CN108311144A - 一种哑铃状纳米金-铂复合催化剂及其制备方法 - Google Patents
一种哑铃状纳米金-铂复合催化剂及其制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 39
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 11
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- QKXCAKZMAORNSR-UHFFFAOYSA-N azane 1-chlorohexadecane Chemical compound N.CCCCCCCCCCCCCCCCCl QKXCAKZMAORNSR-UHFFFAOYSA-N 0.000 claims abstract description 4
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical class Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims abstract description 4
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000036571 hydration Effects 0.000 claims abstract description 4
- 238000006703 hydration reaction Methods 0.000 claims abstract description 4
- -1 enuatrol Chemical compound 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 13
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 10
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 6
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229940088594 vitamin Drugs 0.000 claims 1
- 229930003231 vitamin Natural products 0.000 claims 1
- 235000013343 vitamin Nutrition 0.000 claims 1
- 239000011782 vitamin Substances 0.000 claims 1
- 150000003722 vitamin derivatives Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000000975 dye Substances 0.000 abstract description 4
- 239000010842 industrial wastewater Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000010931 gold Substances 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract 1
- 229910052737 gold Inorganic materials 0.000 abstract 1
- 229910000104 sodium hydride Inorganic materials 0.000 abstract 1
- 239000012312 sodium hydride Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 description 6
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
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- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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Abstract
