CN105879880B - 一种复合纳米材料及其制备方法和用途 - Google Patents
一种复合纳米材料及其制备方法和用途 Download PDFInfo
- Publication number
- CN105879880B CN105879880B CN201610259978.9A CN201610259978A CN105879880B CN 105879880 B CN105879880 B CN 105879880B CN 201610259978 A CN201610259978 A CN 201610259978A CN 105879880 B CN105879880 B CN 105879880B
- Authority
- CN
- China
- Prior art keywords
- rgo
- nano materials
- composite nano
- solution
- hydrogen peroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 61
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 61
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 13
- 238000001291 vacuum drying Methods 0.000 claims abstract description 11
- 235000019441 ethanol Nutrition 0.000 claims abstract description 6
- 239000011219 quaternary composite Substances 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 229910002696 Ag-Au Inorganic materials 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 34
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- 238000007540 photo-reduction reaction Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000002474 experimental method Methods 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000011160 research Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 238000002484 cyclic voltammetry Methods 0.000 claims description 3
- 229910018292 Cu2In Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000013528 metallic particle Substances 0.000 claims description 2
- 239000008055 phosphate buffer solution Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 241000549556 Nanos Species 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000010931 gold Substances 0.000 abstract description 18
- 229910021389 graphene Inorganic materials 0.000 abstract description 17
- 238000000835 electrochemical detection Methods 0.000 abstract description 6
- 229910001922 gold oxide Inorganic materials 0.000 abstract description 5
- 229910052709 silver Inorganic materials 0.000 abstract description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract 1
- 239000004332 silver Substances 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- -1 cuprous oxide compound Chemical class 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229940021013 electrolyte solution Drugs 0.000 description 3
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Electrochemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种石墨烯/银‑金/氧化亚铜(rGO/Ag‑Au/Cu2O)复合材料及其制备方法和用途。称取Ag‑Au/Cu2O固体粉末，用去离子水超声分散、搅拌混合均匀；再称取rGO固体粉末加入到去离子水中搅拌、超声分散，然后加入到搅拌中的Ag‑Au/Cu2O溶液中，搅拌反应后用去离子水和乙醇离心清洗数次，放到真空干燥箱干燥得rGO/Ag‑Au/Cu2O四元复合纳米材料，比rGO和Ag‑Au/Cu2O复合纳米材料以及单纯的玻碳电极在电化学检测过氧化氢方面，表现出更好的电催化性能。
