CN111569892B - 铈基固溶体及其制备方法和用途 - Google Patents
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- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 78
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000006104 solid solution Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 230000008569 process Effects 0.000 title description 2
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 230000015556 catabolic process Effects 0.000 claims abstract description 11
- 238000006731 degradation reaction Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 abstract description 29
- 239000002184 metal Substances 0.000 abstract description 25
- 150000000703 Cerium Chemical class 0.000 abstract description 10
- 239000012716 precipitator Substances 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000000975 dye Substances 0.000 description 19
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 16
- 239000001099 ammonium carbonate Substances 0.000 description 16
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 14
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- -1 cerium ions Chemical class 0.000 description 8
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 8
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical group [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 8
- 229910000420 cerium oxide Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RMAKSEQFVRNWKO-UHFFFAOYSA-N zinc;cerium(3+);oxygen(2-) Chemical compound [O-2].[Zn+2].[Ce+3] RMAKSEQFVRNWKO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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- 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
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Abstract
本发明提供了一种铈基固溶体及其制备方法和用途。该铈基固溶体的制备方法包括如下步骤:(1)将可溶性铈盐和可溶性金属M盐形成混合溶液,将混合溶液与碱性沉淀剂反应,得到铈基固溶体的前驱体;(2)将铈基固溶体的前驱体在150~370℃焙烧,得到铈基固溶体。本发明的制备方法焙烧温度低,且所得铈基固溶体对有机染料的降解效果好。
Description
技术领域
本发明涉及一种铈基固溶体及其制备方法和用途。尤其涉及一种金属元素掺杂的铈基固溶体及其制备方法和用途。
背景技术
氧化铈是广泛应用的催化材料之一,具有萤石晶体结构的氧化铈中同时存在+3价和+4价铈离子,且其中的+3价和+4价铈离子可灵活转换,因而具有较高的储存和释放氧的功能。氧化铈为基体的金属材料广泛地应用于废水处理领域。有机染料废水中含有硝基物、胺类、吡啶等有毒有害物质,给环境造成的极大的污染,且难以降解处理。研究发现,将氧化铈中掺杂其他金属元素能够改善氧化铈的储氧能力和催化性能。制备铈基固溶体需要将前驱体在高温下进行焙烧,经过高温处理后的固溶体比表面积会下降。
CN1449863A公开了一种纳米铈锆基复合氧化物的制备方法:(1)将Ce、Zr和金属元素B的硝酸盐溶于水,制成溶液(I),金属元素B选自Ca、Sr、Ba、Mn、Al、Si或除Ce外的任一稀土元素;(2)取过量的双氧水和氨水溶于水中制成溶液(II);(3)将溶液(I)和溶液(II)加入到氨水溶液中,控制pH值在9.5~10.5,反应0.5~1小时后静止陈化5~30小时,经过滤、干燥后,在500~1000℃范围内焙烧2~6小时,得到铈锆基复合氧化物。该方法需要在500℃以上进行焙烧,影响对有机染料的催化性能。
CN1274416C公开了一种复合氧化物催化剂的制备方法,采用草酸盐共沉淀法制备而成。将草酸溶于水溶液或醇溶液,滴加到含有铈和铈以外的过渡金属的可溶性盐的溶液中,搅拌状态下老化,经离心分离、过夜干燥并在400~1000℃下焙烧2~6小时而制得,所得复合氧化物催化剂中铈含量为10~90%摩尔比,其余组分为过渡金属氧化物。该方法需要在较高的温度下进行焙烧,影响对有机染料的催化性能。
发明内容
有鉴于此,本发明的一个目在于提供一种铈基固溶体的制备方法,该制备方法焙烧温度低,且所得铈基固溶体对有机染料的催化性能高。
本发明的另一个目的在于提供一种铈基固溶体,该铈基固溶体对有机染料的催化性能高。
本发明的再一个目的在于提供一种铈基固溶体在降解有机染料中的用途。
上述目的通过如下技术方案实现。
一方面,本发明提供了一种铈基固溶体的制备方法,包括如下步骤:
(1)将可溶性铈盐和可溶性金属M盐形成混合溶液,将混合溶液与碱性沉淀剂反应,得到铈基固溶体的前驱体;
(2)将铈基固溶体的前驱体在150~370℃焙烧,得到铈基固溶体;
其中,金属M选自满足式(1)所示条件的金属元素:
(RCe-RM)/RCe<0.25 (1)
RCe表示四价铈离子的半径,RM表示金属M离子的半径。
根据本发明的铈基固溶体的制备方法,优选地,铈元素与金属M元素的摩尔比为(2~110):1。
根据本发明的铈基固溶体的制备方法,优选地,所述金属M选自镧、铕、钕、镍、钴、锌、镁中的一种或多种。
根据本发明的铈基固溶体的制备方法,优选地,所述碱性沉淀剂选自碳酸钠、碳酸氢钠、碳酸铵、碳酸氢铵、氨水中的一种或多种。
根据本发明的铈基固溶体的制备方法,优选地,混合溶液与碱性沉淀剂的反应温度为20~90℃,反应环境的pH值为6~9。
根据本发明的铈基固溶体的制备方法,优选地,焙烧时间为40~200min。
另一方面,本发明提供一种铈基固溶体,根据上述制备方法得到。
根据本发明的铈基固溶体,优选地,所述铈基固溶体对有机染料的降解率在90%以上。
再一方面,本发明提供一种铈基固溶体在降解有机染料中的用途。
根据本发明的用途,优选地,所述的有机染料为亚甲基蓝和/或刚果红。
本发明将形成的铈基固溶体的前驱体在较低的温度下进行焙烧,所制得的铈基固溶体对有机染料具有较高的催化性能。根据本发明优选的技术方法,采用合适的沉淀剂在适当的温度和pH环境中形成的前驱体更适合于在较低的温度下进行焙烧。
具体实施方式
下面结合具体实施例对本发明作进一步的说明,但本发明的保护范围并不限于此。
<制备方法>