本发明公开了一种哑铃状纳米金‑铂复合催化剂,其特征在于:制备工艺中用到包括十六烷基氯化铵、油酸钠、氢化钠、十六烷基溴化铵、三水合氯金酸、硝酸银、抗坏血酸、氯铂酸、浓盐酸以及浓硝酸等成份,且制备了具有特殊形貌的复合型催化剂:哑铃状纳米金‑铂复合催化剂,纳米铂颗粒主要锚合在纳米金棒的两端,复合纳米粒子整体外形呈现哑铃状。将其催化特性应用于废水处理,解决了现有技术中的催化剂对工业废水中的染料等废弃物催化效果不够理想的问题,具有较好的氧还原催化活性。
Description
技术领域
本发明属于化学催化剂技术领域,特别是涉及一种哑铃状纳米金-铂复合催化剂及其制备方法。
背景技术
随着化学工业的发展,环境污染日益严重。其中,工业废水中的染料废水的排放量大而难处理,一直是废水处理的主要难点。湿法氧化是处理此类难降解染料废水的重要方法。温和条件下的非均相催化氧化,有较传统芬顿试剂独特优势而受到重视,廉价高效催化剂开发是该处理工艺的关键。肖丰收等((F.S.Xiaoe七alJCata1.2001,199:273-281)首先发现合成的经基磷酸铜是一种具有良好应用前景的新型催化材料,在温和条件下的一系列绿色氧化过程中表现出优异的催化性能。例如,经基磷酸铜在催化经化苯、苯酚和蔡酚等方面性能优越。轻基磷酸铜的催化活性优于著名的钦硅分子筛TS-1。但由于氧化活性过高,易于深度氧化生成焦油,限制了其应用。为了发挥该催化剂高氧化活性的特点,经基磷酸铜还被用于对硝基苯酚废水的降解处理,并且取得了较好效果。王润伟等(高等学校化学学报20081331-1333) 报道了水热条件下快速绿色合成轻基磷酸铜。最近,周翔(郑州大学2010)报道了层状轻基磷酸铜的制备,用于高浓度有机废水的处理效果明显。因此寻求轻基磷酸铜简便的合成方法和提高其催化活性成为催化研究的重点。
发明内容
本发明的目的是针对现有技术中的不足,提供一种哑铃状纳米金-铂复合催化剂及其制备方法,解决了现有技术中的催化剂对工业废水中的染料等废弃物催化效果不够理想的问题。
为了达到上述目的,本发明采用的技术方案是提供了一种哑铃状纳米金-铂复合催化剂,包括十六烷基氯化铵、油酸钠、氯铂酸、硼氢化钠、十六烷基溴化铵、三水合氯金酸、硝酸银、抗坏血酸、浓盐酸以及浓硝酸。
优选的,所述各组分浓度如下
CTAC97%
NaOL97%
H2PtCl6·6H2O98%
NaBH499%
CTAB98%
HAuCl4·3H2O99.99%
AgNO399.99%
AA>99.5%
HCl36.0~37.0%
HNO365.0~68.0%。
本发明还提供了一种哑铃状纳米金-铂复合催化剂的制备方法,包含如下步骤:
S1:将玻璃反应容器均在王水中浸泡12h;
S2:将CTAB加入到称量瓶中,然后加入HAuCl4溶液并搅拌10~20min,再加入新鲜制备的NaBH4溶液,剧烈搅拌2min,溶液颜色由黄色变为棕黄色,在30℃条件下静置30min后备用;
S3:称取CTAB7.0g、NaOL1.234g、H2PtCl6·6H2O1.2g置于500mL锥形瓶中,并加入250mL、 55℃的超纯水,待溶液冷却到30℃,加入AgNO3溶液,并在30℃条件下静置15min;随后加入HAuCl4溶液,在700r/min下搅拌90min,溶液由黄色变为无色;加入HCl,在400r/min搅拌15min;然后将抗坏血酸加入到该混合溶液中并剧烈搅拌30s;最后取0.4mL晶种溶液加入到生长溶液中,剧烈搅拌30s后,30℃静置12h,得到金纳米棒原液,金纳米棒原液离心并水洗两次,所得金纳米棒分散在0.1mol/L50mLCTAC溶液,保存在35℃的烘箱中备用;
S4:将AA与H2PdCl4按照摩尔量之比,制备试样,步骤如下:取CTAC修饰过的AuNRs溶液2mL置于40mL称量瓶中,加水稀释至20mL;加入3mL,0.01mol/L氯铂酸和4mL,1mmol/L硝酸银,再加入0.05mmol/L抗坏血酸,在700r/min下搅拌30s,然后30℃静置12h,产物离心处理水洗两次,最后分散在5mL超纯水中。
作为本方案的一种改进,S4中加入抗坏血酸的体积为60μL、150μL、600μL或300μL。
优选的,S1中所述的王水为浓盐酸与浓硝酸按照体积比为3:1组成的溶液。
优选的,S2中所述的CTAB量为0.2mol/L,5mL;HAuCl4溶液为0.5mmol/L,5mL;NaBH4溶液为6mmol/L,1mL。
优选的,S3中所述的AgNO3溶液为4mmol/L,24mL;HAuCl4溶液为1mmol/L,250mL;HCl 量为37wt%,4.8mL;抗坏血酸为64mmol/L,1.25mL。
