相色谱仪检测每个小时的氢气产量。
实施例4
所述一种Pd单原子BiFeO3压电多孔陶瓷的制备方法,包括以下步骤:
(1)制备BiFeO3颗粒:将硝酸铁、氯化铋与氨水反应,生成BiFeO3颗粒;
(2)造粒:向步骤(1)制得的BiFeO3颗粒中分别加入3.0wt%的淀粉和一定量的聚乙烯醇溶液球磨造粒;
(3)制备陶坯:将步骤(2)制得的BiFeO3颗粒加入到20mm×20mm尺寸的模具中,用压膜机在10MPa压力下压制成陶坯;
(4)造孔与脱胶:将陶坯加热至450℃,恒温1h;继续升温至600℃进行脱胶处理;
(5)成型:脱胶后在温度为950℃条件下处理0.5h,冷却后制得BiFeO3多孔陶瓷;
(6)极化处理:将BiFeO3多孔陶瓷片在3KV/mm电压下极化40min,放置24h后制得BiFeO3压电多孔陶瓷;
(7)Pd单原子BiFeO3压电多孔陶瓷的制备:将BiFeO3压电多孔陶瓷置于0.6mol/LPdCl2溶液中进行超声处理,即制得所述Pd单原BiFeO3压电多孔陶瓷。
制氢反应如下:
步骤一:提供浓度为0.05mol/L的100mL的NH3BH3溶液中,并置于反应器中,再向溶液中加入上述自供能压电多孔陶瓷,盖上石英玻璃板并密封反应器;
步骤二:将步骤一中的制氢系统和低温恒温槽连接好后密封处理,控制低温恒温槽温度为1℃后将系统内抽至真空,待系统内到达真空状态后再通过低温恒温槽将控制系统温度为25℃;
步骤三:将反应器置于28KHz超声波清洗器中,打开超声,将制氢系统调整至系统循环状态后进行实验,每隔一个小时通过气相色谱仪检测每个小时的氢气产量。
实施例5
所述一种Pd单原子BiFeO3压电多孔陶瓷的制备方法,包括以下步骤:
(1)制备BiFeO3颗粒:将硝酸铁、氯化铋与氨水反应,生成BiFeO3颗粒;
(2)造粒:向步骤(1)制得的BiFeO3颗粒中分别加入6.0wt%的淀粉和一定量的聚乙烯醇溶液球磨造粒;
(3)制备陶坯:将步骤(2)制得的BiFeO3颗粒加入到20mm×20mm尺寸的模具中,用压膜机在30MPa压力下压制成陶坯;
(4)造孔与脱胶:将陶坯加热至350℃,恒温1h;继续升温至600℃条件下进行脱胶处理;
(5)成型:脱胶后在温度为860℃条件下处理0.5h,冷却后制得BiFeO3多孔陶瓷;
(6)极化处理:将BiFeO3多孔陶瓷片在4KV/mm电压下极化40min,放置24h后制得BiFeO3压电多孔陶瓷;
(7)Pd单原子BiFeO3压电多孔陶瓷的制备:将BiFeO3压电多孔陶瓷置于1.0mol/LPdCl2溶液中进行超声处理,即制得所述Pd单原BiFeO3压电多孔陶瓷。
制氢反应如下:
步骤一:提供浓度为0.05mol/L的100mL的NH3BH3溶液中,并置于反应器中,再向溶液中加入上述自供能压电多孔陶瓷,盖上石英玻璃板并密封反应器;
步骤二:将步骤一中的制氢系统和低温恒温槽连接好后密封处理,控制低温恒温槽温度为1℃后将系统内抽至真空,待系统内到达真空状态后再通过低温恒温槽将控制系统温度为25℃;
步骤三:将反应器置于28KHz超声波清洗器中,打开超声,将制氢系统调整至系统循环状态后进行实验,每隔一个小时通过气相色谱仪检测每个小时的氢气产量。
实施例6
将实施例1~实施例5制得的Pd单原子BiFeO3压电多孔陶瓷制得的氢气经干燥后置于氢气纯度分析仪中检测不含有一氧化碳、硫化氢、磷化氢、氯离子等使燃料电池中毒的气体,且制得氢气均为高纯氢气。
应当理解,上述实施例仅为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种Pd单原子BiFeO3压电多孔陶瓷,其特征在于,包括BiFeO3压电多孔陶瓷基体以及均匀分散于压电多孔陶瓷表面的Pd单原子;
其中,所述Pd单原子的质量分数为0.01wt%-0.1wt%;
所述BiFeO3压电多孔陶瓷基体的孔径为0.01mm~0.1mm。
2.根据权利要求1所述的Pd单原子BiFeO3压电多孔陶瓷,其特征在于,所述Pd单原子还分散于所述BiFeO3压电多孔陶瓷基体的孔道壁面。
3.一种制备权利要求1-2中任一项所述的Pd单原子BiFeO3压电多孔陶瓷的方法,其特征在于,包括以下步骤:
(1)制备BiFeO3陶坯颗粒:将铋盐、铁盐与碱反应,生成BiFeO3陶坯颗粒;
(2)造粒:向步骤(1)制得的BiFeO3陶坯颗粒中分别加入0.5wt%-8wt%的淀粉和一定量的聚乙烯醇溶液球磨造粒;
(3)制备陶坯:将步骤(2)制得的BiFeO3陶坯颗粒加入到一定尺寸的模具中,用压膜机在10-30MPa压力下压制成陶坯;
(4)造孔与脱胶:将陶坯加热至350-450℃,恒温1-2h;继续升温进行脱胶处理;
(5)成型:脱胶后在温度为860℃~950℃条件下处理0.5h-2h,冷却后制得BiFeO3多孔陶瓷;
(6)极化处理:将BiFeO3多孔陶瓷片在3~5KV/mm电压下极化20-60min,放置24h后制得BiFeO3压电多孔陶瓷;
(7)Pd单原子BiFeO3压电多孔陶瓷的制备:将BiFeO3压电多孔陶瓷置于PdCl2溶液中进行超声处理,即制得所述Pd单原BiFeO3压电多孔陶瓷。
4.根据权利要求3所述的Pd单原子BiFeO3压电多孔陶瓷的制备方法,其特征在于,所述铋盐选自氯化铋、硝酸铋中的至少一种;
优选地,所述铁盐选自硝酸铁、氯化铁中的至少一种;
优选地,所述碱选自氢氧化钠、氢氧化钾和氨水中的至少一种。
5.根据权利要求3所述的Pd单原子BiFeO3压电多孔陶瓷的制备方法,其特征在于,所述聚乙烯醇(PVA)溶液的质量浓度为5.0wt%~8.0wt%。
6.根据权利要求3所述的Pd单原子BiFeO3压电多孔陶瓷的制备方法,其特征在于,所述脱胶处理的温度为500~600℃。
7.根据权利要求3所述的Pd单原子BiFeO3压电多孔陶瓷的制备方法,其特征在于,所述超声处理时间为30~80min,所述超声处理频率为20-60KHz。
8.由权利要求1-2中任一项中所述的Pd单原子BiFeO3压电多孔陶瓷或权利要求3-7任一项中所述制备的Pd单原子BiFeO3压电多孔陶瓷于自供能制氢中的应用。
9.如权利要求8所述的用途,其特征在于,所述超声波的频率为10-60KHz。
10.如权利要求8所述的用途,其特征在于,所述Pd单原子BiFeO3压电多孔陶瓷于车载自供能制氢中的应用。
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