本发明的铈基固溶体的制备方法包括如下步骤:(1)将可溶性铈盐和可溶性金属M盐形成混合溶液,将混合溶液与碱性沉淀剂反应,得到铈基固溶体的前驱体;(2)将铈基固溶体的前驱体低温焙烧,得到铈基固溶体。
在本发明中,可溶性铈盐可以为铈的硝酸盐、铈的氯化物、铈的硫酸盐或铈的醋酸盐中的一种或几种。
金属M选自满足式(1)所示条件的金属元素:
(RCe-RM)/RCe<0.25 (1)
其中,RCe表示四价铈离子的半径,RM表示金属M离子的半径。
优选地,金属M选自镧、铕、钕、镍、钴、锌、镁中的一种或多种。更优选地,金属M选自镍或钴中的至少一种。这样有利于提高铈基固溶体的催化性能。
在本发明中,铈元素和金属M元素的摩尔比可以为(2~110):1;优选为(4~99):1;更优选为(9~99):1。这样的掺杂量有助于提高铈基固溶体的催化性能。
可溶性金属M盐可以选自金属M的硝酸盐、金属M的氯化物、金属M的硫酸盐或金属M的醋酸盐中的一种或几种。
根据本发明的一个实施方式,混合溶液可以由可溶性铈盐溶液和可溶性金属M盐溶液混合而成。优选地,可溶性铈盐溶液为可溶性铈盐的水溶液,可溶性金属M盐溶液为可溶性金属M盐的水溶液。可溶性铈盐溶液的浓度可以为0.01~1.5mol/L;优选为0.02~1mol/L;更优选为0.2~1mol/L。可溶性金属M盐溶液的浓度可以为0.01~1.5mol/L;优选为0.02~1mol/L;更优选为0.2~1mol/L。
在本发明中,碱性沉淀剂选自碳酸钠、碳酸氢钠、碳酸铵、碳酸氢铵、氨水中的一种或多种。优选地,碱性沉淀剂选自碳酸氢铵、碳酸钠或氨水中的一种或多种。更优选地,碱性沉淀剂选自碳酸氢铵或碳酸钠中的一种。根据本发明的一个实施方式,碱性沉淀剂为碳酸钠水溶液。根据本发明的另一个实施方式,碱性沉淀剂为碳酸氢铵水溶液与氨水形成的混合物。混合物中,碳酸氢铵和NH3的摩尔比可以为(6~7):(3~4);优选为6.5~7:3~3.5。这样有助于形成适合在较低温度下进行焙烧的前驱体。
在本发明中,碱性沉淀剂可以以溶液的形式与混合溶液混合后进行反应。溶液中碱性物质的浓度可以为0.01~0.8mol/L;优选为0.03~0.5mol/L;最优选为0.03~0.07mol/L。根据本发明的一个实施方式,碱性沉淀剂为碳酸氢铵水溶液与氨水形成的混合物。混合物中,碳酸氢铵和NH3的摩尔比可以为(6~7):(3~4);优选为6.5~7:3~3.5。碳酸氢铵和NH3的总浓度可以为0.01~0.8mol/L;优选为0.03~0.5mol/L;最优选为0.03~0.07mol/L。
在本发明中,反应温度可以为20~90℃;优选为40~80℃;更优选为50~70℃。反应环境的pH值为6~9;优选为6.5~8;更优选为7~7.8。反应时间可以为0.5~4h;优选为1~3h;更优选为1.5~2.5h。这样有助于形成适合于在较低温度下进行焙烧的前驱体。
混合溶液与碱性沉淀剂反应得到的反应产物可以经过过滤、热水洗涤和干燥从而得到铈基固溶体的前驱体。干燥的温度可以为30~80℃;优选为40~80℃;更优选为50~70℃。干燥的时间可以为2~8h;优选为2~6h;更优选为3~5h。
将铈基固溶体的前驱体焙烧,得到铈基固溶体。焙烧温度可以为150~370℃;优选为200~350℃;更优选为300~350℃。焙烧的时间可以为30~200min;优选为100~180min;更优选为110~170min。这样可以有助于得到催化性能高的固溶体。铈基固溶体对有机染料的降解率大于90%;优选地,大于95%;更优选地,大于98%。有机染料可以为亚甲基蓝或刚果红。
根据本发明的一个实施方式,将可溶性铈盐和可溶性镍盐形成混合溶液(铈元素与镍元素的摩尔比为(95~105):1),在40~80℃,pH值为6.5~8的条件下与碳酸氢铵溶液进行反应得到反应产物;将反应产物过滤,热水洗涤,然后干燥,得到铈基固溶体的前驱体;将铈基固溶体的前驱体在300~350℃下焙烧110~170min得到铈基固溶体。
根据本发明的另一个实施方式,将可溶性铈盐和可溶性钴盐形成混合溶液(铈元素与钴元素的摩尔比为(5~13):1),在40~80℃,pH值为6.5~8的条件下与碳酸钠溶液进行反应得到反应产物;将反应产物过滤,热水洗涤,然后干燥,得到铈基固溶体的前驱体;将铈基固溶体的前驱体在300~350℃下焙烧110~170min得到铈基固溶体。