与现有技术相比,本申请的催化剂表现出良好的催化对硝基苯酚还原性能,其催化活性主要由纳米铂颗粒在金棒两端的分散性和总的催化活性位点决定。以纳米铂颗粒尺寸为 20.7nm的Au/PdNDs(0.04mg/mL)作为催化剂,反应速率常数可达0.44min-1,比大多数钯负载型催化剂的催化活性都要高,证明其是一种非常有效的催化剂。
附图说明
图1是本发明的催化剂在氮气与氧气的循环伏安曲线
图2是本发明的催化剂在氮气与氧气不同转速下的LSV曲线
具体实施方式
下面通过具体实施例的形式为来对本发明的技术方案做进一步的详细的说明,但以下实施例仅起到帮助理解本发明的作用,并不能理解为是对本发明的进一步限定。
一种哑铃状纳米金-铂复合催化剂,包括十六烷基氯化铵、油酸钠、氯铂酸、硼氢化钠、十六烷基溴化铵、三水合氯金酸、硝酸银、抗坏血酸、浓盐酸以及浓硝酸。
优选的,所述各组分浓度如下
CTAC97%
NaOL97%
H2PtCl6·6H2O98%
NaBH499%
CTAB98%
HAuCl4·3H2O99.99%
AgNO399.99%
AA>99.5%
HCl36.0~37.0%
HNO365.0~68.0%。
实施例一:一种哑铃状纳米金-铂复合催化剂的制备方法,包含如下步骤:
S1:将玻璃反应容器均在王水中浸泡12h;
S2:将CTAB加入到称量瓶中,然后加入HAuCl4溶液并搅拌10~20min,再加入新鲜制备的NaBH4溶液,剧烈搅拌2min,溶液颜色由黄色变为棕黄色,在30℃条件下静置30min后备用;
S3:称取CTAB7.0g、NaOL1.234g、H2PtCl6·6H2O1.2g置于500mL锥形瓶中,并加入250mL、 55℃的超纯水,待溶液冷却到30℃,加入AgNO3溶液,并在30℃条件下静置15min;随后加入HAuCl4溶液,在700r/min下搅拌90min,溶液由黄色变为无色;加入HCl,在400r/min搅拌15min;然后将抗坏血酸加入到该混合溶液中并剧烈搅拌30s;最后取0.4mL晶种溶液加入到生长溶液中,剧烈搅拌30s后,30℃静置12h,得到金纳米棒原液,金纳米棒原液离心并水洗两次,所得金纳米棒分散在0.1mol/L50mLCTAC溶液,保存在35℃的烘箱中备用;
S4:改变AA与H2PdCl4的摩尔量之比,制备了AA:H2PdCl4=0.1的试样,并标记为AA:Pd=0.1。
样品AA:Pd=0.1的制备步骤如下:
取CTAC修饰过的AuNRs溶液2mL置于40mL称量瓶中,加水稀释至20mL;
首先加入3mL0.01mol/L氯铂酸和4mL1mmol/L硝酸银,再加入60μL0.05mmol/L抗坏血酸, 在700r/min下搅拌30s,然后30℃静置12h,产物离心处理水洗两次,最后分散在5mL超纯水中。
S1中所述的王水为浓盐酸与浓硝酸按照体积比为3:1组成的溶液。
S2中所述的CTAB量为0.2mol/L,5mL;HAuCl4溶液为0.5mmol/L,5mL;NaBH4溶液为6mmol/L,1mL。
S3中所述的AgNO3溶液为4mmol/L,24mL;HAuCl4溶液为1mmol/L,250mL;HCl量为37wt%,4.8mL;抗坏血酸为64mmol/L,1.25mL。
实施例二:其实施方式与实施例一基本相同,其不同之处在于:
S4:改变AA与H2PdCl4的摩尔量之比,制备了AA:H2PdCl4=0.25的试样,并标记为AA:Pd=0.25。
样品AA:Pd=0.25的制备步骤如下:
取CTAC修饰过的AuNRs溶液2mL置于40mL称量瓶中,加水稀释至20mL;
首先加入3mL0.01mol/L氯铂酸和4mL1mmol/L硝酸银,再加入150μL0.05mmol/L抗坏血酸,在700r/min下搅拌30s,然后30℃静置12h,产物离心处理水洗两次,最后分散在5mL超纯水中。
实施例三:其实施方式与实施例一基本相同,其不同之处在于:
S4:改变AA与H2PdCl4的摩尔量之比,制备了AA:H2PdCl4=0.5的试样,并标记为AA:Pd=0.5。
样品AA:Pd=0.5的制备步骤如下:
取CTAC修饰过的AuNRs溶液2mL置于40mL称量瓶中,加水稀释至20mL;
首先加入3mL0.01mol/L氯铂酸和4mL1mmol/L硝酸银,再加入300μL0.05mmol/L抗坏血酸,在700r/min下搅拌30s,然后30℃静置12h,产物离心处理水洗两次,最后分散在5mL超纯水中;
实施例四:其实施方式与实施例一基本相同,其不同之处在于:
S4:改变AA与H2PdCl4的摩尔量之比,制备了AA:H2PdCl4=1的试样,并标记为AA:Pd=1。
样品AA:Pd=1的制备步骤如下:
取CTAC修饰过的AuNRs溶液2mL置于40mL称量瓶中,加水稀释至20mL;
首先加入3mL0.01mol/L氯铂酸和4mL1mmol/L硝酸银,再加入600μL0.05mmol/L抗坏血酸,在700r/min下搅拌30s,然后30℃静置12h,产物离心处理水洗两次,最后分散在5mL超纯水中。
其中,实施例中催化效率下表1。
表1:
催化剂性质 | 纳米颗粒/纳米 | 催化速率 | |
AuNRs | 0 | 0.03 | |
实施例一 | AA:Pd=0.1 | 10.1 | 0.27 |
实施例二 | AA:Pd=0.25 | 14.5 | 0.31 |
实施例三 | AA:Pd=0.50 | 19.8 | 0.44 |
实施例四 | AA:Pd=1.00 | 31.5 | 0.29 |
本发明的哑铃状纳米金-铂复合催化剂的理化性能分析见附图1和附图2。
图1所示,氮气与氧气的循环伏安曲线图中,在0.1MKOH电解液,100mVs-1扫速。电位窗口-1.2~0.2V。在0.2~-0.6之间发生了氧化还原反应。
图2所示,氮气与氧气不同转速下的LSV曲线图中,在0.1MKOH电解液,10mVs-1扫速。从图中看出,起峰电位为0.8V,半波电位约0.6V。极限电流在2500RPM转速下,约为1.8mAcm-2,说明本申请具有较好的氧还原催化活性。
尽管上面已经示出和描述了本发明的实施例,可以理解的是,上述实施例是示例性的,不能理解为对本发明的限制,本领域的普通技术人员在不脱离本发明的原理和宗旨的情况下在本发明的范围内可以对上述实施例进行变化、修改、替换和变型,对其进行简单的组合变化都列为本发明的保护之内。
Claims (7)
1.一种哑铃状纳米金-铂复合催化剂,其特征在于:包括十六烷基氯化铵、油酸钠、氯铂酸、硼氢化钠、十六烷基溴化铵、三水合氯金酸、硝酸银、抗坏血酸、浓盐酸以及浓硝酸。
2.根据权利要求1所述的哑铃状纳米金-铂复合催化剂,其特征在于:所述各组分浓度如下
CTAC97%
NaOL97%
H2PtCl6·6H2O98%
NaBH499%
CTAB98%
HAuCl4·3H2O99.99%
AgNO399.99%
AA>99.5%
HCl36.0~37.0%
HNO365.0~68.0%。
3.一种权利要求1所述的哑铃状纳米金-铂复合催化剂的制备方法,其特征在于:包含如下步骤:
S1:将玻璃反应容器均在王水中浸泡12h;
S2:将CTAB加入到称量瓶中,然后加入HAuCl4溶液并搅拌10~20min,再加入新鲜制备的NaBH4溶液,剧烈搅拌2min,溶液颜色由黄色变为棕黄色,在30℃条件下静置30min后备用;
S3:称取CTAB7.0g、NaOL1.234g、H2PtCl6·6H2O1.2g,置于500mL锥形瓶中,并加入250mL55℃的超纯水,待溶液冷却到30℃,加入AgNO3溶液,并在30℃条件下静置15min;随后加入HAuCl4溶液,在700r/min下搅拌90min,溶液由黄色变为无色;加入HCl,在400r/min搅拌15min;然后将抗坏血酸加入到该混合溶液中并剧烈搅拌30s;最后取0.4mL晶种溶液加入到生长溶液中,剧烈搅拌30s后,30℃静置12h,得到金纳米棒原液,金纳米棒原液离心并水洗两次,所得金纳米棒分散在0.1mol/L50mLCTAC溶液,保存在35℃的烘箱中备用;
S4:调节AA与H2PdCl4的摩尔量之比为AA:Pd=0.5,制备催化剂。
4.根据权利要求3所述的哑铃状纳米金-铂复合催化剂的制备方法,其特征在于:S4中制备步骤如下:
取CTAC修饰过的AuNRs溶液2mL置于40mL称量瓶中,加水稀释至20mL;
首先加入3mL0.01mol/L氯铂酸和4mL1mmol/L硝酸银,再加入300μL0.05mmol/L抗坏血酸,在700r/min下搅拌30s,然后30℃静置12h,产物离心处理水洗两次,最后分散在5mL超纯水中,得到乳浊液催化剂。
5.根据权利要求3所述的哑铃状纳米金-铂复合催化剂的制备方法,其特征在于:S1中所述的王水为浓盐酸与浓硝酸按照体积比为3:1组成的溶液。
6.根据权利要求3所述的哑铃状纳米金-铂复合催化剂的制备方法,其特征在于:S2中所述的CTAB量为0.2mol/L,5mL;HAuCl4溶液为0.5mmol/L,5mL;NaBH4溶液为6mmol/L,1mL。
