CN107029703B - 三明治结构MnOX/C/MnOX空心球的制备方法 - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011943 nanocatalyst Substances 0.000 abstract description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 239000003550 marker Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Abstract
三明治结构MnOX/C/MnOX空心球的制备方法，涉及纳米催化剂的生产技术领域。先合成PoPD空心球，在酸性条件下，加入KMnO4于常温下通过氧化还原得到MnO2/PoPD/MnO2空心球，在惰性气体的保护下对其进行炭化得到三明治结构MnOX/C/MnOX空心球。本发明弥补了锰氧化物导电性差和活性位点少等缺点，提升了催化剂的电化学催化活性，制备出的催化剂具有大的比表面积，不需要模板可以一步合成空心球，并且催化剂催化活性高、稳定性好，在催化领域有着重要的应用价值。
Description
技术领域
本发明涉及纳米催化剂的生产技术领域。
背景技术
近年来氧还原电催化剂一直是人们研究的焦点之一。过渡金属锰氧化物储量丰富，价格低廉，具有多种氧化物结构，氮掺杂的碳材料具有良好的导电性和电催化活性，氮掺杂的碳材料与过渡金属锰氧化物复合可以提高其电化学催化性能。
锰氧化物具有多种氧化物存在形式，其不同的形态具有不同的空间结构和表面状态，其中MnO2与Mn2O3由于其制备简单，热力学稳定性和氧还原电化学催化性能好而备受关注，但是锰氧化物为半导体，其导电性能较差，活性位点利用率低。碳材料具有良好的导电性和稳定性，可掺杂其他元素使其结构发生改变，其中氮掺杂的碳催化剂研究报道的最为成熟，因此一些研究者认为氮掺杂的碳材料与过渡金属氧化物一起构成催化活性中心。
发明内容
本发明的目的在于提供一种活性位点利用率高的MnOX/C/MnOX三明治结构空心球催化剂的制备方法。
本发明包括以下步骤：
1）将邻苯二胺水溶液与过硫酸铵水溶液混合反应，得聚邻苯二胺（PoPD）空心球；
2）超声条件下，将聚邻苯二胺（PoPD）空心球分散在去离子水中，经调整混合体系的pH至1～2后，再加入KMnO4水溶液，搅拌反应至结束，取得固相，用去离子水及无水乙醇洗涤，经烘干，得三明治结构MnO2/PoPD/MnO2空心球；
3）将三明治结构MnO2/PoPD/MnO2空心球置于坩埚中，于惰性气体保护下煅烧，得三明治结构MnOX/C/MnOX空心球。
本发明采用上述方案制备出了一种高活性、耐腐蚀性强的三明治结构MnOX/C/MnOX空心球。首先合成PoPD空心球，在酸性条件下，加入KMnO4于常温下通过氧化还原得到MnO2/PoPD/MnO2空心球，在惰性气体的保护下对其进行炭化得到三明治结构MnOX/C/MnOX空心球。
本发明碳材料的引入弥补了锰氧化物导电性差和活性位点少等缺点，进一步提升了催化剂的电化学催化活性。本发明的优点在于制备出的催化剂具有大的比表面积，不需要模板可以一步合成空心球，并且催化剂催化活性高、稳定性好，在催化领域有着重要的应用价值。
进一步地，本发明所述步骤1）中反应在0～5℃下进行，反应后取固相，以氨水、去离子水及无水乙醇洗至无色后烘干，得聚邻苯二胺（PoPD）空心球。低温使反应缓慢进行，得到空心球颗粒均一分散且尺寸分布窄。
所述邻苯二胺水溶液中邻苯二胺与过硫酸铵水溶液中过硫酸铵的质量比为26∶55。该用量可保证邻苯二胺反应完全。
所述步骤2）中所述聚邻苯二胺（PoPD）空心球和KMnO4水溶液中KMnO4的混合质量比为35∶7.9。该投料比使得MnO2能够生长在聚邻苯二胺（PoPD）空心球的内外表面且不会有大量MnO2散落在球外，同时在该投料比下得到的材料氧还原反应电催化活性最佳。
所述步骤3）中所述煅烧温度为600～900℃。在此温度范围内，材料的空心球形貌能够保持完整，并且可以使材料得到充分的炭化，锰氧化物结晶性增加，增加材料的活性位点，在此温度范围内氧还原反应催化性能呈现先增大后减小趋势，在800℃下催化性能最优。
附图说明
图1是实施例1制备得到的三明治结构MnO2/C/MnO2空心球的TEM照片。
图2是实施例2制备得到的三明治结构MnO2/C/MnO2空心球的TEM照片。
图3是实施例3制备得到的三明治结构Mn2O3/C/Mn2O3空心球的TEM照片。
图4是实施例4制备得到的三明治结构Mn2O3/C/Mn2O3空心球的TEM照片。
图5是不同催化剂催化氧还原反应的线性扫描伏安曲线图。
具体实施方式
下面通过实施例对本发明作进一步说明。
一、制备示例：
实施例1
（1）聚邻苯二胺（PoPD）空心球的合成：
取0.26 g邻苯二胺放入锥形瓶中，加入20 mL去离子水，室温下搅拌10 min至样品完全溶解，将其保持在0～5℃下30 min。
将0.55 g过硫酸铵用2.75 mL去离子水溶解后，加入上述混合溶液，保持0～5℃的反应温度，静置反应12 h后，取得固相产物。
将固相产物用0.1 M氨水、去离子水及无水乙醇洗至无色，烘干，即得PoPD空心球。
