CN106423177B - 表面石墨化的微米金刚石负载钙钛矿复合材料及制备方法 - Google Patents
表面石墨化的微米金刚石负载钙钛矿复合材料及制备方法 Download PDFInfo
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 57
- 239000010432 diamond Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 16
- 239000010439 graphite Substances 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005087 graphitization Methods 0.000 claims abstract description 7
- -1 alkyl phenol Chemical compound 0.000 claims abstract description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 239000000908 ammonium hydroxide Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000003483 aging Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- LITYQKYYGUGQLY-UHFFFAOYSA-N iron nitric acid Chemical compound [Fe].O[N+]([O-])=O LITYQKYYGUGQLY-UHFFFAOYSA-N 0.000 claims 1
- 239000003595 mist Substances 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
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- 229910001960 metal nitrate Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 235000015165 citric acid Nutrition 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 239000002113 nanodiamond Substances 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- NDTZMEKCGHOCBU-UHFFFAOYSA-N strontium;dioxido(dioxo)manganese Chemical compound [Sr+2].[O-][Mn]([O-])(=O)=O NDTZMEKCGHOCBU-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
一种表面石墨化的微米金刚石负载钙钛矿复合材料,它是一种粒径为10~20nm的钙钛矿颗粒均匀地分布在粒径为1~20μm的表面石墨化的微米金刚石上复合材料,其制备方法主要是对微米金刚石进行净化处理,再将微米金刚石进行表面石墨化,然后将其制备成悬浮液;将硝酸盐、柠檬酸和烷基酚聚氧乙烯醚加入到上述悬浮液中,使金属硝酸盐水解形成溶胶,再聚合生成凝胶,最后经干燥、焙烧得到表面石墨化的微米金刚石负载钙钛矿复合材料。本发明工艺简单、成本低,化学均匀性好,增加催化活性位点,使催化剂具有更好的催化能力;由于表层石墨的导电性,能够起到电子传递通道的作用,使得复合材料具有良好的电导率。
Description
技术领域 本发明涉及一种电催化材料及其制备方法。