Description
技术领域
本发明涉及一种石墨烯/银-金/氧化亚铜(rGO/Ag-Au/Cu2O)复合材料及其制备方法和用途，尤其是一种制备工艺简单，产品性能稳定，具有良好电催化检测双氧水性能的复合材料制备方法。
技术背景
过氧化氢(H2O2)是一种被广泛应用于食品、制药、造纸、和化工行业的化学品。同时，它也是大量氧化酶催化反应的副产物，所以精确和快速检测H2O2在生物化学和环境科学中具有重要意义。与H2O2测定的常规技术相比，电化学生物传感无酶检测H2O2具有成本低、易于制备、快速检测、高选择性、灵敏度等许多优点。同时，可利用无酶参与的H2O2生物传感器初步测试所制备的rGO/Ag-Au/Cu2O纳米复合材料的电催化性能。
石墨烯自被发现以来，已在物理、化学和电子工业等领域得到广泛研究和应用。石墨烯具有大的比表面积、高的电导率、化学惰性、廉价和易于制备等诸多优势，可用于制备优异性能的电化学材料。将石墨烯与金属或者金属氧化物复合，会增强材料的导电性、电催化活性和提高金属或者金属氧化物纳米材料的稳定性。
目前，石墨烯/氧化亚铜复合物、石墨烯/贵金属复合物以及氧化亚铜/贵金属复合物在作为电催化材料都有过报道，但rGO/Ag-Au/Cu2O四元复合纳米材料的合成及其在电催化检测H2O2方面的研究，至今还未有报道。rGO化学和物理性质稳定，制备原材料廉价易得，无毒，且以其为载体制备的rGO/Ag-Au/Cu2O，其工艺简单，所得产品电催化活性好，在电化学检测双氧水领域具有重大应用前景。
发明内容
本发明要解决的技术问题是提供一种制备工艺简单、产品性能稳定，具有良好电催化性能的石墨烯/银-金/氧化亚铜复合纳米材料的制备方法和应用，可用来检测过氧化氢含量。
为解决上述技术问题，本发明提供一种石墨烯/银-金/氧化亚铜复合纳米材料的制备方法，制备原料包括石墨烯、氧化亚铜、含Ag+和Au+的盐溶液，制备方法包括如下步骤：
(1)制备氧化亚铜Cu2O：称取抗坏血酸和氢氧化钠溶于纯净水中，磁力搅拌至充分溶解后，缓缓加入一水醋酸铜溶液，反应至少0.5h后，再用蒸馏水和无水乙醇洗净产物，离心，烘干，得立方体的氧化亚铜Cu2O粉末(Materials Letters,2014,114,88-91)。
(2)制备Ag-Au/Cu2O复合电催化材料：(a)称取Cu2O粉体溶于纯净水中，超声分散，再加入HAucl4溶液，磁力搅拌至混合均匀后，在钨灯下光照还原反应，反应后洗涤、离心分离、干燥后得到Au/Cu2O复合纳米材料。(b)具体实验步骤同步骤(a)所述，但Cu2O粉体由Au/Cu2O粉体代替，加入的HAucl4溶液由AgNO3溶液代替，得到Ag-Au/Cu2O复合纳米材料。
(3)制备石墨烯(rGO)：将浓H2SO4和NaNO3在烧杯里搅拌混合均匀，冰浴使其温度为0℃，称取石墨粉末加入其中，搅拌至少0.5h。边搅拌边缓慢的加入KMnO4，再搅拌至少0.5h，整个过程保持温度在10℃以下。之后升温保持恒温再搅拌至少4h，直到溶液颜色变为褐色，然后用去离子水稀释，再搅拌至少0.5h，接着将30％H2O2加入其中来去除其中的KMnO4，此时溶液变为亮黄色。然后固体反复用HCl和去离子水过滤洗涤数次，在真空干燥箱干燥制得氧化石墨烯(GO)。称取制备好的GO加入到水-乙二醇溶液中超声分散，然后将水合肼缓慢加入其中，搅拌至少10min后，将混合液体转移到反应釜中，高温反应。制备好的黑色固体用水和乙醇离心收集和洗涤数次，放置在真空干燥箱中干燥，得氧化还原石墨烯(rGO，简称石墨烯)(Journal of the American Chemical Society,1958,80，1339-1339)。
(4)制备rGO/Ag-Au/Cu2O复合电催化材料：称取制备好的Ag-Au/Cu2O固体粉末，用去离子水超声分散、搅拌混合均匀；再称取制备好的rGO固体粉末加入到去离子水中搅拌、超声分散，然后加入到搅拌中的Ag-Au/Cu2O溶液中，搅拌反应后用去离子水和乙醇离心清洗数次，放到真空干燥箱干燥得rGO/Ag-Au/Cu2O复合电催化材料。
其中，步骤(2)中，Cu2O、HAuCl4和AgNO3的质量比为：100：25.8：23.6；所述HAuCl4溶液浓度为0.03mol·L-1，AgNO3溶液浓度为0.05mol·L-1；其中，光照还原反应条件为：钨灯光催化反应器功率500W，光照时间0.5～2h；所述Cu2O和纯净水的质量比为：1：1000。
步骤(3)中，GO、NaNO3、石墨和KMnO4的质量比为：1：5：10：60；所述水合肼、H2O2、水-乙二醇和H2SO4的体积比为：2：15：40：100。
步骤(4)中，Ag-Au/Cu2O和rGO的质量比为250：13，搅拌反应的时间为1h。
步骤(2)～步骤(4)中超声分散的条件为：超声机功率250W，超声时间为0.5h；
本发明还提供一种上述的石墨烯/银-金/氧化亚铜复合纳米材料在检测过氧化氢含量中的应用，利用所制备的rGO/Ag-Au/Cu2O复合纳米材料修饰玻碳电极，并在N2饱和的0.2mol·L-1的PBS溶液中进行过氧化氢检测的电催化性能研究。
称取rGO/Ag-Au/Cu2O复合纳米材料和电解质溶液分散在水-异丙醇混合溶剂中，超声分散得到均相溶液；然后，将催化剂溶液滴在预处理过的玻碳电极上(GCE)，在室温下晾干后得到Au-Ag/Cu2O修饰的玻碳电极。
在双氧水存在情况下，对其进行检测双氧水的循环伏安(CV)实验。
