CN105833861A - 一种二氧化锰/石墨烯复合催化剂的制备方法 - Google Patents
一种二氧化锰/石墨烯复合催化剂的制备方法 Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 159
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000725 suspension Substances 0.000 claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000015556 catabolic process Effects 0.000 claims abstract description 7
- 238000006731 degradation reaction Methods 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 229940099596 manganese sulfate Drugs 0.000 claims description 13
- 235000007079 manganese sulphate Nutrition 0.000 claims description 13
- 239000011702 manganese sulphate Substances 0.000 claims description 13
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 3
- UBXWAYGQRZFPGU-UHFFFAOYSA-N manganese(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Mn++] UBXWAYGQRZFPGU-UHFFFAOYSA-N 0.000 claims 1
- KNLQKHUBPCXPQD-UHFFFAOYSA-N manganese;sulfuric acid Chemical compound [Mn].OS(O)(=O)=O KNLQKHUBPCXPQD-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 241000790917 Dioxys <bee> Species 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Polymers [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 graphene modified manganese dioxide Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910003144 α-MnO2 Inorganic materials 0.000 description 1
- 229910006287 γ-MnO2 Inorganic materials 0.000 description 1
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- 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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- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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Abstract
一种二氧化锰/石墨烯复合催化剂的制备方法，属于无机催化材料领域。本发明先制备二氧化锰/氧化石墨烯悬浮液，后以氨水为还原剂，95℃下对二氧化锰/氧化石墨烯还原2h，过滤，洗涤，制得二氧化锰/石墨烯复合催化剂。本发明方法工艺简单，所用设备少，制备周期短，成本低。本发明制备的复合催化剂活性高，5mg催化剂、2mL过氧化氢加入到100mL、5mg/L罗丹明B溶液中，40min时罗丹明B的降解率达95％。采用本发明制备出的复合催化剂可广泛用于催化降解有机污染物的领域中。
Description
技术领域
本发明涉及一种二氧化锰/石墨烯复合催化剂的制备方法，属于无机催化材料技术领域。
背景技术
