CN106925316B - Gold/cementite C-base composte material and its preparation method and application - Google Patents
Gold/cementite C-base composte material and its preparation method and application Download PDFInfo
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- 239000010931 gold Substances 0.000 title claims abstract description 131
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 73
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910001567 cementite Inorganic materials 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title claims description 27
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 title claims 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002105 nanoparticle Substances 0.000 claims abstract description 65
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 64
- 239000011258 core-shell material Substances 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 150000002825 nitriles Chemical class 0.000 claims abstract description 11
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 11
- -1 octadecylene Chemical group 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 9
- 239000003093 cationic surfactant Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 239000011363 dried mixture Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims 4
- 229910017356 Fe2C Inorganic materials 0.000 claims 3
- 238000005255 carburizing Methods 0.000 claims 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 2
- 238000009833 condensation Methods 0.000 claims 2
- 230000005494 condensation Effects 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical group [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 230000026030 halogenation Effects 0.000 claims 1
- 238000005658 halogenation reaction Methods 0.000 claims 1
- 238000006479 redox reaction Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 55
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 23
- 239000001301 oxygen Substances 0.000 abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 abstract description 23
- 238000006722 reduction reaction Methods 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000010970 precious metal Substances 0.000 abstract description 6
- 238000010000 carbonizing Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 10
- 239000000446 fuel Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910005335 FePt Inorganic materials 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- PVYPHUYXKVVURH-UHFFFAOYSA-N boron;2-methylpropan-2-amine Chemical compound [B].CC(C)(C)N PVYPHUYXKVVURH-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 229910018979 CoPt Inorganic materials 0.000 description 1
- 206010057175 Mass conditions Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
本发明提供一种金/碳化铁碳基复合材料及其制备方法和应用。本发明的金/碳化铁碳基复合材料是使核壳结构的Au/Fe2C纳米颗粒与腈基化合物发生碳化反应所得到的。该金/碳化铁碳基复合材料减少了贵金属用量，从而降低了成本；特别是，该金/碳化铁碳基复合材料在使用时用量低，并且在催化氧还原反应时表现出优异的催化活性和稳定性。
The invention provides a gold/iron carbide carbon-based composite material and a preparation method and application thereof. The gold/iron carbide carbon-based composite material of the present invention is obtained by carbonizing the Au/Fe 2 C nanoparticles with the core-shell structure and the nitrile-based compound. The gold/iron carbide carbon-based composite material reduces the amount of precious metals, thereby reducing the cost; in particular, the gold/iron carbide carbon-based composite material is used in a low amount and exhibits excellent catalytic activity in catalyzing oxygen reduction reactions and stability.
Description
技术领域technical field
本发明涉及一种碳基复合材料，特别是涉及一种金/碳化铁碳基复合材料及其制备方法和应用。The invention relates to a carbon-based composite material, in particular to a gold/iron carbide carbon-based composite material and a preparation method and application thereof.
背景技术Background technique
燃料电池是一种将存在于燃料与氧化剂中的化学能直接转化为电能的发电装置，该发电方式能量转换率高、高效并且环境友好，是新能源技术领域的热点。聚合物燃料电池是目前最具发展前景的一种燃料电池，目前在聚合物燃料电池的阴极与阳极部分均使用贵金属Pt作为催化剂，尤其是在发生氧还原反应的阴极部分，Pt的用量约占总用量的80％，大量使用贵金属极大地提高了燃料电池的成本，从而成为制约其普及的瓶颈问题。Fuel cell is a power generation device that directly converts chemical energy in fuel and oxidant into electrical energy. This power generation method has high energy conversion rate, high efficiency and environmental friendliness, and is a hot spot in the field of new energy technology. Polymer fuel cells are the most promising fuel cells at present. At present, precious metal Pt is used as a catalyst in the cathode and anode parts of polymer fuel cells, especially in the cathode part where the oxygen reduction reaction occurs, the amount of Pt accounts for about 80% of the total consumption, the large amount of precious metals used greatly increases the cost of fuel cells, thus becoming a bottleneck restricting their popularization.