其中，所述的rGO/Ag-Au/Cu2O复合纳米材料质量为0.5mg，电解质溶液体积为10μL，水-异丙醇混合溶剂(3:1v/v)体积为1mL，滴在预处理过的玻碳电极上的催化剂溶液的体积为10μL，双氧水的浓度为5mM。
利用rGO和Ag-Au/Cu2O复合纳米材料作为对比，可以看出，rGO/Ag-Au/Cu2O复合纳米材料有较强的还原峰和电流响应，在电化学检测过氧化氢方面，表现出更好的电催化性能。
利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)以及透射电子显微镜(TEM)，对产物进行形貌结构分析，利用所制备的Au-Ag/Cu2O复合纳米材料修饰玻碳电极，并在N2饱和的0.2mol·L-1的PBS溶液中进行过氧化氢检测的电催化性能研究。其中PBS溶液为0.2mol·L-1Na2HPO4溶液和0.2mol·L-1NaH2PO4溶液以体积比为81：19的混合溶液，pH＝7.4。
本发明合成的rGO/Ag-Au/Cu2O复合电催化材料是一种四元复合纳米材料，目前未见报道，而rGO/Cu2O复合物、rGO/贵金属复合物以及Cu2O/贵金属复合物等作为电催化材料都有过报道，并且方法以水热法，还原剂湿化学法，光照还原法为主。本发明第一次采用简单的一步超声搅拌的方法，将石墨烯与Au-Ag/Cu2O复合纳米材料进行负载，得到rGO/Ag-Au/Cu2O复合材料，操作十分简单，在室温下就能进行，石墨烯大的比表面积和良好的导电性为电子的转移提供了快速的通道，Au-Ag/Cu2O复合纳米材料也能进而解决石墨烯薄片容易聚集的缺陷，两者有效的结合，通过他们之间彼此的协同作用，大大增加了rGO/Ag-Au/Cu2O复合纳米材料的电催化检测H2O2的性能。以望为制备高性能的复合纳米材料H2O2传感器提供依据。
本发明的上述技术方案的有益效果如下：
利用本发明提供的制备方法制备的rGO/Ag-Au/Cu2O复合纳米材料比rGO和Ag-Au/Cu2O复合纳米材料以及单纯的玻碳电极在电化学检测过氧化氢方面，表现出更好的电催化性能。
附图说明
图1为利用本发明制备的GO、rGO、Ag-Au/Cu2O和rGO/Ag-Au/Cu2O的X射线衍射图谱；从图中可以看出，样品中是由rGO、Cu2O、Ag和Au组成，说明GO、rGO、Ag-Au/Cu2O和rGO/Ag-Au/Cu2O复合纳米材料很好的合成。
图2为为利用本发明制备的rGO/Ag-Au/Cu2O复合纳米材料的透射电镜照片。由图中可以看出，样品中的金属颗粒很均匀的负载在立方体氧化亚铜表面上，氧化亚铜负载在薄片的rGO上。
图3为单纯玻碳电极、rGO、Ag-Au/Cu2O和rGO/Ag-Au/Cu2O复合电催化材料对双氧水检测的循环伏安曲线图。由图中可以看出，rGO/Ag-Au/Cu2O复合纳米材料比单纯玻碳电极、rGO和Ag-Au/Cu2O纳米材料在电化学检测双氧水方面，表现出更好的电催化性能。
具体实施方式
实施例1：制备立方体的氧化亚铜Cu2O
Cu2O的制备采用的水热合成方法；将20ml、0.009mol·L-1抗坏血酸溶液加入到32ml、0.391mol·L-1的氢氧化钠溶液中，搅拌5min，再加入32ml、0.005mol·L-1的一水醋酸铜溶液，搅拌15min，反应0.5h后用纯净水和无水乙醇洗涤、离心分离，最后于60℃真空干燥箱中干燥12h，得到立方体的氧化亚铜Cu2O粉末。
实施例2 15％-15％Au-Ag/Cu2O复合纳米材料的制备
称取0.05g Cu2O粉体溶于50ml纯净水中，然后功率为250W的超声机中超声分散0.5h，再加入1.3ml 0.03mol·L-1HAuCl4，搅拌0.5h；然后功率为500W的钨灯下光还原0.5h，反应后用纯净水和无水乙醇洗涤、离心分离、60℃真空干燥箱中干燥后得到Au与Cu2O质量比为15％的Au/Cu2O复合纳米材料；称取0.05g 15％Au/Cu2O粉体溶于50ml纯净水中，然后功率为250W的超声机中超声分散0.5h，再加入1.4ml 0.05mol·L-1AgNO3，搅拌0.5h；然后功率为500W的钨灯下光还原0.5h，反应后用纯净水和无水乙醇洗涤、离心分离、60℃真空干燥箱中干燥后得到Au、Ag与Cu2O质量比均为15％的15％-15％Au-Ag/Cu2O复合纳米材料。
实施例3 rGO纳米材料的制备
将100mL浓H2SO4和0.5g的NaNO3在500mL的烧杯里搅拌混合均匀，冰浴使其温度为0℃，称取1.0g的石墨粉末加入其中，搅拌30min。边搅拌边缓慢的加入6.0g的KMnO4，再搅拌0.5h，整个过程保持温度在10℃以下。之后升温至35℃，保持恒温再搅拌4h，直到溶液颜色变为褐色，然后用去离子水稀释至400ml，再搅拌0.5h，接着将15mL 30％的H2O2加入其中来去除其中的KMnO4，此时溶液变为亮黄色。然后固体反复用5％HCl和去离子水过滤洗涤数次，在真空干燥箱中60℃干燥24h制得GO。称取100mg制备好的GO加入到40mL的水-乙二醇溶液中超声1h，然后将2.0ml水合肼缓慢加入其中，搅拌10min后，将混合液体转移到50mL反应釜中，180℃反应10h。制备好的rGO黑色固体用水和乙醇离心收集和洗涤数次，放置在45℃的真空干燥箱中干燥，得氧化还原石墨烯(rGO，简称石墨烯)。
实施例4 5％rGO/Ag-Au/Cu2O复合纳米材料的制备
称取制备好的Ag-Au/Cu2O固体粉末50mg，用50mL去离子水超声、搅拌混合均匀，再称取制备好的rGO固体粉末2.6mg加入到20mL去离子水中搅拌、超声，然后加入到搅拌中的Ag-Au/Cu2O溶液中，搅拌1h，用去离子水和乙醇离心清洗数次，放到真空干燥箱中50℃干燥5h。
实施例5 5％rGO/Ag-Au/Cu2O复合纳米材料电化学检测H2O2