7.根据权利要求3所述的哑铃状纳米金-铂复合催化剂的制备方法,其特征在于:S3中所述的AgNO3溶液为4mmol/L,24mL;HAuCl4溶液为1mmol/L,250mL;HCl量为37wt%,4.8mL;抗坏血酸为64mmol/L,1.25mL。
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109158121A (zh) * | 2018-08-15 | 2019-01-08 | 临沂大学 | 具有优异催化双氧水性能的哑铃状纳米金的制备方法 |
CN112756623A (zh) * | 2020-12-31 | 2021-05-07 | 杭州电子科技大学 | 一种特殊结构的金-铂材料的合成方法 |
CN112809018A (zh) * | 2020-12-31 | 2021-05-18 | 杭州电子科技大学 | 一种金-铂双金属结构材料的合成方法 |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101450380A (zh) * | 2007-12-03 | 2009-06-10 | 国家纳米科学中心 | 一种树枝状金核/铂壳结构的双金属纳米棒及制备方法 |
CN101623762A (zh) * | 2008-07-09 | 2010-01-13 | 国家纳米科学中心 | 金核/银铂合金壳结构的岛状多孔三金属纳米棒及其制法 |
CN102019179A (zh) * | 2009-09-17 | 2011-04-20 | 国家纳米科学中心 | 一种金核/铂壳纳米棒模拟酶溶液及其制备方法 |
CN102039124A (zh) * | 2009-10-21 | 2011-05-04 | 国家纳米科学中心 | 铂诱导的金核/钯铂岛状合金壳结构纳米棒溶液及制法 |
CN104907578A (zh) * | 2015-04-29 | 2015-09-16 | 福州大学 | 一种金纳米棒的制备方法 |
-
2018
- 2018-01-04 CN CN201810009155.XA patent/CN108311144A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101450380A (zh) * | 2007-12-03 | 2009-06-10 | 国家纳米科学中心 | 一种树枝状金核/铂壳结构的双金属纳米棒及制备方法 |
CN101623762A (zh) * | 2008-07-09 | 2010-01-13 | 国家纳米科学中心 | 金核/银铂合金壳结构的岛状多孔三金属纳米棒及其制法 |
CN102019179A (zh) * | 2009-09-17 | 2011-04-20 | 国家纳米科学中心 | 一种金核/铂壳纳米棒模拟酶溶液及其制备方法 |
CN102039124A (zh) * | 2009-10-21 | 2011-05-04 | 国家纳米科学中心 | 铂诱导的金核/钯铂岛状合金壳结构纳米棒溶液及制法 |
CN104907578A (zh) * | 2015-04-29 | 2015-09-16 | 福州大学 | 一种金纳米棒的制备方法 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109158121A (zh) * | 2018-08-15 | 2019-01-08 | 临沂大学 | 具有优异催化双氧水性能的哑铃状纳米金的制备方法 |
CN109158121B (zh) * | 2018-08-15 | 2022-01-07 | 临沂大学 | 具有优异催化双氧水性能的哑铃状纳米金的制备方法 |
CN112756623A (zh) * | 2020-12-31 | 2021-05-07 | 杭州电子科技大学 | 一种特殊结构的金-铂材料的合成方法 |
CN112809018A (zh) * | 2020-12-31 | 2021-05-18 | 杭州电子科技大学 | 一种金-铂双金属结构材料的合成方法 |
CN112809018B (zh) * | 2020-12-31 | 2023-08-11 | 杭州电子科技大学 | 一种金-铂双金属结构材料的合成方法 |
CN113385687A (zh) * | 2021-06-11 | 2021-09-14 | 杭州电子科技大学 | 一种不对称的金-银-铂-银多层复合材料及其合成方法 |
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