CN106350833B - 三维大孔结构二氧化钼负载氧化钴颗粒材料作为阳极电催化剂的应用 - Google Patents
三维大孔结构二氧化钼负载氧化钴颗粒材料作为阳极电催化剂的应用 Download PDFInfo
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- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 title claims abstract description 99
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- 239000000463 material Substances 0.000 title claims abstract description 17
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims abstract description 16
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- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910015221 MoCl5 Inorganic materials 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
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- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- GZPBVLUEICLBOA-UHFFFAOYSA-N 4-(dimethylamino)-3,5-dimethylphenol Chemical compound CN(C)C1=C(C)C=C(O)C=C1C GZPBVLUEICLBOA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
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- UQJSLVWCKFZHFO-UHFFFAOYSA-N molybdenum(4+) oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Mo+4] UQJSLVWCKFZHFO-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C25B11/031—Porous electrodes
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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Abstract
本发明公开三维大孔结构二氧化钼负载氧化钴颗粒材料作为阳极电催化剂的应用,二氧化钼与氧化钴的质量比为9:(0.4‑2),二氧化钼的孔径为200—400nm,氧化钴颗粒为5—10nm,利用有序排列的聚甲基丙烯酸甲酯微球胶晶模板制备三维大孔二氧化钼结构,在三维大孔二氧化钼结构上进行氧化钴颗粒的负载。本发明实施费用低、操作简便,污染低,是一种高效经济的合成方法,同时本发明的材料结构稳定且具有阳极电催化性能。
Description
本发明申请是母案申请“一种三维大孔结构二氧化钼负载氧化钴颗粒材料及其合成方法”的分案申请,母案申请的申请号为2015101633222,申请日为2015年4月8日。
技术领域
本发明涉及一种新型纳米材料及其合成方法,尤其涉及一种三维大孔结构二氧化钼负载氧化钴颗粒材料及其合成方法。
背景技术
过渡金属氧化物MoO2属于单斜晶系,具有畸变的金红石晶体结构,MoO2是拥有高电导率、高熔点、高化学稳定性的过渡金属氧化物,其高效的电荷传输特性使它在催化剂、传感器、电致变色显示器、记录材料、电化学超级电容器、Li离子电池以及场发射材料等方面应用前景广泛。层状结构MoO2具有低电阻率,高的电化学活性和高稳定性,表现出良好的催化性能,在催化材料应用方面范围越来越广泛,并且在电催化析氢领域已经有所应用。但由于不可逆体积膨胀可导致塑性变形和性能下降,所以有必要在其结构上作进一步研究。