背景技术 在金属-空气电池中,钙钛矿型氧化物(ABO3)由于结构稳定、晶格结构中存在氧空位、且价格低廉等优点成为一种被广泛研究的空气电极催化剂。空气电极反应是在气、固、液三相界面上进行,电极内部能否形成尽可能多的有效三相界面将影响电催化剂的利用率和电极的传质过程,而且电解质溶液可以接触的活性位点越大,电池的储电容量就越高,所以其催化剂载体材料的研究一直是关注的焦点。金刚石作为一种典型的原子晶体,其禁带宽度高达5.47eV,导电能力很差,过去普遍认为它是一种绝缘材料。但研究发现,可以通过掺杂,表面官能化,表面修饰及表面石墨化来提高金刚石的导电能力,使其可以在多种电化学技术中显现出较好的性能,包括:抗腐蚀性,低背景电流和高的响应灵敏度等。对于金刚石电化学载体材料来说,目前主要的研究对象为硼掺杂金刚石和纳米金刚石。但含硼金刚石的表面积相对较小,且合成成本高,产量低,使得含硼金刚石在大规模生产、应用上仍旧受限。对于纳米金刚石,由于粒度分布不集中,因此与负载物的亲和力差,使负载物容易发生迁移和团聚,并且纳米金刚石颗粒本身也易发生团聚。
发明内容 本发明的目的在于提供一种工艺简单、成本低、化学均匀性好,反应过程易于控制、具有良好的电导率的表面石墨化的微米金刚石负载钙钛矿复合材料及制备方法。
本发明的表面石墨化的微米金刚石负载钙钛矿复合材料是一种粒径为10~20nm的钙钛矿纳米粒子均匀地分布在粒径为1~20μm的金刚石微粉上的复合材料。
本发明的制备方法如下:
1、微米金刚石的净化处理:
将粒径为1~20微米的金刚石微粉加入到含量为25~28%的分析纯氨水中,加入量为每升氨水中加入金刚石微粉20克,搅拌均匀后,超声振荡1小时,频率为40kHz,功率180W,依次用无水乙醇和蒸馏水漂洗三遍,40~50℃烘干, 制得干净的金刚石微粉。
2、微米金刚石的表面石墨化:
将上述干净的金刚石微粉放入放电等离子体烧结(SPS)系统的石墨模具中,在石墨模具内壁以及上下压头之间垫上石墨纸,并在模具外表面包裹碳毡,待系统的真空度达到10-3Pa后,调节加热电流,使其升温速率为100℃/min,达到1300~1500℃后,保温15~40min后随炉冷却至室温取出,制得表面石墨化的金刚石微粉。
3、表面石墨化的微米金刚石负载钙钛矿复合材料的制备:
按100ml无水乙醇加入0.49~1.52g金刚石微粉的比例关系,将上述表面石墨化的金刚石微粉加入到无水乙醇中,经超声分散60min后制成悬浮液;按摩尔比为1:1的比例将甲组硝酸盐中的一种和乙组硝酸盐中的一种加入到上述金刚石悬浮液中,两种硝酸盐质量的和与金刚石微粉的质量比为0.4~2.9:1,其中甲组硝酸盐包括硝酸镧、硝酸锶和硝酸钡,乙组硝酸盐包括硝酸锰、硝酸铁和硝酸镍;磁力搅拌30min后,加入与硝酸盐质量比分别为2:1的柠檬酸和3:20的烷基酚聚氧乙烯醚(OP-10),待柠檬酸完全溶解后,向溶液中滴加氨水调节其pH值为10~11,得到所需的前驱体溶液;将该前驱体溶液在水浴下50~70℃陈化8~24h后,在80℃干燥箱中烘干并装入坩埚。先在空气中350℃煅烧2h,使柠檬酸盐充分分解,并随炉冷却至室温,然后将煅烧后的粉体放入真空炉中,以1℃/min的升温速度升到550~650℃煅烧2~5h,随炉冷却至室温,即得到表面石墨化的微米金刚石负载钙钛矿复合材料。
本发明与现有技术相比具有如下优点:
1、本发明制备的表面石墨化的微米金刚石负载钙钛矿复合材料,钙钛矿纳米粒子在表面石墨化的微米金刚石上分布较均匀。
2、工艺简单、成本低、化学均匀性好、反应过程易于控制。
3、表面石墨化的微米金刚石是一种核壳结构,它同时具有稳定的核心和导电的表面,将其作为载体物质可以提高钙钛矿纳米粒子的分散度,增多催化活性位点,使催化剂具有更好的催化能力;由于表层石墨的导电性,能够起到电子传递通道的作用,使得复合材料具有良好的电导率。
