CN108126703A - 绣球状CuZnOX纳米材料的制备方法及其在电催化中的应用 - Google Patents
绣球状CuZnOX纳米材料的制备方法及其在电催化中的应用 Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 11
- 239000010457 zeolite Substances 0.000 claims abstract description 11
- -1 zeolite imidazoles Chemical class 0.000 claims abstract description 11
- 150000003751 zinc Chemical class 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000013110 organic ligand Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019441 ethanol Nutrition 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000557 Nafion® Polymers 0.000 claims description 4
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 210000000988 bone and bone Anatomy 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
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- 238000012360 testing method Methods 0.000 description 7
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 230000002779 inactivation Effects 0.000 description 1
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- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing 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
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
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Abstract
绣球状CuZnOX纳米材料的制备方法及其在电催化中的应用,属于纳米材料的制备技术领域,将锌盐水溶液和有机配体水溶液混合后,在室温条件下进行搅拌反应,将得到的锌金属沸石咪唑类骨架材料与硫酸铜水溶液再混合,在室温条件下进行搅拌反应至结束,用水和乙醇清洗,得锌铜金属有机骨架材料,经煅烧,得到绣球状CuZnOX纳米材料。本发明操作简单,采用的原材料无毒、环保、成本低,工艺简单,易于操作控制,适于连续大规模生产,制备过程无污染,安全性好。
Description
技术领域
本发明属于纳米材料的制备技术领域,具体涉及绣球状的CuZnOX纳米材料的制备方法。
背景技术
由于有害气体CO2浓度不断增加激励更多研究者寻求更清洁的可再生能源取代化石燃料。作为无碳能源载体,H2受到了研究者的欢迎,作为一种理想的替代方案,由于其转换效率高。到目前为止,水电解被认为是生产H2的主要和最简单的方法,但效率仍然有限,主要是由于阳极氧化的性能,即析氧反应(OER)。OER展现出缓慢的动力学特征,同时引起电极材料结构的变化,导致电极性能差异很大。目前,钌(Ru)和铱(Ir)氧化物已经证明是最好的OER催化剂,但它们是稀缺性金属氧化物,高的成本和迅速的失活严重阻碍了它们的使用。在这些贵金属催化剂的各种替代品中,过渡金属氧化物已经取得了巨大的成功由于其高的能量密度,低的成本,生态友好和相当大的OER催化性能。尽管在合成路线和结构有很大的进步,但是为了发展高的活性,需要进行优化实际应用的电催化剂。