为了减少阴极催化剂上贵金属的用量，提升催化剂的活性与稳定性，开发低Pt、低贵金属用量的催化剂，在氧还原催化剂领域的应用受到广泛关注。例如将fct相的FePt/Pt纳米颗粒、FePt纳米线、CoPt纳米线等低Pt与低贵金属含量的材料用作氧还原催化剂，均取得了较好的氧还原催化活性。使用Au、Pt、Pd等贵金属的掺杂材料减少了贵金属用量，因此可以在一定程度上起到降低燃料电池整体成本的作用。In order to reduce the amount of noble metal on the cathode catalyst and improve the activity and stability of the catalyst, the development of catalysts with low Pt and low noble metal consumption has attracted extensive attention in the field of oxygen reduction catalysts. For example, FePt/Pt nanoparticles in the fct phase, FePt nanowires, CoPt nanowires and other materials with low Pt and low noble metal content are used as oxygen reduction catalysts, all of which have achieved good oxygen reduction catalytic activity. The use of doping materials of noble metals such as Au, Pt, and Pd reduces the amount of noble metals, so it can play a role in reducing the overall cost of the fuel cell to a certain extent.
另外，目前所开发的一些非贵金属催化剂，例如负载非贵金属、金属氧化物、金属硫化物或者金属-N4结构的大环化合物的碳基复合材料也能有效提高催化氧还原反应的能力，但是为了得到和Pt/C催化剂等贵金属催化剂相近的电流密度，这些碳基复合材料的负载量通常为Pt/C催化剂的数倍，等质量条件下的催化活性较低。In addition, some non-precious metal catalysts currently developed, such as carbon-based composites loaded with non-precious metals, metal oxides, metal sulfides or macrocyclic compounds with metal-N4 structures, can also effectively improve the ability to catalyze the oxygen reduction reaction, but in order to The current density is similar to that of noble metal catalysts such as Pt/C catalysts. The loading of these carbon-based composites is usually several times that of Pt/C catalysts, and the catalytic activity is lower under the same mass conditions.
发明内容SUMMARY OF THE INVENTION
本发明提供一种金/碳化铁碳基复合材料及其制备方法和应用，用于解决现有技术中的碳基复合材料负载量大、等质量条件下催化活性低等技术缺陷。The invention provides a gold/iron carbide carbon-based composite material and a preparation method and application thereof, which are used to solve the technical defects of the carbon-based composite material in the prior art such as large loading and low catalytic activity under the same quality conditions.
本发明提供一种金/碳化铁碳基复合材料，所述金/碳化铁碳基复合材料是使核壳结构的Au/Fe2C纳米颗粒与腈基化合物发生碳化反应所制得的。The invention provides a gold/iron carbide carbon-based composite material, which is prepared by carbonizing Au/Fe 2 C nanoparticles with a core-shell structure and a nitrile-based compound.
在本发明中，核壳结构是指由纳米Fe2C将纳米Au包覆起来形成的纳米尺度的有序组装结构；具体地，核壳结构的Au/Fe2C纳米颗粒以Au为核、以Fe2C为壳层，可以采用本领域常规方法制备得到该纳米颗粒。此外，腈基化合物为含腈基(-CN)的有机化合物，对其不作严格限定，例如可以为二氰二胺、三聚氰胺、苯甲腈等。In the present invention, the core-shell structure refers to a nano-scale ordered assembly structure formed by coating nano-Au with nano-Fe 2 C ; Using Fe 2 C as the shell layer, the nanoparticles can be prepared by conventional methods in the art. In addition, the nitrile group compound is an organic compound containing a nitrile group (—CN), which is not strictly limited, and may be, for example, dicyandiamine, melamine, benzonitrile, or the like.
进一步地，本发明的碳化反应可以通过在保护气氛条件下在一定温度保温一定时间来实现。具体地，温度可以为600-850℃，进一步为700-800℃；保温时间可以为1-4h，进一步为2-3h。上述碳化反应可以使腈基化合物形成氮掺杂碳的碳基底材料，Au/Fe2C纳米颗粒分布在该碳基底材料上；其中，形成的碳基基底材料是一种多孔、疏松的碳结构材料，该碳结构材料由多个碳层组装、堆叠而成，形成了丰富的孔隙结构。Further, the carbonization reaction of the present invention can be realized by maintaining the temperature at a certain temperature for a certain period of time under a protective atmosphere. Specifically, the temperature may be 600-850°C, further 700-800°C; the holding time may be 1-4h, further 2-3h. The above carbonization reaction can make the nitrile-based compound form a nitrogen-doped carbon carbon base material, and Au/Fe 2 C nanoparticles are distributed on the carbon base material; wherein, the formed carbon-based base material is a porous, loose carbon structure The carbon structural material is assembled and stacked by multiple carbon layers, forming a rich pore structure.