（2）三明治结构MnO2/PoPD/MnO2空心球的合成：
取0.35 gPoPD空心球加入8 mL H2O中，以盐酸溶液调溶液的pH在1～2，然后超声10 min使PoPD空心球充分分散。然后再在上述混合体系中加入5 mL 0.1 MKMnO4水溶液，搅拌反应4 h后，取固相。再用去离子水及无水乙醇对固相进行洗涤，再经烘干，得三明治结构MnO2/PoPD/MnO2空心球。
（3）三明治结构MnO2/C/MnO2空心球的合成：
将三明治结构MnO2/PoPD/MnO2空心球置于坩埚中，于氮气惰性气体保护下，600℃高温煅烧，即得三明治结构MnO2/C/MnO2空心球。
如图1所示的TEM形貌特征图可见：
三明治结构MnO2/C/MnO2空心球具有三层夹心壳层的空心球形貌特征。根据其煅烧温度标记为MnO2/C/MnO2(600)。
实施例2
按实施例1中步骤（1）和（2）的方法，取得MnO2/PoPD/MnO2材料。
（3）三明治结构MnO2/C/MnO2空心球的合成：
将三明治结构MnO2/PoPD/MnO2空心球置于坩埚中，于氮气惰性气体保护下，700℃高温煅烧，即得三明治结构MnO2/C/MnO2空心球。
如图2所示的TEM形貌特征图可见：
三明治结构MnO2/C/MnO2空心球具有三层夹心壳层的空心球形貌特征。根据其煅烧温度标记为MnO2/C/MnO2(700)。
实施例3
按实施例1中步骤（1）和（2）的方法，取得MnO2/PoPD/MnO2材料。
（3）三明治结构Mn2O3/C/Mn2O3空心球的合成：
将三明治结构MnO2/PoPD/MnO2空心球置于坩埚中，于氮气惰性气体保护下，800℃高温煅烧，即得三明治结构Mn2O3/C/Mn2O3空心球。
如图3所示的TEM形貌特征图可见：
三明治结构Mn2O3/C/Mn2O3空心球具有三层夹心壳层的空心球形貌特征。根据其煅烧温度标记为Mn2O3/C/Mn2O3 (800)。
实施例4
按实施例1中步骤（1）和（2）的方法，取得MnO2/PoPD/MnO2材料。
（3）三明治结构Mn2O3/C/Mn2O3空心球的合成：
将三明治结构MnO2/PoPD/MnO2空心球置于坩埚中，于氮气惰性气体保护下，900℃高温煅烧，即得三明治结构Mn2O3/C/Mn2O3空心球。
如图4所示的TEM形貌特征图可见：
三明治结构Mn2O3/C/Mn2O3空心球具有三层夹心壳层的空心球形貌特征。根据其煅烧温度标记为Mn2O3/C/Mn2O3 (900)。
以上各例说明：通过控制对MnO2/PoPD/MnO2材料的煅烧温度，可以获得三明治结构空心球可以是Mn2O3/C/Mn2O3或MnO2/C/MnO2。
二、应用及效果验证：
取以上各例材料3 mg，与7 mg导电碳黑 Vulcan XC-72、50 μL 5wt%的Nafion溶液、950 μL水与异丙醇的溶液混合后经超声分散，制备工作电极，测定氧还原反应电催化活性。
如图5所示，当煅烧温度为800℃时得到的三明治结构Mn2O3/C/Mn2O3材料极限电流密度最大，超过10 wt% 的商业Pt/C催化剂，其初始电位也接近Pt/C催化剂。说明三明治结构Mn2O3/C/Mn2O3空心球不仅具有独特的形貌结构，同时具有良好的氧还原反应电催化活性。
Claims (2)
1.三明治结构MnOX/C/MnOX空心球的制备方法，其特征在于包括以下步骤：
1）将邻苯二胺水溶液与过硫酸铵水溶液混合反应，所述邻苯二胺水溶液中邻苯二胺与过硫酸铵水溶液中过硫酸铵的质量比为26∶55，反应在0～5℃下进行，反应后取固相，以氨水、去离子水及无水乙醇洗至无色后烘干，得聚邻苯二胺空心球；
2）超声条件下，将聚邻苯二胺空心球分散在去离子水中，经调整混合体系的pH至1～2后，再加入KMnO4水溶液，所述聚邻苯二胺空心球和KMnO4水溶液中KMnO4的质量比为35∶7.9，搅拌反应至结束，取得固相，用去离子水及无水乙醇洗涤，经烘干，得三明治结构MnO2/PoPD/MnO2空心球；
3）将三明治结构MnO2/PoPD/MnO2空心球置于坩埚中，于惰性气体保护下煅烧，得三明治结构MnOX/C/MnOX空心球；所述煅烧温度为600～900℃。
2.根据权利要求1所述三明治结构MnOX/C/MnOX空心球的制备方法，其特征在于：所述步骤3）中所述煅烧温度为800℃。
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| CN102408712B (zh) * | 2011-09-22 | 2013-01-23 | 扬州大学 | 聚苯胺纳米纤维/二氧化锰纳米棒复合材料及其制备方法 |
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| CN103936987B (zh) * | 2014-05-08 | 2017-01-18 | 扬州大学 | 一种碳纳米管复合材料及其制备方法 |
| CN104681823B (zh) * | 2015-01-23 | 2017-10-03 | 西华师范大学 | 一种氮掺杂石墨烯与Co3O4空心纳米球复合材料及其制备方法和应用 |
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