0.5mg 5％rGO/Ag-Au/Cu2O复合纳米材料和10μL电解质溶液(5wt％)分散在1mL水-异丙醇混合溶剂中(3:1v/v)，超声分散至少30min得到催化剂溶液；然后，将10μL催化剂溶液滴在预处理过的玻碳电极上(GCE)，在室温下晾干后得到5％rGO/Ag-Au/Cu2O修饰的玻碳电极。
电流和循环伏安法(CV)实验是在CHI 650d电化学分析仪(CH仪器有限公司、上海)中进行的，采用自制的三电极电化学装置的组成为：一个扭曲的铂丝为辅助电极，饱和甘汞电极作为参比电极(SCE)和修饰的玻碳电极作为工作电极(0.07cm2)，所有实验温度均为环境温度，电解液为0.2M的磷酸盐缓冲溶液(PBS，pH＝7.4)，用高纯氮气进行至少30min并维持在氮气氛围中。
利用单纯玻碳电极、rGO、Ag-Au/Cu2O纳米材料作为对比，由图3中可以看出，5％rGO/Ag-Au/Cu2O复合纳米材料比其他电催化材料在电化学检测双氧水方面，表现出更好的电催化性能。
Claims (7)
1.一种复合纳米材料，其特征在于：所述复合纳米材料为rGO/Ag-Au/Cu2O四元复合纳米材料，金属颗粒均匀地负载在立方体氧化亚铜表面上，氧化亚铜负载在薄片的rGO上，所述复合纳米材料的制备方法如下：称取Ag-Au/Cu2O固体粉末，用去离子水超声分散、搅拌混合均匀；再称取rGO固体粉末加入到去离子水中搅拌、超声分散，然后加入到搅拌中的Ag-Au/Cu2O溶液中，搅拌反应后用去离子水和乙醇离心清洗数次，放到真空干燥箱干燥得rGO/Ag-Au/Cu2O四元复合纳米材料；Ag-Au/Cu2O和rGO的质量比为250：13，搅拌反应的时间为1h；超声分散的条件为：超声机功率250W，超声时间为0.5h。
2.如权利要求1所述的一种复合纳米材料，其特征在于，所述Ag-Au/Cu2O固体粉末的制备方法如下：(a)称取立方体的Cu2O粉体溶于纯净水中，超声分散，再加入HAuCl4溶液，磁力搅拌至混合均匀后，在钨灯下光照还原反应，反应后洗涤、离心分离、干燥后得到Au/Cu2O复合纳米材料；(b)具体实验步骤同步骤(a)所述，但Cu2O粉体由Au/Cu2O粉体代替，加入的HAuCl4溶液由AgNO3溶液代替，得到Ag-Au/Cu2O复合纳米材料。
3.如权利要求2所述的一种复合纳米材料，其特征在于：Cu2O、HAuCl4和AgNO3的质量比为：100：25.8：23.6；所述HAuCl4溶液浓度为0.03mol·L-1，AgNO3溶液浓度为0.05mol·L-1；其中，光照还原反应条件为：钨灯光催化反应器功率500W，光照时间0.5～2h；所述Cu2O和纯净水的质量比为：1：1000；超声分散的条件为：超声机功率250W，超声时间为0.5h。
4.如权利要求1所述的一种复合纳米材料在检测过氧化氢含量中的用途。
5.如权利要求4所述的一种复合纳米材料在检测过氧化氢含量中的用途，其特征在于按照如下步骤进行：称取rGO/Ag-Au/Cu2O复合纳米材料和电解质溶液分散在水-异丙醇混合溶剂中，超声分散得到催化剂溶液；然后，将催化剂溶液滴在预处理过的玻碳电极上(GCE)，在室温下晾干后得到rGO/Ag-Au/Cu2O修饰的玻碳电极，在双氧水存在情况下，对其进行检测双氧水的循环伏安(CV)实验。
6.如权利要求5所述的一种复合纳米材料在检测过氧化氢含量中的用途，其特征在于：所述rGO/Ag-Au/Cu2O复合纳米材料质量为0.5mg，电解质溶液体积为10μL，按照体积比3:1混合的水-异丙醇混合溶剂体积为1mL，催化剂溶液体积为10μL，双氧水的浓度为5mM。
7.如权利要求5所述的一种复合纳米材料在检测过氧化氢含量中的用途，其特征在于：循环伏安法(CV)实验是在CHI 650d电化学分析仪中进行的，采用自制的三电极电化学装置，其组成为：一个扭曲的铂丝为辅助电极，饱和甘汞电极作为参比电极(SCE)和修饰的玻碳电极作为工作电极，所有实验温度均为环境温度，并在N2饱和的电解质溶液中进行过氧化氢检测的电催化性能研究，电解质溶液为0.2M的pH为7.4的磷酸盐缓冲溶液。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610259978.9A CN105879880B (zh) | 2016-04-25 | 2016-04-25 | 一种复合纳米材料及其制备方法和用途 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610259978.9A CN105879880B (zh) | 2016-04-25 | 2016-04-25 | 一种复合纳米材料及其制备方法和用途 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105879880A CN105879880A (zh) | 2016-08-24 |
| CN105879880B true CN105879880B (zh) | 2018-10-09 |
Family
ID=56704613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610259978.9A Active CN105879880B (zh) | 2016-04-25 | 2016-04-25 | 一种复合纳米材料及其制备方法和用途 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105879880B (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108889959B (zh) * | 2018-06-20 | 2021-09-28 | 湖南大学 | 一种rGO/Cu复合材料及其制备方法 |
| CN109603846B (zh) * | 2018-11-28 | 2022-03-22 | 西安理工大学 | 一种形貌可控的Ag/Cu2O异质结构材料的制备方法 |