在本发明中，在与腈基化合物发生碳化反应之前，可以先采用本领域常规方法将核壳结构的Au/Fe2C纳米颗粒由油溶性转为水溶性，从而使Au/Fe2C纳米颗粒与腈基化合物均匀分散。In the present invention, prior to the carbonization reaction with the nitrile compound, the Au/Fe 2 C nanoparticles with core-shell structure can be converted from oil-soluble to water-soluble by conventional methods in the art, so that the Au/Fe 2 C nanoparticles can be converted from oil-soluble to water-soluble. The particles are uniformly dispersed with the nitrile-based compound.
在一实施方式中，所述核壳结构的Au/Fe2C纳米颗粒在与腈基化合物发生碳化反应之前先经阳离子表面活性剂改性；即，所述金/碳化铁碳基复合材料是使经阳离子表面活性剂改性的核壳结构的Au/Fe2C纳米颗粒与腈基化合物发生碳化反应所制得的。采用阳离子表面活性剂对Au/Fe2C纳米颗粒进行改性，有利于Au/Fe2C纳米颗粒与腈基化合物均匀分散；阳离子表面活性剂例如可以为十六烷基三甲基溴化铵等。In one embodiment, the core-shell structured Au/Fe 2 C nanoparticles are modified with a cationic surfactant before the carbonization reaction with the nitrile compound; that is, the gold/iron carbide carbon-based composite is It is prepared by carbonization reaction of Au/Fe 2 C nanoparticles with core-shell structure modified by cationic surfactant and nitrile compound. Au/Fe 2 C nanoparticles are modified by cationic surfactant, which is conducive to the uniform dispersion of Au/Fe 2 C nanoparticles and nitrile compounds; for example, the cationic surfactant can be cetyltrimethylammonium bromide Wait.
进一步地，本发明的核壳结构的Au/Fe2C纳米颗粒的粒度可以为15-20nm，壳层的厚度可以为1.5-3nm。以该尺寸的Au/Fe2C纳米颗粒作为反应原料，可以有效调控金/碳化铁碳基复合材料中所负载纳米颗粒的尺寸大小和纳米颗粒的负载量，从而有利于提升氧还原催化活性。Further, the particle size of the Au/Fe 2 C nanoparticles of the core-shell structure of the present invention may be 15-20 nm, and the thickness of the shell layer may be 1.5-3 nm. Using Au/Fe 2 C nanoparticles of this size as the reaction raw material can effectively control the size and loading of nanoparticles loaded in the gold/iron carbide carbon matrix composite, which is beneficial to improve the catalytic activity of oxygen reduction.
进一步地，所述金/碳化铁碳基复合材料具有Fe4C相。该Fe4C相是核壳结构的Au/Fe2C纳米颗粒经碳化反应所生成，并且可以通过与碳基底材料之间的相互作用有效地限制生成的Fe4C相的尺寸，从而最大化活性位点密度。Further, the gold/iron carbide carbon-based composite material has a Fe 4 C phase. The Fe 4 C phase is generated by the carbonization reaction of Au/Fe 2 C nanoparticles with core-shell structure, and the size of the generated Fe 4 C phase can be effectively limited by the interaction with the carbon base material, thereby maximizing the Active site density.
在本发明的金/碳化铁碳基复合材料中，含有适当的铁原子和氮原子有利于提高其催化氧还原反应的能力。具体地，所述金/碳化铁碳基复合材料中铁原子百分含量可以为0.5-2％，氮原子百分含量可以为5-11％；其中，原子百分含量指的是该原子个数的百分比。In the gold/iron carbide carbon-based composite material of the present invention, containing appropriate iron atoms and nitrogen atoms is beneficial to improve its ability to catalyze the oxygen reduction reaction. Specifically, the atomic percentage of iron in the gold/iron carbide carbon-based composite material may be 0.5-2%, and the atomic percentage of nitrogen may be 5-11%; wherein, the atomic percentage refers to the number of atoms percentage.
