CN109126889A - 一种适于电催化水氧化的锰氧化物/金属卟啉复合层状夹心纳米材料 - Google Patents
一种适于电催化水氧化的锰氧化物/金属卟啉复合层状夹心纳米材料 Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910001868 water Inorganic materials 0.000 title claims abstract description 35
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000001301 oxygen Substances 0.000 title claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 13
- 239000002086 nanomaterial Substances 0.000 title abstract description 10
- 229910006364 δ-MnO2 Inorganic materials 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 21
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- 238000000034 method Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 239000011229 interlayer Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 2
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 150000007529 inorganic bases Chemical class 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000007848 Bronsted acid Substances 0.000 claims 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000011565 manganese chloride Substances 0.000 claims 1
- 229910001437 manganese ion Inorganic materials 0.000 claims 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229940038773 trisodium citrate Drugs 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- GFERWFAWHAQLLF-UHFFFAOYSA-N [N]1C2=CC=C1C=C(N1)C=C(N)C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 Chemical class [N]1C2=CC=C1C=C(N1)C=C(N)C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 GFERWFAWHAQLLF-UHFFFAOYSA-N 0.000 abstract description 3
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical class O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 5
- 238000004502 linear sweep voltammetry Methods 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 230000010718 Oxidation Activity Effects 0.000 description 4
- 229940075397 calomel Drugs 0.000 description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
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- 229910052697 platinum Inorganic materials 0.000 description 4
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- 235000009566 rice Nutrition 0.000 description 2