MOFs(金属有机骨架化合物)具有大表面积,均匀的、可调的微孔结构,这对各种应用都很有希望,包括对 OER催化性能的测试。它们的形状、大小和孔结构都是可以通过合理的设计,具有可控性。努力完善MOFs纳米结构,以提高电化学的性能或探索新的属性是我们一直以来的追求。增加活性位点的活性和数量是提高OER电催化性能的有效方法。混合金属氧化物,通常具有复杂的微观协调结构,提供了很大的帮助对于内部活动进行微调的优点。
发明内容
基于以上现有技术及市场的需要,本发明提供绣球状的CuZnOX纳米材料的制备方法。
本发明包括以下步骤:
1)将锌盐水溶液和有机配体水溶液混合后,在室温条件下进行搅拌反应,得到锌金属沸石咪唑类骨架材料;
该步骤的反应式为:
Zn(CH3COO)2 + C4H6N2 = Zn(C4H5N2)2+ CH3COOH
2)将所述锌金属沸石咪唑类骨架材料与硫酸铜水溶液再混合,在室温条件下进行搅拌反应;
该步骤的部分反应式为:
Zn(C4H5N2)2 + CuSO4•5H2O = Cu(C4H5N2)2 + ZnSO4 +5H2O
3)反应结束后,用水和乙醇清洗去除杂质,得锌铜金属有机骨架材料;
4)将锌铜金属有机骨架材料在氧气条件下进行煅烧,得到绣球状CuZnOX纳米材料,其中x为1~或2。
本发明利用无毒的原料合成一系列的高质量的锌铜金属有机骨架材料,且设计合理,操作简单,采用的原材料无毒、环保、成本低,工艺简单,易于操作控制,适于连续大规模生产,制备过程无污染,安全性好,绿色环保。
在上述步骤1和2)中,室温条件下搅拌24小时能增加分子的运动速度,通过共沉淀的方法使反应进行的更加快速和彻底。
本发明所述锌盐为Zn(CH3COO)2,在实际实验中,由于乙酸根易脱去,更易得到所需的产物,因此优先采这种锌盐。
所述CuSO4•5H2O廉价易得,相对比较稳定,因此优先采用这种盐。
所述有机配体为2-甲基咪唑。2-甲基咪唑为常见有机配体,价廉且易得,因此优先采用。
另外,本发明所述步骤1)中锌盐水溶液和有机配体水溶液中Zn(CH3COO)2与2-甲基咪唑的混合质量比为2.195∶1.642。此比例下的反应物进行反应,得到的产物形貌更加均匀,性能更加优良。
所述步骤2)所述锌金属沸石咪唑类骨架材料与硫酸铜水溶液中硫酸铜的混合质量比为1.58∶1.25。此比例下的反应物进行反应,得到的产物的形貌更加均匀,性能更加优良。
本发明通过控制锌盐与硫酸铜的比例进行反应,最终所制得形状好看的锌铜金属有机骨架材料。
所述的煅烧温度为750℃。在氧气条件下,煅烧温度条件为750℃,使产物分解的更彻底,并且保持良好的形貌特征。
本发明另一目的还提出采用以上方法制成的锌铜金属氧化物纳米材料在电催化中的应用。
将绣球状CuZnOX纳米材料与乙醇、Nafion在超声条件下混合后修饰在玻碳电极表面,干燥后得绣球状的CuZnOX电催化电极。
该应用的特点及优点:
(1)绣球状的CuZnOX纳米材料虽然其导电性较差,但其特殊的球状的纳米结构,大大提高了在氧析出反应(OER)等方面的电催化性能。
(2)利用电子传递,只需要通过很薄的膜层,电子就可以到达载体电极上。
(3)氧析出反应(OER)被认为是对环境友好和可再生的能源系统。
附图说明
图1为本发明制备的片状的锌金属有机骨架电极材料的扫描电镜图(SEM)。
图2为本发明制备的锌铜金属有机骨架材料的扫描电镜图(SEM)。
图3为本发明制备的绣球状的CuZnOX的电极材料的扫描电镜图(SEM)。
图4为本发明制备的绣球状的CuZnOX电极材料的X射线衍射图(XRD)。
图5为本发明制备的绣球状的CuZnOX电极材料的OER的循环伏安曲线图 (CV)。
图6为本发明制备的绣球状的CuZnOX电极材料的OER的线性扫描曲线图(LSV)。
具体实施方式
下面实施例对本发明做进一步说明,但不限于此。
一、制备绣球状的CuZnOX纳米材料:
(1)称取2.195g的Zn(CH3COO)2,溶解在50mL的去离子水中,取得50mL锌盐水溶液。
(2)称取1.642g的2-甲基咪唑溶于60mL去离子水中,形成60mL的有机配体水溶液。
(3)称取1.25g 的CuSO4•5H2O溶于10mL去离子水中,形成10mL的硫酸铜水溶液。
(4)将锌盐水溶液迅速滴加到步骤(2)取得的有机配体水溶液中,并室温搅拌24小时得到中间产物,用水和乙醇离心洗涤,并自然凉干,取得1.58g 锌金属沸石咪唑类骨架材料。
对锌金属沸石咪唑类骨架纳米材料进行SEM测试,结果如下:
图1为片状的锌金属沸石咪唑类骨架材料在放大10000倍下的扫描电子显微镜照片,其显示典型的笼状结晶结构,可以为扩散和储存电解质离子提供大的比表面积。