本发明还提供上述任一所述金/碳化铁碳基复合材料的制备方法，包括如下步骤：The present invention also provides a preparation method of any of the above-mentioned gold/iron carbide carbon-based composite materials, comprising the following steps:
1)将9-11nm的金纳米颗粒与卤化物和十八烯与油胺的混合溶液混合，所述混合溶液中十八烯与油胺的体积比为(60-100):1，在保护气氛下升温至160-200℃，注入0.05-0.3mL的五羰基铁，保温20-80min，得到核壳结构的Au/Fe纳米颗粒；1) Mix the gold nanoparticles of 9-11 nm with the mixed solution of halide and octadecene and oleylamine, the volume ratio of octadecene and oleylamine in the mixed solution is (60-100): 1. The temperature is raised to 160-200 °C under the atmosphere, 0.05-0.3 mL of iron pentacarbonyl is injected, and the temperature is kept for 20-80 min to obtain Au/Fe nanoparticles with core-shell structure;
2)将所述核壳结构的Au/Fe纳米颗粒与十八胺和油胺混合，升温至300-350℃，保温40-80min，得到所述核壳结构的Au/Fe2C纳米颗粒；2) mixing the core-shell structured Au/Fe nanoparticles with octadecylamine and oleylamine, heating to 300-350° C., and maintaining the temperature for 40-80 min to obtain the core-shell structured Au/Fe 2 C nanoparticles;
3)将所述核壳结构的Au/Fe2C纳米颗粒与腈基化合物混合，随后在保护气氛下升温至600-850℃，保温1-4h(即碳化反应)，得到所述金/碳化铁碳基复合材料。3) Mix the core-shell structured Au/Fe 2 C nanoparticles with the nitrile-based compound, and then raise the temperature to 600-850° C. under a protective atmosphere for 1-4 hours (ie, carbonization reaction) to obtain the gold/carbonized Iron-carbon matrix composites.
进一步地，步骤3)包括：Further, step 3) includes:
将所述核壳结构的Au/Fe2C纳米颗粒与阳离子表面活性剂的水溶液和腈基化合物混合，随后干燥混合物，再在保护气氛下将干燥后的混合物升温至600-800℃，保温1-4h，得到所述金/碳化铁碳基复合材料。The core-shell structured Au/Fe 2 C nanoparticles are mixed with an aqueous solution of a cationic surfactant and a nitrile compound, then the mixture is dried, and the dried mixture is heated to 600-800° C. under a protective atmosphere, and kept for 1 -4h, the gold/iron carbide carbon-based composite material was obtained.
其中，所述腈基化合物为二氰二胺、三聚氰胺和苯甲腈中的一种或多种；所述阳离子表面活性剂为十六烷基三甲基溴化铵；所述卤化物为NH4Br。Wherein, the nitrile compound is one or more of dicyandiamide, melamine and benzonitrile; the cationic surfactant is cetyltrimethylammonium bromide; the halide is NH 4Br .
进一步地，所述9-11nm的金纳米颗粒的制备方法包括：Further, the preparation method of the 9-11nm gold nanoparticles includes:
将30-100mg的HAuCl4·3H2O与十八烯和油胺的混合溶液混合，所述混合溶液中十八烯与油胺的体积比为(10-30):1，随后升温至45-75℃，注入4-6nm的纳米金溶液，保温至得到9-11nm的金纳米颗粒。Mix 30-100 mg of HAuCl 4 ·3H 2 O with a mixed solution of octadecene and oleylamine, where the volume ratio of octadecene to oleylamine in the mixed solution is (10-30): 1, and then the temperature is raised to 45 -75°C, inject 4-6nm nano-gold solution, and keep warm until gold nanoparticles of 9-11nm are obtained.