二氧化锰(MnO2)具有良好的催化性、吸附性、电化学性能和环境友好性。二氧化锰晶型主要有α、β、γ、δ和ε等，α-MnO2可用作催化氧化剂，γ-MnO2主要用作电器元件。二氧化锰的制备方法主要有水热法、氧化还原法、热分解法、电沉积法和溶胶凝胶法等。纯二氧化锰的催化性能较差，对二氧化锰进行掺杂改性已有报道，“Journal of Materials Chemistry A”2013年第1期“Reactive template strategy for fabrication of MnO2/polyaniline coaxial nanocablesand their catalytic application in the oxidative decolorization of rhodamine B”(对比文件1)一文，报道了负载聚苯胺改性二氧化锰，制备的二氧化锰/聚苯胺复合材料的催化性能有所提高，该方法存在的不足是：(1)催化剂耗量较大，用量达1g/L，(2)催化剂的效能不高，对污染物的处理效果不佳，5mg/L的罗丹明B降解率只有85％左右。
石墨烯具有较大的表面积、较好的吸附性能和良好的导电性。用石墨烯修饰二氧化锰可以提高材料的性能。二氧化锰/石墨烯复合材料的制备方法主要有：(1)利用碳和高锰酸钾的氧化还原法，该方法的明显缺陷是反应比较难进行，耗时，至少需要反应12小时；(2)水热法，不足之处是：需要反应釜提供高温、高压条件致使成本较高，且制备产量较低，反应时间较长；(3)共沉淀法，“硅酸盐学报”2013年第41卷第1期“石墨烯/二氧化锰复合材料的电化学性能”(对比文件2)一文中采用共沉淀法制备了二氧化锰/石墨烯复合材料，用作超级电容器材料，此方法的不足之处是：采用1050℃高温对石墨烯进行热解来还原氧化石墨烯，且二价锰离子氧化成二氧化锰所添加的高锰酸钾也氧化了部分石墨烯，导致消耗过多石墨烯。
发明内容
本发明的目的是针对二氧化锰催化性较低、改性制备方法比较复杂等问题，提出一种二氧化锰/石墨烯复合催化剂的制备方法，制得的复合催化剂具有较好的性能，能够有效地催化过氧化氢氧化降解废水中的有机污染物，方法简单，成本低。
本发明二氧化锰/石墨烯复合催化剂的制备方法如下：
(1)二氧化锰/氧化石墨烯悬浮液的制备
用高锰酸钾将石墨氧化制得氧化石墨烯分散液；称取适量的硫酸锰，溶解在去离子水中配制成浓度为0.1mol/L硫酸锰溶液，按照氧化石墨烯和锰的质量比为5～15∶100，量取一定量的氧化石墨烯分散液置于烧杯中，加入适量去离子水，将硫酸锰溶液加入到氧化石墨烯分散液中，超声震荡0.5h，得到混合液A；称取适量高锰酸钾溶解在去离子水中配制成浓度为0.1mol/L高锰酸钾溶液，按照硫酸锰和高锰酸钾的摩尔比为1∶1.5，将高锰酸钾溶液缓慢滴加至混合液A中并不断搅拌，在80℃下反应2h，即得二氧化锰/氧化石墨烯悬浮液；
(2)二氧化锰/石墨烯复合催化剂的制备
用氨水调节制备的二氧化锰/石墨烯悬浮液的pH为9～11，在95℃下反应1～3h，将得到的反应溶液冷却至室温，抽滤，用去离子水洗涤沉淀并在105℃下干燥12h，即制得二氧化锰/石墨烯复合催化剂。
本发明采用上述技术方案，主要有以下效果：
(1)在0.05g/L催化剂(明显低于对比文件1中1g/L的催化剂用量)、2mL30％过氧化氢的条件下，本发明制备的二氧化锰/石墨烯复合催化剂催化100mL、5mg/L罗丹明B的氧化降解，40min时的降解率达95％，明显高于对比文件1中85％的降解率。
(2)本发明制备的二氧化锰/石墨烯复合催化剂的电荷转移电阻为二氧化锰的0.18倍，较小的电阻有利于电子的传递，提高了催化剂的活性。
(3)本发明制备的二氧化锰/石墨烯复合催化剂的比表面积是二氧化锰的1.6倍，较大的比表面积可提高催化剂的吸附性能，提供更多的活性中心，有利于污染物的迅速降解。
(4)本发明采用先负载后还原的方法制备二氧化锰/石墨烯复合催化剂，避免了石墨烯被再次氧化，增强了负载效果，优于对比文件2中的方法，采用氨水作为还原剂，有效减少了杂质离子的嵌入。
(5)本发明方法的步骤简单，条件温和，所用设备少，成本低。
附图说明
图1为二氧化锰/石墨烯的X-射线衍射图；
图2为二氧化锰、二氧化锰/石墨烯的拉曼光谱图；
图3为二氧化锰、二氧化锰/氧化石墨烯以及二氧化锰/石墨烯的交流阻抗图；
图4为二氧化锰、二氧化锰/石墨烯的吸附等温线图。
具体实施方式
下面结合具体实施方式，进一步说明本发明。
实施例1
(1)二氧化锰/氧化石墨烯悬浮液的制备
用高锰酸钾将石墨氧化制得氧化石墨烯分散液，称取0.53g硫酸锰，溶解在去离子水中配制0.1mol/L硫酸锰溶液，按氧化石墨烯和锰的质量比为10∶100，取2.75mL、浓度为7mg/mL的氧化石墨烯分散液置于烧杯中，加入20mL去离子水，将硫酸锰溶液加入到氧化石墨烯分散液中，超声震荡0.5h，得到混合液A；按照硫酸锰和高锰酸钾的摩尔比为1∶1.5，称取0.33g高锰酸钾，溶解在去离子水中配制0.1mol/L高锰酸钾溶液，在强力机械搅拌下，将高锰酸钾溶液缓慢滴加至混合液A中，80℃下反应2h，即得二氧化锰/氧化石墨烯悬浮液；