| CN111777063A (zh) * | 2020-07-09 | 2020-10-16 | 西安交通大学 | 一种纳米材料的制备方法 |
| CN113881100B (zh) * | 2021-09-24 | 2023-04-25 | 深圳环能石墨烯科技有限公司 | Ag/Cu2O/rGO纳米复合抗菌剂、抗菌母粒及其制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030170A (zh) * | 2013-01-16 | 2013-04-10 | 哈尔滨工业大学 | 一种氧化亚铜/还原氧化石墨烯复合功能材料的制备方法 |
| CN103094540A (zh) * | 2013-01-06 | 2013-05-08 | 中物院成都科学技术发展中心 | 石墨烯与金属氧化物/金属化合物的复合方法及其复合材料 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9005816B2 (en) * | 2013-03-06 | 2015-04-14 | Uchicago Argonne, Llc | Coating of porous carbon for use in lithium air batteries |
-
2016
- 2016-04-25 CN CN201610259978.9A patent/CN105879880B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103094540A (zh) * | 2013-01-06 | 2013-05-08 | 中物院成都科学技术发展中心 | 石墨烯与金属氧化物/金属化合物的复合方法及其复合材料 |
| CN103030170A (zh) * | 2013-01-16 | 2013-04-10 | 哈尔滨工业大学 | 一种氧化亚铜/还原氧化石墨烯复合功能材料的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105879880A (zh) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105664966A (zh) | 金属/氧化亚铜复合纳米材料的制备方法和应用 | |
| Huang et al. | A strategy for effective electrochemical detection of hydroquinone and catechol: Decoration of alkalization-intercalated Ti3C2 with MOF-derived N-doped porous carbon | |
| Jeromiyas et al. | Bismuth nanoparticles decorated graphenated carbon nanotubes modified screen-printed electrode for mercury detection | |
| Li et al. | Three-dimensional porous MXene/NiCo-LDH composite for high performance non-enzymatic glucose sensor | |
| Zhu et al. | Alkaline intercalation of Ti3C2 MXene for simultaneous electrochemical detection of Cd (II), Pb (II), Cu (II) and Hg (II) | |
| Shen et al. | Highly sensitive nonenzymatic glucose sensor based on Nickel nanoparticle–attapulgite-reduced graphene oxide-modified glassy carbon electrode | |
| CN105879880B (zh) | 一种复合纳米材料及其制备方法和用途 | |
| Yan et al. | A non-enzymatic glucose sensor based on the CuS nanoflakes–reduced graphene oxide nanocomposite | |
| Long et al. | Novel helical TiO2 nanotube arrays modified by Cu2O for enzyme-free glucose oxidation | |
| He et al. | Non-enzymatic hydrogen peroxide electrochemical sensor based on a three-dimensional MnO 2 nanosheets/carbon foam composite | |
| Moolayadukkam et al. | Role of transition metals in layered double hydroxides for differentiating the oxygen evolution and nonenzymatic glucose sensing | |
| Zhan et al. | A hydrogen peroxide electrochemical sensor based on silver nanoparticles decorated three-dimensional graphene | |