在本发明中，选择上述碳化反应温度(即600-850℃)和保温时间(即1-4h)，有利于对得到的金/碳化铁碳基复合材料中碳化铁的物相和含量进行控制。具体地，温度过低或保温时间过短会导致腈基化合物分解不完全，无法与金/碳化铁纳米颗粒形成有效的复合；温度过高或保温时间过长则会导致碳基底材料氮掺杂量与缺陷数下降，催化活性降低。本发明的具体方案中，碳化反应温度可以为700-800℃，保温时间可以为2-3h，例如2h左右。In the present invention, selecting the above-mentioned carbonization reaction temperature (ie, 600-850° C.) and holding time (ie, 1-4 h) is beneficial to control the phase and content of iron carbide in the obtained gold/iron carbide carbon-based composite material. . Specifically, if the temperature is too low or the holding time is too short, the nitrile-based compound will not be decomposed completely and cannot form an effective composite with the gold/iron carbide nanoparticles; if the temperature is too high or the holding time is too long, the carbon base material will be doped with nitrogen. The amount and number of defects decreased, and the catalytic activity decreased. In a specific solution of the present invention, the carbonization reaction temperature can be 700-800° C., and the holding time can be 2-3h, for example, about 2h.
在一实施方式中，金/碳化铁碳基复合材料的制备方法，包括如下步骤：In one embodiment, the preparation method of gold/iron carbide carbon matrix composite material comprises the following steps:
1)将30-100mg的HAuCl4·3H2O溶于十八烯和油胺的混合溶液中，混合溶液中十八烯与油胺的体积比为(10-30):1，随后升温至45-75℃，注入0.2mL浓度为3-15mg/mL的5nm左右的纳米金溶液，保温4-7h，得到10nm左右的金纳米颗粒；1) Dissolve 30-100 mg of HAuCl 4 ·3H 2 O in the mixed solution of octadecene and oleylamine, and the volume ratio of octadecene to oleylamine in the mixed solution is (10-30): 1, then be heated to At 45-75°C, inject 0.2 mL of nano-gold solution with a concentration of 3-15 mg/mL of about 5 nm, and keep it for 4-7 h to obtain gold nanoparticles of about 10 nm;
2)向上述10nm左右的金纳米颗粒中加入8-15mg的NH4Br，随后加入十八烯与油胺的混合溶液，混合溶液中十八烯与油胺的体积比为(60-100):1，在保护气氛下升温至160-200℃，注入0.05-0.3mL的五羰基铁，保温20-80min，得到核壳结构的Au/Fe纳米颗粒；2) Add 8-15 mg of NH 4 Br to the above-mentioned gold nanoparticles of about 10 nm, and then add a mixed solution of octadecene and oleylamine, and the volume ratio of octadecene to oleylamine in the mixed solution is (60-100) : 1, raise the temperature to 160-200 ℃ under a protective atmosphere, inject 0.05-0.3 mL of iron pentacarbonyl, and keep the temperature for 20-80 min to obtain Au/Fe nanoparticles with core-shell structure;
3)向上述核壳结构的Au/Fe纳米颗粒中加入10-35g的十八胺和0.2-0.8mL的油胺，升温至300-350℃，保温1h，得到所述核壳结构的Au/Fe2C纳米颗粒；3) Add 10-35 g of octadecylamine and 0.2-0.8 mL of oleylamine to the above-mentioned core-shell structured Au/Fe nanoparticles, heat up to 300-350° C., and keep the temperature for 1 h to obtain the core-shell structured Au/Fe nanoparticles. Fe 2 C nanoparticles;
4)将所述核壳结构的Au/Fe2C纳米颗粒溶于十六烷基三甲基溴化铵的水溶液中，再加入二氰二胺，随后干燥，再在保护气氛下升温至600-800℃，保温1-4h，得到所述金/碳化铁碳基复合材料。4) Dissolving the core-shell structured Au/Fe 2 C nanoparticles in an aqueous solution of cetyltrimethylammonium bromide, adding dicyandiamide, drying, and heating up to 600 under a protective atmosphere -800 DEG C, heat preservation for 1-4 hours, to obtain the gold/iron carbide carbon-based composite material.
本发明还提供上述任一所述金/碳化铁碳基复合材料作为氧化还原反应催化剂的应用。The present invention also provides the application of any of the above-mentioned gold/iron carbide carbon-based composite materials as a redox catalyst.