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
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- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
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Abstract
本发明公开了一种适于电催化水氧化的锰氧化物/卟啉复合层状夹心纳米材料的制备方法,属于光电催化分解水制氢催化材料领域。其制备方法为:通过使用络合剂合成高纯的水钠锰矿型δ‑MnO2,然后剥离成单层的水钠锰矿型δ‑MnO2薄片。通过合成带有正电性的氨基卟啉,将两者置于烧杯中搅拌,让其重组为新型的层状夹心结构的纳米导电复合催化材料。本发明所得材料展现出优越了电催化水氧化(OER)性能,在5mA cm‑2的电流密度时,电势保持在0.91V,相比水钠锰矿型δ‑MnO2提高了很多,并且在大电流密度(10mA cm‑2)的条件下持续时间达4000s,能保持很高的稳定性。
Description
技术领域
本发明涉及一种适于电催化水氧化的锰氧化物/金属卟啉复合层状夹心纳米材料的制备方法及应用性能。
背景技术
经济和社会的发展,人类对能源需求不断增加,煤,石油,天然气等传统能源日趋枯竭。高效,清洁,可再生的新能源已得到世界各国的高度关注,在众多制氢技术中,利用太阳能进行光电催化分解水制氢是最佳途径。这个过程需要大量的电子和质子做为还原剂。而水氧化过程可以为这个过程提供充足的电子和质子。因此水氧化过程是制氢技术的关键步骤。但是水氧化过程存在热力学不利条件,需要外界提供更高的能量。因此促进水氧化过程,必须研制出高效,稳定,廉价的电催化剂。但是现在性能较好的水氧化电催化剂如Pt,RuO2和IrO2价格昂贵,自然界储量小,限制了其商业应用。
δ-MnO2是一种层间含有阳离子的层状无机材料,它的基本结构为锰氧八面体,它们以共棱和共边的方式结合在一起。依照化学理论来说,δ-MnO2中锰元素的化合价应该以+4价存在,但由于受到各种制备及条件因素的影响,致使层间出现结构缺陷,这样就导致了一部分的Mn4+被Mn3+取代,从而致使整个片层呈现为负电性。因此层间会存在一些阳离子以此来中和负电性,使整个层间保持为电中性,通常存在于层间的阳离子为Na+。此外,也会有一些其他的阳离子或一些水分子存在于层间,两者都有稳定δ-MnO2层状结构的作用。在材料应用方面,δ-MnO2具有很多优势,比如它的价格低廉,对环境没有污染,因此受到广大科研工作者的关注。但是,δ-MnO2由于导电率低,循环性能差,限制其广泛的应用。金属卟啉化合物具有优异的电子结构及光电性能,它对光和热具有很好的稳定性,使其在生命科学,药物化学,光化学,分析化学,电化学有重要的应用前景。此外,将金属卟啉引入δ-MnO2层间既可以增强其稳定性和改善电导率的特点,也可以优化循环性能差的缺点。考虑到δ-MnO2特殊的层状结构,可以通过减小层间的作用力,以此让片层得到分离,从而得到单片层的δ-MnO2。然后引入带正电的金属卟啉分子。运用剥离/重组技术,合成具有金属卟啉插层的δ-MnO2的复合材料。
本发明首先通过使用络合剂合成高纯的δ-MnO2,然后将产物至于酸性溶液中进行H+的交换,其后再加入四甲基氢氧化铵,使四甲基铵离子与H+交换,致使层间距得到膨胀,随后再用去离子水冲洗,得到剥离态的单层δ-MnO2薄片。通过合成带有正电性的5,10,15,20-四(4-氨基苯基)锰卟啉,将两者置于烧杯中搅拌,让其重组为新型的导电复合材料。这样将带有正电荷的氨基卟啉嵌入到层状MnO2的层间,既能改善层状MnO2的结构稳定性和电导率,又能降低导电有机物的制备成本,从而增强其电催化水氧化性能。
对锰氧化物/金属卟啉复合层状夹心纳米材料进行了水氧化性能测试,该复合纳米材料展现出优越了OER性能,在5mA cm-2时,电势大小为V=0.91,其电催化活性比δ-MnO2大幅提高,通过计时电流测试,新材料也在4000s内表现出优秀的稳定性。
发明内容
为了弥补现有技术的不足,本发明首要目的是提供一种锰氧化物/金属卟啉复合层状夹心纳米电催化水氧化材料的制备方法。本发明另一目的是提供上述复合纳米材料作为电催化水氧化的应用性能。
本发明通过以下技术方案实现:
(1)锰氧化物/卟啉复合纳米材料的制备
(a)将MnSO4·H2O等无机锰盐和络合剂如EDTA-2Na溶于去离子水中,缓慢加入为NaOH并搅拌,得到高纯水钠锰矿型δ-MnO2;(b)先将制备好的水钠锰矿型δ-MnO2放入H+浓度为0.1-10mol/L的酸性溶液中搅拌,抽滤,干燥,研磨,制备出不含碱金属的δ-MnO2;再将产物分散到四甲基氢氧化铵等有机碱性溶液中,搅拌,离心,干燥,得到层片剥离的δ-MnO2;(c)将单层片的δ-MnO2加入到一定浓度的5,10,15,20-四(4-氨基苯基)锰卟啉溶液中搅拌反应,即得到重新自组装的、金属卟啉插层的、层状夹心的锰氧化物/金属卟啉复合纳米催化剂。
制备路线如图1所示。