| Lin et al. | Fast preparation of MoS 2 nanoflowers decorated with platinum nanoparticles for electrochemical detection of hydrogen peroxide | |
| Wang et al. | Carbon functionalized metal organic framework/Nafion composites as novel electrode materials for ultrasensitive determination of dopamine | |
| Xie et al. | Cu metal-organic framework-derived Cu Nanospheres@ Porous carbon/macroporous carbon for electrochemical sensing glucose | |
| Zou et al. | Au nanoparticles supported on functionalized two-dimensional titanium carbide for the sensitive detection of nitrite | |
| CN104525239A (zh) | 一种金钯合金/氮化碳复合纳米材料及其制备方法和用途 | |
| CN103018303A (zh) | 一种镍铝层状双金属氢氧化物修饰电极的制备方法 | |
| Wei et al. | Economical, green and rapid synthesis of CDs-Cu2O/CuO nanotube from the biomass waste reed as sensitive sensing platform for the electrochemical detection of hydrazine | |
| CN102847533B (zh) | 微波法合成凹土/钯纳米复合材料催化剂的方法 | |
| Jia et al. | Electrocatalytically active cuprous oxide nanocubes anchored onto macroporous carbon composite for hydrazine detection | |
| Cooray et al. | Cobalt selenide nanoflake decorated reduced graphene oxide nanocomposite for efficient glucose electro-oxidation in alkaline medium | |
| Kazici et al. | Synthesis of Pd-Ni/C bimetallic materials and their application in non-enzymatic hydrogen peroxide detection | |
| CN102151529B (zh) | 一种酚醛树脂包覆碳纳米管复合材料及其化学制备方法 | |
| Wu et al. | A molecularly imprinted electrochemical enzymeless sensor based on functionalized gold nanoparticle decorated carbon nanotubes for methyl-parathion detection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221123 Address after: 230000 Room 203, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee after: Hefei Jiuzhou Longteng scientific and technological achievement transformation Co.,Ltd. Address before: 212013 No. 301, Xuefu Road, Zhenjiang, Jiangsu Patentee before: JIANGSU University |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20240523 Address after: Room 506, 5th Floor, Building B, Innovation and Entrepreneurship Service Center, No. 460 Jinshan Road, Jinshan Street, Hetang District, Zhuzhou City, Hunan Province, 412000 Patentee after: Hunan Dechuang Yonghe Environmental Protection Technology Co.,Ltd. Country or region after: China Address before: 230000 Room 203, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee before: Hefei Jiuzhou Longteng scientific and technological achievement transformation Co.,Ltd. Country or region before: China |