本发明的实施，至少具有以下优势：The implementation of the present invention has at least the following advantages:
1、本发明提供的金/碳化铁碳基复合材料能够高效地催化氧还原反应，特别是其显著减少了贵金属用量，极大地降低了成本。1. The gold/iron carbide carbon-based composite material provided by the present invention can efficiently catalyze the oxygen reduction reaction, and in particular, it significantly reduces the amount of precious metals and greatly reduces the cost.
2、本发明提供的金/碳化铁碳基复合材料的制备方法，以核壳结构的Au/Fe2C纳米颗粒为反应原料，可有效调控金/碳化铁碳基复合材料中所负载颗粒的尺寸大小与纳米颗粒的负载量，有利于提升氧还原催化活性。2. The preparation method of the gold/iron carbide carbon-based composite material provided by the present invention uses Au/Fe 2 C nanoparticles with a core-shell structure as the reaction raw material, which can effectively control the amount of particles loaded in the gold/iron carbide carbon-based composite material. The size and loading of nanoparticles are beneficial to improve the catalytic activity of oxygen reduction.
3、本发明提供的金/碳化铁碳基复合材料在催化氧还原反应时表现出优异的性能，其催化活性在相同用量的情况下与商用Pt/C催化剂相当，同时还具有更优越的稳定性。3. The gold/iron carbide carbon-based composite material provided by the present invention exhibits excellent performance in catalyzing the oxygen reduction reaction, and its catalytic activity is comparable to that of commercial Pt/C catalysts under the same dosage, and also has better stability. sex.
附图说明Description of drawings
图1是本发明实施例1制备的核壳结构的Au/Fe2C纳米颗粒的透射电子显微镜图；1 is a transmission electron microscope image of Au/Fe 2 C nanoparticles of core-shell structure prepared in Example 1 of the present invention;
图2是本发明实施例1制备的核壳结构的Au/Fe2C纳米颗粒的X射线衍射图；2 is an X-ray diffraction pattern of the core-shell structured Au/Fe 2 C nanoparticles prepared in Example 1 of the present invention;
图3是本发明实施例1制备的金/碳化铁碳基复合材料的扫描电子显微镜图；3 is a scanning electron microscope image of the gold/iron carbide carbon-based composite material prepared in Example 1 of the present invention;
图4是本发明实施例1制备的金/碳化铁碳基复合材料的透射电子显微镜图；4 is a transmission electron microscope image of the gold/iron carbide carbon-based composite material prepared in Example 1 of the present invention;
图5是本发明实施例1制备的金/碳化铁碳基复合材料的X射线衍射图；Fig. 5 is the X-ray diffraction pattern of the gold/iron carbide carbon-based composite material prepared in Example 1 of the present invention;
图6是本发明实施例1制备的金/碳化铁碳基复合材料的X射线光电子能谱图；6 is an X-ray photoelectron spectrogram of the gold/iron carbide carbon-based composite material prepared in Example 1 of the present invention;
图7为图6中N峰的放大显示图；Fig. 7 is the enlarged display figure of N peak in Fig. 6;
图8是本发明实施例1制备的金/碳化铁碳基复合材料催化氧还原反应的循环伏安曲线；8 is the cyclic voltammetry curve of the gold/iron carbide carbon-based composite material catalyzed by the oxygen reduction reaction prepared in Example 1 of the present invention;
图9为本发明实施例1制备的金/碳化铁碳基复合材料的线性扫描伏安图。9 is a linear sweep voltammogram of the gold/iron carbide carbon-based composite material prepared in Example 1 of the present invention.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明的实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the implementation of the present invention. examples, but not all examples. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例1Example 1
1、制备核壳结构的Au/Fe2C纳米颗粒1. Preparation of Au/Fe 2 C nanoparticles with core-shell structure
(1)制备5nm的Au纳米颗粒(1) Preparation of 5nm Au nanoparticles
取0.5mmol的HAuCl4·3H2O溶解于10mL正己烷和10mL油胺的混合溶液中，混合均匀后转入四口瓶，于5℃进行搅拌，并通入Ar气保护，搅拌20min后，注入含有16mg叔丁基胺-硼烷的溶液(16mg叔丁基胺-硼烷溶于1mL正己烷与1mL油胺的混合溶液中)，反应2h，得到5nm的Au纳米颗粒，将其制成浓度为5mg/mL的纳米Au溶液。Dissolve 0.5 mmol of HAuCl 4 ·3H 2 O in a mixed solution of 10 mL of n-hexane and 10 mL of oleylamine, mix it well, transfer it into a four-necked flask, stir at 5°C, and introduce Ar gas for protection, and after stirring for 20 min, Inject a solution containing 16 mg of tert-butylamine-borane (16 mg of tert-butylamine-borane is dissolved in a mixed solution of 1 mL of n-hexane and 1 mL of oleylamine), and react for 2 h to obtain 5 nm Au nanoparticles, which are made into A nano-Au solution with a concentration of 5 mg/mL.