(2)电催化水氧化的应用
锰氧化物/金属卟啉复合纳米催化剂的电催化水氧化活性通过三电极体系检测,其中旋转圆盘电极作为工作电极,铂电极作为对电极,甘汞电极作为参比电极。具体的工作电极制作步骤为:将5mg样品分散在980μL乙醇溶液中,加入20μL 5%的Nafion溶液,然后将催化剂浆料涂敷在旋转圆盘电极上,用1M的KOH作为电解液。该复合催化材料相比δ-MnO2展现出了更优越的催化水氧化性能,在线性扫描伏安法测试中,电流为5mA cm-2时,电势大小为V=0.91;计时电流测试中,复合催化材料在4000s内表现出了优秀的稳定性。
与现有技术相比,本发明具有如下优点:
(1)本发明将带有正电荷的氨基卟啉嵌入到层状MnO2的层间,能改善层状MnO2的结构稳定性和电导率,显著提升电催化活性。
(2)本发明所用的原料价格低廉,工艺简单无污染,具有大规模工业生产的潜能。
(3)本发明的锰氧化物/金属卟啉复合纳米材料用于电催化水氧化时,相比δ-MnO2展现出更优越了水氧化性能。
附图说明
图1为从水钠锰矿型δ-MnO2制备锰氧化物/金属卟啉复合层状夹心纳米材料的路线图示意;
图2分别是水钠锰矿型δ-MnO2,剥离后的水钠锰矿型δ-MnO2,酸化后的水钠锰矿型δ-MnO2,MnTAPP@bir的XRD图;
图3a,3b分别为水钠锰矿型δ-MnO2与酸化后的水钠锰矿型δ-MnO2,水钠锰矿型δ-MnO2与MnTAPP@bir的红外图谱;
图4a,4b为水钠锰矿型δ-MnO2的SEM图;4c,4d为MnTAPP@bir的SEM图;
图5a,5b为剥离后的水钠锰矿型δ-MnO2的TEM图;图5c,5d为MnTAPP@bir的TEM图;
图6为水钠锰矿型δ-MnO2和MnTAPP@bir的循环伏安图;
图7为MnTAPP@bir和水钠锰矿型δ-MnO2的LSV曲线;
图8为MnTAPP@bir和水钠锰矿型δ-MnO2的计时电流曲线。
具体实施方式
下面结合实施例对本发明作进一步详细描述,但本发明的实施方式不限于此。
实施例1
称取1.35g MnSO4·H2O和3.0EDTA-2Na溶于去离子水中,搅拌30min得到白色悬浊溶液,称为Sa。将1.2gNaOH溶于50ml去离子水中搅拌至完全溶解,称为Sb。快速搅拌下,将Sb缓慢滴加到Sa中,滴加完毕后继续搅拌2h后,过滤沉淀,用去离子水洗涤数次,后置真空干燥箱40℃下放置12h最后得到水钠锰矿型δ-MnO2粉末(XRD、IR、SEM的测试结果分别如图2,图3,图4)。称取2g的水钠锰矿型δ-MnO2与300ml 1mol/L HNO3溶液混合于室温下搅拌12h,抽滤,将沉淀洗涤到中性,70℃干燥,研磨,最后得到没有碱金属离子的酸化水钠锰矿型δ-MnO2(XRD、IR的测试结果如图2,图3)。称取1g酸化后的水钠锰矿型δ-MnO2,将其分散在120ml的去离子水中,再加入12ml四甲基氢氧化铵,在室温中搅拌120h,将混合液在12000rpm下离心30min,将得到的固体用去离子水冲洗三次,在70℃干燥后,得到剥离态δ-MnO2(XRD、TEM的测试结果分别如图2,图4)。称取5,10,15,20-四(4-氨基苯基)锰卟啉粉末0.0679g与0.4g剥离态δ-MnO2于100ml 50℃去离子水中搅拌24h,剥离态δ-MnO2层片与锰卟啉发生自组装反应,形成复合层状夹心纳米材料,然后过滤,用去离子水冲洗3次,干燥,最后得到产物(XRD、IR、SEM、TEM的测试结果分别如图2,图3,图4,图5)。
产物的电催化水氧化活性通过三电极体系检测,旋转圆盘电极作为工作电极,铂电极作为对电极,甘汞电极作为参比电极。具体的工作电极制作步骤为:将5mg样品分散在980μL乙醇溶液中,加入20μL 5%的Nafion溶液,然后将催化剂浆料涂敷在旋转圆盘电极上,用1M的KOH作为电解液。该复合催化材料相比水钠锰矿型δ-MnO2展现出了更优越的催化水氧化性能,在线性扫描伏安法测试中,电流为5mA cm-2时,电势大小为V=0.91;计时电流测试中,复合催化材料在4000s内表现出了优秀的稳定性(测试结果如图6-8)。
实施例2
称取2.7MnSO4·H2O和6.0EDTA溶于去离子水中,搅拌30min得到白色悬浊溶液,称为Sa。将2.4g KOH溶于50ml去离子水中搅拌至完全溶解,称为Sb。快速搅拌下,将Sb缓慢滴加到Sa中,滴加完毕后继续搅拌2h后,过滤沉淀,用去离子水洗涤数次,后置真空干燥箱40℃下放置12h最后产物:得到水钠锰矿型δ-MnO2粉末。称取4g的水钠锰矿型δ-MnO2与300ml2mol/L HCl溶液混合于室温下搅拌8h,抽滤,将沉淀洗涤到中性,70℃干燥,研磨,最后得到没有碱金属离子的酸化水钠锰矿型δ-MnO2。称取1g酸化后的水钠锰矿型δ-MnO2,将其分散在120ml的去离子水中,再加入30ml四乙基氢氧化铵,在室温中搅拌48h,将混合液在12000rpm下离心30min,将得到的固体用去离子水冲洗三次,在70℃干燥后,得到剥离态δ-MnO2。称取5,10,15,20-四(4-氨基苯基)锰卟啉粉末0.125g与0.6g剥离态δ-MnO2,于100ml 40℃去离子水中搅拌30h,剥离态δ-MnO2层片与锰卟啉发生自组装反应,形成复合层状夹心纳米材料,然后过滤,用去离子水冲洗3次,干燥,最后得到产物。