(2)二氧化锰/石墨烯复合催化剂的制备
用氨水调节制备的二氧化锰/氧化石墨烯悬浮液的pH为11，在95℃下反应2h，将得到的反应溶液冷却至室温，抽滤，用去离子水洗涤沉淀并在105℃下干燥12h，即制得二氧化锰/石墨烯复合催化剂。
实施例2
(1)二氧化锰/氧化石墨烯悬浮液的制备
按氧化石墨烯和锰的质量比为5∶100，取1.38mL、浓度为7mg/mL的氧化石墨烯悬浮液，称取0.53g硫酸锰，其余步骤同实施例1的步骤(1)；
(2)二氧化锰/石墨烯复合催化剂的制备
用氨水调节制备的二氧化锰/氧化石墨烯悬浮液的pH至10，在95℃下反应3h，其余步骤同实施例1的步骤(2)。
实施例3
(1)二氧化锰/氧化石墨烯悬浮液的制备
按氧化石墨烯和锰的质量比为15∶100，取4.13mL、浓度为7mg/mL的氧化石墨烯悬浮液，称取0.53g硫酸锰，其余步骤同实施例1的步骤(1)；
(2)二氧化锰/石墨烯复合催化剂的制备
用氨水将制备的二氧化锰/氧化石墨烯悬浮液的pH调至9，在95℃下反应1h，其余步骤同实施例1的步骤(2)。
实验结果
用实施例1制备出的二氧化锰/石墨烯的X-射线衍射图谱如图1所示，图1表明二氧化锰/石墨烯复合催化剂在21.0°、37.1°、42.4°、56.0°和66.7°处出现明显的衍射峰，与卡片号为JCPDS30-0820的ε-MnO2相吻合，其中37.1°、42.4°、56.0°和66.7°对应的晶面指数分别为(100)、(101)、(102)和(110)。
实施例1制备出的二氧化锰/石墨烯的拉曼光谱如图2所示，图2显示复合催化剂在630cm-1附近出现二氧化锰的特征峰，并且在1400cm-1和1600cm-1附近分别出现石墨烯的D带峰和G带峰。实施例1中制得的二氧化锰/石墨烯及对比实验得到的二氧化锰、二氧化锰/氧化石墨烯的交流阻抗谱如图3所示。图3看出，二氧化锰/石墨烯的电荷转移电阻小于二氧化锰/氧化石墨烯的电阻，且明显小于二氧化锰的电阻，二氧化锰、二氧化锰/氧化石墨烯和二氧化锰/石墨烯的电荷转移电阻分别为12.67Ω·cm-2、7.05Ω·cm-2和2.36Ω·cm-2，二氧化锰/石墨烯的电荷转移电阻仅是二氧化锰的0.18倍。
实施例1制备的二氧化锰/石墨烯和对比实验制得的二氧化锰的氮气吸脱附等温线如图4。结果表明，二氧化锰的比表面积为88m2/g，二氧化锰/石墨烯的比表面积为143m2/g，是二氧化锰的1.6倍。该方法制备的二氧化锰/石墨烯复合催化剂属于介孔材料，孔径主要分布在20nm～40nm，而二氧化锰属于大孔材料，孔径主要分布在100nm～500nm。
复合催化剂的催化效果好，加入催化剂0.05g/L和2mL过氧化氢，在40min时对100mL、浓度为5mg/L的罗丹明B的降解率达到95％。
Claims (5)
1.一种二氧化锰/石墨烯复合催化剂的制备方法，其特征在于包括以下步骤：
(1)二氧化锰/氧化石墨烯悬浮液的制备
取适量高锰酸钾将石墨氧化制得氧化石墨烯分散液，取适量硫酸锰溶解在去离子水中制得浓度为0.1mol/L硫酸锰溶液，按氧化石墨烯和锰的质量比为5～15∶100，将硫酸锰溶液加入到氧化石墨烯分散液中，超声震荡0.5h，得到混合液A，按硫酸锰和高锰酸钾的摩尔比为1∶1.5，将浓度为0.1mol/L的高锰酸钾溶液缓慢滴加至混合液A中并连续搅拌，在80℃下反应2h，即得二氧化锰/氧化石墨烯悬浮液；
(2)二氧化锰/石墨烯复合催化剂的制备
用氨水调节制备的二氧化锰/氧化石墨烯悬浮液的pH为9～11，在95℃下反应1～3h，将得到的反应溶液冷却至室温，抽滤，用去离子水洗涤沉淀并在105℃下干燥12h，制得二氧化锰/石墨烯复合催化剂。
2.根据权利要求1所述的二氧化锰/石墨烯复合催化剂的制备方法，其特征在于采用先负载氧化石墨烯、后用氨水还原的步骤，负载效果好，有效避免了杂质离子的嵌入，制备方法简单，成本低。
3.根据权利要求1所述的二氧化锰/石墨烯复合催化剂的制备方法，其特征在于制得的复合催化剂具有较大的比表面积，是二氧化锰的1.6倍。
4.根据权利要求1所述的二氧化锰/石墨烯复合催化剂的制备方法，其特征在于制得的复合催化剂具有较小的电荷转移电阻，仅是二氧化锰的0.18倍。
5.根据权利要求1所述的二氧化锰/石墨烯复合催化剂的制备方法，其特征在于制得的复合催化剂的活性高，催化过氧化氢氧化罗丹明B的降解率达到95％。
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