发明内容
本发明的目的是提供三维大孔结构二氧化钼负载氧化钴颗粒材料及其合成方法,获得一种比表面积大、结构稳定且具有电催化性能的纳米结构,此方法具有成本低、制备过程简单的特点。
本发明的目的通过下述技术方案予以实现:
一种三维大孔结构二氧化钼负载氧化钴颗粒材料,MoO2与CoO的质量比为9:(0.4-2),二氧化钼的孔径为200—400nm,氧化钴颗粒为5—10nm且均匀的分布在二氧化钼的孔壁上,并按照下述步骤进行:
步骤1,三维大孔MoO2结构的制备:将有序排列的聚甲基丙烯酸甲酯(PMMA)微球胶晶模板置于MoCl5水溶液中,氧化后反复抽滤并干燥,而后在流通保护气体气氛下640—650℃热处理1—2h,得到孔径大小为200-400nm的三维大孔MoO2,所述MoCl5水溶液浓度为0.05M,自室温20—25摄氏度上升至640—650℃,加热温度的上升速率为5—8℃/min,所述保护气体气氛为氩气,或者氦气,或者氮气;
在步骤1中,有序排列的聚甲基丙烯酸甲酯(PMMA)微球胶晶模板依照现有技术进行制备:(1)Sadakane,M.;Takahashi,C.;Kato,N.;Ogihara,H.;Nodasaka,Y.;Doi,Y.;Hinatsu,Y.and Ueda,W.Three-Dimensionally Ordered Macroporous(3DOM)Materialsof Spinel-Type Mixed Iron Oxides.Synthesis,Structural Characterization,andFormation Mechanism of Inverse Opals with a SkeletonStructure.Bull.Chem.Soc.Jpn.2007,80(4),677-685;(2)Yuxi Liu,Hongxing Dai,Jiguang Deng,Lei Zhang,Chak Tong Au Three-dimensional ordered macroporousbismuth vanadates:PMMA-templating fabrication and excellent visible light-driven photocatalytic performance for phenol degradation.Nanoscale,2012,4,2317–2325。
步骤2在三维大孔MoO2结构上进行CoO颗粒的负载:将步骤2中制得的MoO2放入Co(NO3)2的水和乙二醇溶液中,密封置于50℃保温箱,放置12-13小时后抽滤,得到黑色固体,干燥后真空350℃-400℃加热2小时,随炉冷却得到负载CoO颗粒三维大孔结构MoO2;
步骤2中所述Co(NO3)2的水和乙二醇溶液的浓度为2-10M,其中溶剂水和乙二醇的比例1:1;所述MoO2的质量(mg)与Co(NO3)2的溶液的体积(mL)比为5:1;所得到的负载CoO颗粒三维大孔结构MoO2中MoO2与CoO的质量比为9:(0.4-2)。
本发明的方法成本费用低,操作简便,耗时较短,与传统制备方法相比,主要有以下几个优势:(1)可以有效控制三维大孔MoO2结构的孔径大小(2)解决了颗粒团聚的特点,使CoO颗粒均匀分布在三维大孔MoO2结构上(如附图2和3所示)二氧化钼具有(110)、(101)、(220)晶面,氧化钴颗粒具有(111)、(200)和(220)晶面;(3)反应时间大大缩短,且操作简单,是一种高效经济的合成方法;(4)使用电化学工作站Gamry reference 600进行测试,用于测试的溶液为PH=14,1M的KOH水溶液,进行线性伏安扫描的速率为50mV/s,负载CoO颗粒的大孔MoO2的电流密度明显增大(如附图6所示),表明这种材料催化性能大幅提高,可作为阳极电催化剂。
附图说明
图1为本发明单独200nm大小孔径的三维大孔MoO2的10K倍SEM形貌照片(FE-SEM,Hitachi S-4800);
图2为本发明负载CoO颗粒的三维大孔MoO2的20K倍SEM形貌照片(FE-SEM,HitachiS-4800);