(2)制备10nm的Au纳米颗粒(2) Preparation of 10nm Au nanoparticles
取30mg的HAuCl4·3H2O溶于8mL十八烯和0.5mL油胺的混合溶液中，混合均匀后升温至65℃，注入0.2mL上述浓度为5mg/mL的5nm的Au颗粒，保温5h，得到10nm的Au纳米颗粒。Dissolve 30 mg of HAuCl 4 ·3H 2 O in a mixed solution of 8 mL of octadecene and 0.5 mL of oleylamine, mix well, heat up to 65°C, inject 0.2 mL of Au particles with a concentration of 5 mg/mL above 5 nm, and keep the temperature for 5 h , to obtain 10 nm Au nanoparticles.
(3)制备核壳结构的Au/Fe纳米颗粒(3) Preparation of Au/Fe nanoparticles with core-shell structure
取上述10nm的Au纳米颗粒，加入8mg的NH4Br，20mL十八烯与0.3mL油胺，通入Ar，升温至180℃，注入0.1mL的五羰基铁，保温30min，得到核壳结构的Au/Fe纳米颗粒。Take the above 10 nm Au nanoparticles, add 8 mg of NH 4 Br, 20 mL of octadecene and 0.3 mL of oleylamine, pass Ar, heat it up to 180 ° C, inject 0.1 mL of pentacarbonyl iron, and keep it for 30 min to obtain a core-shell structure. Au/Fe nanoparticles.
(4)制备核壳结构的Au/Fe2C纳米颗粒(4) Preparation of Au/Fe 2 C nanoparticles with core-shell structure
向上述核壳结构的Au/Fe纳米颗粒中加入15g十八胺和0.3mL油胺，升温至300℃，保温1h，得到核壳结构的Au/Fe2C纳米颗粒。15 g of octadecylamine and 0.3 mL of oleylamine were added to the Au/Fe nanoparticles with the core-shell structure, the temperature was raised to 300° C., and the temperature was maintained for 1 h to obtain the Au/Fe 2 C nanoparticles with the core-shell structure.
使用透射电子显微镜对上述制备的核壳结构的Au/Fe2C纳米颗粒进行微观形貌表征，结果如图1所示。由图1可以清晰地看出上述制备的Au/Fe2C纳米颗粒为具有核壳结构的纳米颗粒。The micromorphological characterization of the core-shell structured Au/Fe 2 C nanoparticles prepared above was carried out using transmission electron microscopy, and the results are shown in Figure 1 . It can be clearly seen from FIG. 1 that the Au/Fe 2 C nanoparticles prepared above are nanoparticles with a core-shell structure.
图2为上述制备的核壳结构的Au/Fe2C纳米颗粒的X射线衍射图。由图2可知，38°的峰对应于Au的(111)面，43°的峰对应于Fe2C的(101)面，由此说明本实施例中制备的纳米颗粒为核壳结构的Au/Fe2C纳米颗粒。FIG. 2 is an X-ray diffraction pattern of the core-shell structured Au/Fe 2 C nanoparticles prepared above. It can be seen from Figure 2 that the peak at 38° corresponds to the (111) plane of Au, and the peak at 43° corresponds to the (101) plane of Fe 2 C, which indicates that the nanoparticles prepared in this example are Au with a core-shell structure /Fe 2 C nanoparticles.