复合纳米催化剂的电催化水氧化活性通过三电极体系检测,其中旋转圆盘电极作为工作电极,铂电极作为对电极,甘汞电极作为参比电极。具体的工作电极制作步骤为:将5mg样品分散在980μL乙醇溶液中,加入20μL 5%的Nafion溶液,然后将催化剂浆料涂敷在旋转圆盘电极上,用1M的KOH作为电解液。该复合催化材料相比δ-MnO2展现出了更优越的催化水氧化性能,在线性扫描伏安法测试中,电流为5mA cm-2时,电势大小为V=0.93;计时电流测试中,复合催化材料在4000s内表现出了优秀的稳定性。
(注:对中间产物及目标产物进行了如实施例1的各项测试表征,结果与实施例1相似。)
实施例3
称取3.2MnSO4·H2O和4.8柠檬酸钠溶于去离子水中,搅拌30min得到白色悬浊溶液,称为Sa。将2.9g LiOH溶于50ml去离子水中搅拌至完全溶解,称为Sb。快速搅拌下,将Sb缓慢滴加到Sa中,滴加完毕后继续搅拌2h后,过滤沉淀,用去离子水洗涤数次,后置真空干燥箱40℃下放置12h最后产物:得到水钠锰矿型δ-MnO2粉末。称取2g的水钠锰矿型δ-MnO2与300ml 1mol/L HNO3溶液混合于室温下搅拌12h,抽滤,将沉淀洗涤到中性,70℃干燥,研磨,最后得到没有碱金属离子的酸化水钠锰矿型δ-MnO2。称取1g酸化后的水钠锰矿型δ-MnO2,将其分散在120ml的去离子水中,再加入20ml三乙醇胺,在室温中搅拌72h,将混合液在12000rpm下离心30min,将得到的固体用去离子水冲洗三次,在70℃干燥后,得到剥离态δ-MnO2。称取5,10,15,20-四(4-氨基苯基)锰卟啉粉末0.0679g与0.4g剥离态δ-MnO2与100ml40℃去离子水中搅拌20h,剥离δ-MnO2层片与锰卟啉发生自组装反应,形成复合层状夹心纳米材料,然后过滤,用去离子水冲洗3次,干燥,最后得到产物。然后进行电化学水氧化测试。
复合纳米催化剂的电催化水氧化活性通过三电极体系检测,其中旋转圆盘电极作为工作电极,铂电极作为对电极,甘汞电极作为参比电极。具体的工作电极制作步骤为:将5mg样品分散在980μL乙醇溶液中,加入20μL 5%的Nafion溶液,然后将催化剂浆料涂敷在旋转圆盘电极上,用1M的KOH作为电解液。该复合催化材料相比水钠锰矿型δ-MnO2展现出了更优越的催化水氧化性能,在线性扫描伏安法测试中,电流为5mA cm-2时,电势大小为V=0.92;计时电流测试中,复合催化材料在4000s内表现出了优秀的稳定性。
(注:对中间产物及目标产物进行了如实施例1的各项测试表征,结果与实施例1相似。)
Claims (6)
1.一种应用于电催化水氧化的锰氧化物/金属卟啉复合层状夹心纳米催化剂的制备方法,其特征包括以下步骤:(1)将无机锰盐和络合剂溶于去离子水中,缓慢加入无机碱并搅拌,得到高纯水钠锰矿型δ-MnO2;(2)先将制备好的水钠锰矿型δ-MnO2放入酸性溶液中搅拌,抽滤,干燥,研磨,制备出不含碱金属的δ-MnO2;再将产物分散到碱性溶液中,搅拌,离心,干燥,得到层片剥离的δ-MnO2;(3)将单层片的δ-MnO2加入到一定浓度的5,10,15,20-四(4-氨基苯基)锰卟啉溶液中搅拌反应,即得到重新自组装的、金属卟啉插层的、层状夹心的锰氧化物/金属卟啉复合纳米催化剂。
2.根据权利要求1所述的方法,其特征在于,所述(1)的无机锰盐为MnSO4·H2O,MnCl2,Mn(NO3)2;络合剂为EDTA-2Na,EDTA,柠檬酸三钠;无机碱为NaOH,LiOH,KOH。
3.根据权利要求1所述的方法,其特征在于,所述(2)中的酸性溶液,是指硝酸、硫酸、盐酸等质子酸的单组份或多组分混合物,其H+浓度为0.1-10mol/L,搅拌温度为15-45℃,搅拌时间为5-20h。
4.根据权利要求1所述的制备方法,其特征在于,所述(2)中的碱性溶液,是指氢氧化铵、四甲基氢氧化铵、四乙基氢氧化铵、三乙醇胺等碱的单组份或多组分混合物,浓度为0.01-5mol/L的水溶液,搅拌温度为10-50℃,搅拌时间为6-120h。
5.根据权利要求1所述的制备方法,其特征在于,加入的5,10,15,20-四(4-氨基苯基)锰卟啉与δ-MnO2的物质量之比为(0.1-1):1;搅拌温度为10-60℃,搅拌时间为2-48h;在电荷力及氨基与锰离子配位作用力的驱动下,单层片δ-MnO2与金属卟啉自动夹层组装成三明治型的纳米复合物。
6.根据权利要求1所述方法制得的锰氧化物/金属卟啉复合纳米催化材料,其特征在于,应用于阳极析氧材料时,相比δ-MnO2展现出了更优越的催化水氧化性能,在线性扫描伏安法测试中,电流为5mA cm-2时,电势大小为V=0.91;计时电流测试中,复合催化材料在4000s内表现出了优秀的稳定性。
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