<铈基固溶体>
本发明的铈基固溶体采用上述方法制备得到。铈基固溶体对有机染料的降解率大于90%;优选地,大于95%;更优选地,大于98%。有机染料可以为亚甲基蓝或刚果红。
<用途>
本发明的铈基固溶体对有机染料具有较高的催化性能,因而可以用于降解有机染料。优选地,有机染料选自亚甲基蓝和/或刚果红。
下面介绍实施例的测试方法:
降解率:采用紫外-可见分光光度计在最大吸收波长处分别检测未降解染料和经过催化剂降解的染料,计算其降解率。
实施例1~2和对比例1~3
将99mL硝酸铈溶液(浓度为0.2mol/L)和1mL金属M的硝酸盐溶液(浓度为0.2mol/L)混合均匀,形成混合溶液;将混合溶液与沉淀剂在60℃且pH为7.8的条件下反应2h,过滤得到固体产物;将固体产物用热水洗涤,然后于60℃下干燥4h,得到铈基固溶体的前驱体。
将铈基固溶体的前驱体焙烧120min,得到铈基固溶体。将30mg铈基固溶体与100mL亚甲基蓝溶液(浓度为50mg/L)混合均匀,然后在可见光下辐射0.5h。检测亚甲基蓝的降解率。
表1
实施例3~4和对比例4~6
将90mL氯化铈溶液(浓度为1mol/L)和10mL金属M的氯化物溶液(浓度为1mol/L)混合均匀,形成混合溶液;将混合溶液与沉淀剂在60℃且pH为7的条件下反应2h,过滤得到固体产物;将固体产物用热水洗涤,然后于60℃下干燥4h,得到铈基固溶体的前驱体。
将铈基固溶体的前驱体焙烧150min,得到铈基固溶体。将30mg铈基固溶体与100mL亚甲基蓝溶液(浓度为50mg/L)混合均匀,然后在可见光下辐射0.5h。检测亚甲基蓝的降解率。
表2
实施例5
将95mL硫酸铈溶液(浓度为0.02mol/L)和5mL硫酸锌溶液(浓度为0.02mol/L)混合均匀,形成混合溶液;将混合溶液与碱性物质总浓度为0.5mol/L的碳酸氢铵水溶液与氨水形成的混合物(碳酸氢铵:NH3的摩尔浓度比为7:3)在60℃且pH为8的条件下反应2h,过滤得到固体产物;将固体产物用热水洗涤,然后于60℃下干燥4h,得到锌-氧化铈固溶体的前驱体。
将锌-氧化铈固溶体的前驱体在350℃下焙烧60min,得到锌-氧化铈固溶体。将30mg锌-氧化铈固溶体与100mL刚果红溶液(浓度为50mg/L)混合均匀,然后在可见光下辐射1h。检测刚果红的降解率为95%。
实施例6
将80mL硝酸铈溶液(浓度为0.15mol/L)、10mL硝酸镁溶液(浓度为0.15mol/L)和10mL硝酸钴溶液(浓度为0.15mol/L)混合均匀,形成混合溶液;将混合溶液与碱性物质总浓度为1.5mol/L的碳酸氢铵水溶液与氨水形成的混合物(碳酸氢铵:NH3的摩尔浓度比为6:4)在60℃且pH为8.1的条件下反应2h,过滤得到固体产物;将固体产物用热水洗涤,然后于60℃下干燥4h,得到镁-钴-氧化铈固溶体的前驱体。
将镁-钴-氧化铈固溶体的前驱体在350℃下焙烧150min,得到镁-钴-氧化铈固溶体。将30mg镁-钴-氧化铈固溶体与100mL刚果红溶液(浓度为50mg/L)混合均匀,然后在可见光下辐射1h。检测刚果红的降解率为93%。
本发明并不限于上述实施方式,在不背离本发明的实质内容的情况下,本领域技术人员可以想到的任何变形、改进、替换均落入本发明的范围。
Claims (1)
1.一种铈基固溶体的制备方法,其特征在于,包括如下步骤:
将90mL氯化铈溶液和10mL氯化钴溶液混合均匀,形成混合溶液;将混合溶液与0.05mol/L碳酸钠溶液在60℃且pH为7的条件下反应2h,过滤得到固体产物;将固体产物用热水洗涤,然后于60℃下干燥4h,得到铈基固溶体的前驱体;其中,所述氯化铈溶液的浓度为1mol/L,所述氯化钴溶液的浓度为1mol/L;
将铈基固溶体的前驱体在350℃下焙烧150min,得到铈基固溶体;
30mg铈基固溶体与100mL浓度为50mg/L的亚甲基蓝溶液混合均匀,然后在可见光下辐射0.5h,测得亚甲基蓝的降解率为99%。
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