4、制备的复合材料和钙钛矿材料作为锌-空气电池中空气电极的氧还原催化剂进行对比,本复合材料降低了阴极极化,使得氧还原过程的开始电位和半波电位均分别向正的方向移动了0.35V和0.2V,且动力学电流密度增大了约60%;同时该复合材料使得锌-空气电池在放电电压为1.38V,放电电流密度为150mA/cm2时,持续稳定的放电时间长达55h,大大地提高了电池的放电容量。
附图说明
图1是本发明实施例1获得的表面石墨化的微米金刚石负载铁酸镧复合材料的扫描电镜图。
图2是本发明实施例2获得的表面石墨化的微米金刚石负载镍酸钡矿复合材料的扫描电镜图。
具体实施方式
实施例1
1、微米金刚石的净化处理:
将粒径为1~2微米的金刚石微粉加入到含量为25%的分析纯氨水中,加入量为每升氨水中加入金刚石微粉20克,搅拌均匀后,超声振荡1小时(频率为40kHz、功率180W),依次用无水乙醇和蒸馏水漂洗三遍,50℃烘干,制得干净的金刚石微粉。
2、微米金刚石的表面石墨化:
将上述干净的金刚石微粉10克放入放电等离子体烧结(SPS)系统的石墨模具中,在石墨模具内壁以及上下压头之间垫上石墨纸,并在模具外表面包裹碳毡,待系统的真空度达到10-3Pa后,调节加热电流,使其升温速率为100℃/min。达到1350℃后,保温40min后随炉冷却至室温取出,制得表面石墨化的金刚石微粉。
3、表面石墨化的微米金刚石负载钙钛矿复合材料的制备:
将上述表面石墨化的金刚石微粉0.97g,加入100ml无水乙醇中,经超声分散60min后制成悬浮液;将硝酸镧1.73g和硝酸铁0.72g加入到上述金刚石悬浮液中,磁力搅拌30min后,加入4.9g柠檬酸和0.37g烷基酚聚氧乙烯醚(OP-10),待柠檬酸完全溶解后,向溶液中滴加氨水调节其pH值为10,得到所需的前驱 体溶液;将该前驱体溶液在水浴下70℃陈化8h后,在80℃干燥箱中烘干并装入坩埚;先在空气中350℃煅烧2h,使柠檬酸盐充分分解,并随炉冷却至室温,然后将煅烧后的粉体放入真空炉中,以1℃/min的升温速度升到600℃煅烧3h,随炉冷却至室温,得到表面石墨化的微米金刚石负载铁酸镧复合材料,其中铁酸镧的负载量为50%。
如图1所示,制得的石墨化的微米金刚石表面生长了大量的铁酸镧纳米粒子,复合材料的整体形貌为苔藓状,纳米铁酸镧粒子在表面石墨化的1~2微米的金刚石上分布较均匀,XRD分析表明为钙钛矿结构,属正交晶系,平均粒径约为20nm。
实施例2
1、微米金刚石的净化处理:
将粒径为1~2微米的金刚石微粉加入到含量为28%的分析纯氨水中,加入量为每升氨水中加入金刚石微粉20克,搅拌均匀后,超声振荡1小时(频率为40kHz、功率180W),依次用无水乙醇和蒸馏水漂洗三遍,50℃烘干,制得干净的金刚石微粉。
2、微米金刚石的表面石墨化:
将上述干净的金刚石微粉10克放入放电等离子体烧结(SPS)系统的石墨模具中,在石墨模具内壁以及上下压头之间垫上石墨纸,并在模具外表面包裹碳毡,待系统的真空度达到10-3Pa后,调节加热电流,使其升温速率为100℃/min。达到1500℃后,保温15min后随炉冷却至室温取出,制得表面石墨化的金刚石微粉。
3、表面石墨化的微米金刚石负载钙钛矿复合材料的制备:
将上述表面带有氨基团的金刚石微粉0.49g,加入到100mL无水乙醇中,经超声分散60min后制成金刚石悬浮液,将硝酸钡0.26g和硝酸镍0.29g加入到上述金刚石悬浮液中,磁力搅拌30min后,加入1.1g柠檬酸和0.08g烷基酚聚氧乙烯醚(OP-10),待柠檬酸完全溶解后,向溶液中滴加氨水调节其pH值为11,得到所需的钙钛矿/金刚石前驱体溶液;将该前驱体溶液在水浴下50℃陈化24h后,在80℃干燥箱中烘干并装入坩埚;先在空气中350℃煅烧2h,使柠檬酸 盐充分分解,并随炉冷却至室温,然后将煅烧后的粉体放入真空炉中,以1℃/min的升温速度升到550℃煅烧5h,随炉冷却至室温,得到表面石墨化的微米金刚石负载镍酸钡复合材料,其中镍酸钡的负载量为33%。
如图2所示,制得的石墨化的微米金刚石表面生长了大量的镍酸钡纳米粒子,复合材料的整体形貌为海葵状,纳米镍酸钡粒子在表面石墨化的1~2微米的金刚石上分布较均匀,XRD分析表明为钙钛矿结构,属正交晶系,平均粒径约为10nm。