对锌铜金属有机骨架纳米材料进行SEM测试:图2为锌铜金属有机骨架材料的扫描电镜图,其样品表面为片状的球形结构。
(5)将1.58g锌金属沸石咪唑类骨架材料,放在步骤(3)取得的硫酸铜水溶液中浸泡24小时进行反应。反应完成后,取固相用水和乙醇多次洗涤,得到产物。
(6)将产物在氧气750℃条件下煅烧,得到0.34g绣球状CuZnOX纳米材料,其中x为1~或2。
对绣球状CuZnOX纳米材料进行SEM测试:图3为绣球状的CuZnOX的扫描电镜图,其样品由球状颗粒组成的一个大球。
对绣球状的CuZnOX纳米材料进行XRD测试:图4为绣球状的CuZnOX纳米材料的X射线衍射图,可见其峰锌铜金属氧化物的峰。
二、电催化电极的制备:
1、将直径为3 mm的玻碳电极分别用吸附了1 μm氧化铝悬浮液的砂纸和吸附了0.3 μm氧化铝悬浮液的砂纸打磨抛光。
2、将打磨抛光好的玻碳电极依次放在去离子水中超声清洗1分钟后,在由KCl和K3[Fe(CN)6]、水组成的浓度为0.5 M的水溶液中扫描循环伏安曲线,以测试电极是否磨好,最后取得洁净的玻碳电极,晾干以待用。
3、取3.5mg步骤(6)制备的绣球状的CuZnOX纳米材料加入由500 μL 乙醇和50μLNafion混合组成的Nafion水溶液中,超声混合,制成混合溶液,随后将5μL混合溶液采用涂覆的方法修饰在直径为3 mm的洁净的玻碳电极表面,自然晾干后即得绣球状的CuZnOX电催化电极。
三、配置电解液:
以氢氧化钾作为电解液,其中,氢氧化钾浓度为1 mol/L。
四、检测电极的电催化性能:
将绣球状的CuZnOX电催化电极放置在1 mol/L的KOH水溶液中进行测定。
利用电化学工作站,将制备的待测电极在事先通入大约半小时氮气的电解质溶液中,在0.5~2.0 V之间的电位下,扫描速率控制为0.01 V/s,先进行循环伏安扫描,然后在0.4~1.5 V之间的电位下,扫描速率控制为10 mV/s,进行线性伏安扫描,测试样品的电化学性能。
图5显示了绣球状的CuZnOX电催化电极在电位(相对于标准氢电极)为1.8~2.8 V范围内显示无明显的氧化还原峰。
图6显示了绣球状的CuZnOX电催化电极在电位(相对于标准氢电极)为1.4~2.5 V在1 mol/L氢氧化钾电解质溶液中显示出良好的OER电催化性能,在电流密度为10 mA cm-2时对应的电压为2.38 V,其相对于其他Cu极材料,性能有所提升。
五、绣球状的CuZnOX电催化电极可能的应用前景及优势:
根据调研的相关文献可知,绣球状的CuZnOX电化学性能优越于其它非贵金属,这使得它从MOFs派生物的OER中脱颖而出。混合金属氧化物,通常具有复杂的微观协调能力,提供了很大的帮助对于内部活动进行微调的优点。更重要的是,它具有比较高的电子导电率,大的比表面积,促进其高的OER催化活性。努力完善多金属氧化物纳米结构,以提高电化学的性能是我们一直以来的追求。
Claims (7)
1.绣球状CuZnOX纳米材料的制备方法,其特征在于包括以下步骤:
1)将锌盐水溶液和有机配体水溶液混合后,在室温条件下进行搅拌反应,得到锌金属沸石咪唑类骨架材料;
2)将所述锌金属沸石咪唑类骨架材料与硫酸铜水溶液再混合,在室温条件下进行搅拌反应;
3)反应结束后,用水和乙醇清洗,得锌铜金属有机骨架材料;
4)将锌铜金属有机骨架材料在氧气条件下进行煅烧,得到绣球状CuZnOX纳米材料,其中x为1或2。
2.根据权利要求1所述的制备方法,其特征在于所述锌盐为Zn(CH3COO)2。
3.根据权利要求2所述的制备方法,其特征在于所述有机配体为2-甲基咪唑。
4.根据权利要求3所述的制备方法,其特征在于所述步骤1)中锌盐水溶液和有机配体水溶液中Zn(CH3COO)2与2-甲基咪唑的混合质量比为2.195∶1.642。
5.根据权利要求4所述的制备方法,其特征在于所述步骤2)所述锌金属沸石咪唑类骨架材料与硫酸铜水溶液中硫酸铜的混合质量比为1.58∶1.25。
6.根据权利要求1所述的制备方法,其特征在于所述的煅烧温度为750℃。
7.如权利要求1所述制备方法取得的绣球状CuZnOX纳米材料在电催化中的应用,其特征在于:将绣球状CuZnOX纳米材料与乙醇、Nafion在超声条件下混合后修饰在玻碳电极表面,干燥后得绣球状的CuZnOX电催化电极。
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