图3为本发明负载CoO颗粒的三维大孔MoO2的100K倍SEM形貌照片(FE-SEM,HitachiS-4800);
图4为本发明负载CoO颗粒的三维大孔MoO2的TEM形貌照片(TEM,Philips TecnaiG2F20);
图5为本发明负载CoO颗粒的三维大孔MoO2的XRD图谱(XRD,RIGAKU/DMAX),其中圆点代表MoO2的晶面,方块代表CoO的晶面;
图6为本发明几种材料的线性伏安扫描电流测试图线,曲线Ⅰ为所制备单独大孔MoO2的测试图线,曲线Ⅱ为负载CoO颗粒的大孔MoO2复合物的测试图线,曲线Ⅲ为单独Ni网的测试图线。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面对本发明实施方式作进一步地详细描述。
首先依照现有技术进行有序排列的聚甲基丙烯酸甲酯(PMMA)微球胶晶模板的制备,具体来说:取60-88mL去离子水,5-16mL甲基丙烯酸甲酯,在流通氮气保护下置于磁力搅拌器上进行搅拌15分钟,加入7.5-24mL过硫酸钾水溶液(含过硫酸钾0.059-0.1888g),充分搅拌溶解。停止通氮气后,设置加热程序,使其缓慢升温至70℃并保温1.5h。而后极冷,离心、干燥得到白色固体。取白色固体,研磨成细粉末后,按照质量比1:40的比例与水混合在一起,搅拌并超声分散使其重新变成乳液状。将其倒入烧杯,置于干燥箱中50℃下干燥。干燥完毕后在玻璃片和烧杯壁上会出现条状的白色固体薄片,即为胶晶模板。
实施例1
取2g模板放入盛有10毫升0.05M的MoCl5的烧杯,将烧杯放入50℃的保温箱,密封好烧杯防止水分的挥发,大约两天时间溶液氧化,多次抽滤并干燥,得到蓝色的固体。将此固体置于坩埚放入可通保护气氛的加热炉中,在流动氩气气氛保护下自20℃上升至650℃热处理2个小时,其中升温速率为5℃/min,而后随炉冷却得到孔径大小为200nm的三维大孔MoO2。
所得MoO2 20毫克放入4ml 5M的Co(NO3)2的水和乙二醇溶液,其中溶剂水和乙二醇的比例1:1,密封置于50℃保温箱,放置12小时后抽滤,得到黑色固体,干燥后真空350℃加热2小时,随炉冷却得到负载CoO颗粒孔径大小200nm的三维大孔结构MoO2,MoO2与CoO的质量比为9:1。
实施例2
取2g模板放入盛有10毫升0.05M的MoCl5的烧杯,将烧杯放入50℃的保温箱,密封好烧杯防止水分的挥发,大约两天时间溶液氧化,多次抽滤并干燥,得到蓝色的固体。将此固体置于坩埚放入可通保护气氛的加热炉中,在流动氩气气氛保护下自25℃上升至640℃热处理1.5个小时,其中升温速率约为8℃/min。而后随炉冷却得到孔径大小为350nm的三维大孔MoO2。
所得MoO2 20毫克放入4ml 5M的Co(NO3)2的水和乙二醇溶液,其中溶剂水和乙二醇的比例1:1,密封置于50℃保温箱,放置13小时后抽滤,得到黑色固体,干燥后真空400℃加热2小时,随炉冷却得到负载CoO颗粒孔径大小350nm的三维大孔结构MoO2,MoO2与CoO的质量比为9:1。
实施例3
取2g模板放入盛有10毫升0.05M的MoCl5的烧杯,将烧杯放入50℃的保温箱,密封好烧杯防止水分的挥发,大约两天时间溶液氧化,多次抽滤并干燥,得到蓝色的固体。将此固体置于坩埚放入可通保护气氛的加热炉中,在流动氩气气氛保护下自22℃上升至645℃热处理2个小时,其中升温速率约为8℃/min。而后随炉冷却得到孔径大小为400nm的三维大孔MoO2。
所得MoO2 20毫克放入4ml5M的Co(NO3)2的水和乙二醇溶液,其中溶剂水和乙二醇的比例1:1,密封置于50℃保温箱,放置12小时后抽滤,得到黑色固体,干燥后真空380℃加热2小时,随炉冷却得到负载CoO颗粒孔径大小400nm的三维大孔结构MoO2,MoO2与CoO的质量比为9:1
实施例4
取2g模板放入盛有10毫升0.05M的MoCl5的烧杯,将烧杯放入50℃的保温箱,密封好烧杯防止水分的挥发,大约两天时间溶液氧化,多次抽滤并干燥,得到蓝色的固体。将此固体置于坩埚放入可通保护气氛的加热炉中,在流动氩气气氛保护下自25℃上升至650℃热处理1个小时,其中升温速率约为8℃/min。而后随炉冷却得到孔径大小为200nm的三维大孔MoO2。