实施例3
1、微米金刚石的净化处理:
将粒径为15~20微米的金刚石微粉加入到含量为26%的分析纯氨水中,加入量为每升氨水中加入金刚石微粉20克,搅拌均匀后,超声振荡1小时(频率为40kHz、功率180W),依次用无水乙醇和蒸馏水漂洗三遍,40℃烘干,制得干净的金刚石微粉。
2、微米金刚石的表面石墨化:
将上述干净的金刚石微粉10克放入放电等离子体烧结(SPS)系统的石墨模具中,在石墨模具内壁以及上下压头之间垫上石墨纸,并在模具外表面包裹碳毡,待系统的真空度达到10-3Pa后,调节加热电流,使其升温速率为100℃/min。达到1400℃后,保温25min后随炉冷却至室温取出,制得表面石墨化的金刚石微粉。
3、表面石墨化的微米金刚石负载钙钛矿复合材料的制备:
将上述表面带有氨基团的金刚石微粉1.52g,加入到100mL无水乙醇中,经超声分散60min后制成金刚石悬浮液,将硝酸锶0.42g和硝酸锰0.5g加入到上述金刚石悬浮液中,磁力搅拌30min后,加入1.84g柠檬酸和0.14g烷基酚聚氧乙烯醚(OP-10),待柠檬酸完全溶解后,向溶液中滴加氨水调节其pH值为11,得到所需的钙钛矿/金刚石前驱体溶液。将该前驱体溶液在水浴下60℃陈化12h后,在80℃干燥箱中烘干并装入坩埚。先在空气中350℃煅烧2h,使柠檬酸盐充分分解,并随炉冷却至室温,然后将煅烧后的粉体放入真空炉中,以1℃/min的升温速度升到650℃煅烧2h,随炉冷却至室温,得到表面石墨化的微米金刚 石负载锰酸锶复合材料,其中锰酸锶的负载量为20%。
Claims (3)
1.一种表面石墨化的微米金刚石负载钙钛矿复合材料,其特征在于:它是一种粒径为10~20nm的钙钛矿纳米粒子均匀地分布在粒径为1~20μm的金刚石微粉上的复合材料。
2.权利要求1的表面石墨化的微米金刚石负载钙钛矿复合材料的制备方法,其特征在于:
(1)微米金刚石的净化处理:
将粒径为1~20微米的金刚石微粉加入到含量为25~28%的分析纯氨水中,加入量为每升氨水中加入金刚石微粉20克,搅拌均匀后,超声振荡1小时,频率为40kHz,功率180W,依次用无水乙醇和蒸馏水漂洗三遍,40~50℃烘干,制得干净的金刚石微粉;
(2)微米金刚石的表面石墨化:
将上述干净的金刚石微粉放入放电等离子体烧结(SPS)系统的石墨模具中,在石墨模具内壁以及上下压头之间垫上石墨纸,并在模具外表面包裹碳毡,待系统的真空度达到10- 3Pa后,调节加热电流,使其升温速率为100℃/min,达到1300~1500℃后,保温15~40min后随炉冷却至室温取出,制得表面石墨化的金刚石微粉;
(3)表面石墨化的微米金刚石负载钙钛矿复合材料的制备:
按100ml无水乙醇加入0.49~1.52g金刚石微粉的比例,将上述表面石墨化的金刚石微粉加入到无水乙醇中,经超声分散60min后制成悬浮液;按摩尔比为1:1的比例将甲组硝酸盐中的一种和乙组硝酸盐中的一种加入到上述金刚石悬浮液中,两种硝酸盐质量的和与金刚石微粉的质量比为0.4~2.9:1,磁力搅拌30min后,加入与两种硝酸盐质量和的比分别为2:1的柠檬酸和3:20的烷基酚聚氧乙烯醚,待柠檬酸完全溶解后,向溶液中滴加氨水调节其pH值为10~11,得到所需的前驱体溶液;将该前驱体溶液在水浴下50~70℃陈化8~24h后,在80℃干燥箱中烘干并装入坩埚,先在空气中350℃煅烧2h,使柠檬酸盐充分分解,并随炉冷却至室温,然后将煅烧后的粉体放入真空炉中,以1℃/min的升温速度升到550~650℃煅烧2~5h,随炉冷却至室温,即得到表面石墨化的微米金刚石负载钙钛矿复合材料。
3.根据权利要求2所述的表面石墨化的微米金刚石负载钙钛矿复合材料的制备方法,其特征在于:所述甲组硝酸盐包括硝酸镧、硝酸锶和硝酸钡,乙组硝酸盐包括硝酸锰、硝酸铁和硝酸镍。
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