所得MoO2 20毫克放入4ml 10M的Co(NO3)2的水和乙二醇溶液,其中溶剂水和乙二醇的比例1:1,密封置于50℃保温箱,放置12小时后抽滤,得到黑色固体,干燥后真空350℃加热2小时,随炉冷却得到负载CoO颗粒孔径大小200nm的三维大孔结构MoO2,MoO2与CoO的质量比为9:2。
实施例5
取2g模板放入盛有10毫升0.05M的MoCl5的烧杯,将烧杯放入50℃的保温箱,密封好烧杯防止水分的挥发,大约两天时间溶液氧化,多次抽滤并干燥,得到蓝色的固体。将此固体置于坩埚放入可通保护气氛的加热炉中,在流动氩气气氛保护下自20℃-650℃热处理2个小时,其中升温速率约为6℃/min。而后随炉冷却得到孔径大小为200nm的三维大孔MoO2。
所得MoO2 20毫克放入4ml 2M的Co(NO3)2的水和乙二醇溶液,其中溶剂水和乙二醇的比例1:1,密封置于50℃保温箱,放置12小时后抽滤,得到黑色固体,干燥后真空360℃加热2小时,随炉冷却得到负载CoO颗粒孔径大小200nm的三维大孔结构MoO2,MoO2与CoO的质量比为9:0.4。
实施例6
取2g模板放入盛有10毫升0.05M的MoCl5的烧杯,将烧杯放入50℃的保温箱,密封好烧杯防止水分的挥发,大约两天时间溶液氧化,多次抽滤并干燥,得到蓝色的固体。将此固体置于坩埚放入可通保护气氛的加热炉中,在流动氩气气氛保护下自20℃-640℃热处理2个小时,其中升温速率约为5℃/min。而后随炉冷却得到孔径大小为400nm的三维大孔MoO2。
所得MoO2 20毫克放入4ml 2M的Co(NO3)2的水和乙二醇溶液,其中溶剂水和乙二醇的比例1:1,密封置于50℃保温箱,放置12小时后抽滤,得到黑色固体,干燥后真空350℃加热2小时,随炉冷却得到负载CoO颗粒孔径大小400nm的三维大孔结构MoO2,MoO2与CoO的质量比为9:0.4。
以上对本发明做了示例性的描述,应该说明的是,在不脱离本发明的核心的情况下,任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。
Claims (3)
1.三维大孔结构二氧化钼负载氧化钴颗粒材料作为阳极电催化剂的应用,其特征在于,MoO2与CoO的质量比为9:(0.4-2),二氧化钼的孔径为200—400nm,氧化钴颗粒为5—10nm且均匀的分布在二氧化钼的孔壁上,并按照下述步骤进行:
步骤1,三维大孔MoO2结构的制备:将有序排列的聚甲基丙烯酸甲酯微球胶晶模板置于MoCl5水溶液中,氧化后反复抽滤并干燥,而后在流通保护气体气氛下640—650℃热处理1—2h,得到孔径大小为200-400nm的三维大孔MoO2,所述MoCl5水溶液浓度为0.05M,自室温20—25摄氏度上升至640—650℃,加热温度的上升速率为5—8℃/min,所述保护气体气氛为氩气,或者氦气,或者氮气;
步骤2,在三维大孔MoO2结构上进行CoO颗粒的负载:将步骤1中制得的MoO2放入Co(NO3)2的水和乙二醇溶液中,密封置于50℃保温箱,放置12-13小时后抽滤,得到黑色固体,干燥后真空350℃-400℃加热2小时,随炉冷却得到负载CoO颗粒三维大孔结构MoO2;在所述步骤2中Co(NO3)2的水和乙二醇溶液的浓度为2-10M,其中溶剂水和乙二醇的比例1:1;所述MoO2的质量与Co(NO3)2的溶液的体积比为5:1,上述质量的单位为mg,体积的单位mL;所得到的负载CoO颗粒三维大孔结构MoO2中MoO2与CoO的质量比为9:(0.4-2)。
2.根据权利要求1所述的三维大孔结构二氧化钼负载氧化钴颗粒材料作为阳极电催化剂的应用,其特征在于,在所述步骤1中,将有序排列的聚甲基丙烯酸甲酯(PMMA)微球胶晶模板置于MoCl5水溶液中,氧化后反复抽滤并干燥,而后在流通保护气体气氛下645—650℃热处理2h。
3.根据权利要求1所述的三维大孔结构二氧化钼负载氧化钴颗粒材料作为阳极电催化剂的应用,其特征在于,在所述步骤2中Co(NO3)2的水和乙二醇溶液的浓度为5-10M,所得到的负载CoO颗粒三维大孔结构MoO2中MoO2与CoO的质量比为9:(1-2)。
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