2、制备金/碳化铁碳基复合材料2. Preparation of gold/iron carbide carbon matrix composites
将20mg上述核壳结构的Au/Fe2C纳米颗粒溶于2mL三氯甲烷中，将该溶液加入盛有10mL 0.1M的十六烷基三甲基溴化铵与300mg二氰二胺溶液的烧杯中，搅拌3h。随后将该烧杯放入真空干燥箱内，并于70℃下进行干燥。Dissolve 20 mg of the above-mentioned core-shell structured Au/Fe 2 C nanoparticles in 2 mL of chloroform, and add the solution to a mixture containing 10 mL of 0.1 M hexadecyl trimethyl ammonium bromide and 300 mg of dicyandiamide solution. In the beaker, stir for 3h. The beaker was then placed in a vacuum drying oven and dried at 70°C.
收集干燥后的材料，在氮气气氛以及700℃的条件下，保温(退火)处理2h，得到金/碳化铁碳基复合材料。The dried material was collected, and the gold/iron carbide carbon matrix composite material was obtained by thermal insulation (annealing) treatment under the condition of nitrogen atmosphere and 700 ℃ for 2 hours.
使用扫描电子显微镜以及透射电子显微镜对本实施例制备的金/碳化铁碳基复合材料进行微观形貌的表征，结果见图3和图4。如图3和图4可知，碳化所形成的碳基基底材料是一种多孔、疏松的碳结构材料，该碳结构材料由多个碳层组装、堆叠而成，形成了丰富的孔隙结构；与此同时，在碳基底上负载有纳米颗粒。Scanning electron microscope and transmission electron microscope were used to characterize the microscopic morphology of the gold/iron carbide carbon-based composite material prepared in this example, and the results are shown in FIG. 3 and FIG. 4 . As can be seen from Figures 3 and 4, the carbon-based base material formed by carbonization is a porous and loose carbon structural material, which is assembled and stacked by multiple carbon layers, forming a rich pore structure; and At the same time, nanoparticles are supported on the carbon substrate.
图5为本实施例制备的金/碳化铁碳基复合材料的X射线衍射图。由图5可以看出，38°的峰对应于Au的(111)面，40°对应于Fe4C的(111)面。由此说明，上述制备的金/碳化铁碳基复合材料具有Fe4C相。FIG. 5 is an X-ray diffraction pattern of the gold/iron carbide carbon-based composite material prepared in this example. It can be seen from Fig. 5 that the peak at 38° corresponds to the (111) plane of Au, and the peak at 40° corresponds to the (111) plane of Fe 4 C. This shows that the gold/iron carbide carbon-based composite material prepared above has a Fe 4 C phase.
图6为本实施例制备的金/碳化铁碳基复合材料的X射线光电子能谱图。由图6可以看出，上述制备的金/碳化铁碳基复合材料的表面部分元素组成含有含碳、氮、氧、铁四种元素，无其他杂质；并且，通过对峰强度的换算可以得出各元素原子数的相对百分含量，其中铁原子数占总原子数的0.8％，氮原子数占总原子数的10.6％。FIG. 6 is an X-ray photoelectron spectrum diagram of the gold/iron carbide carbon-based composite material prepared in this example. As can be seen from Figure 6, the surface part of the prepared gold/iron carbide carbon-based composite material contains four elements including carbon, nitrogen, oxygen and iron, and no other impurities; and, by converting the peak intensity, it can be obtained. The relative percentage of the atomic number of each element is calculated, in which the number of iron atoms accounts for 0.8% of the total number of atoms, and the number of nitrogen atoms accounts for 10.6% of the total number of atoms.
图7为图6中N(2p)峰的放大显示图，即本实施例制备的金/碳化铁碳基复合材料氮元素的X射线光电子能谱图。如图7所示，可以看到明显的398.0eV的吡啶氮，398.9eV的Fe-N，400.3eV的吡咯氮，以及402.9eV的氧化的氮的峰，除了进一步证实所获得的金/碳化铁碳基复合材料中含有氮元素外，还表明存在Fe-N-C键结构，其有利于提高催化氧还原反应能力。FIG. 7 is an enlarged display diagram of the N(2p) peak in FIG. 6 , that is, an X-ray photoelectron spectrum diagram of nitrogen element of the gold/iron carbide carbon-based composite material prepared in this example. As shown in Figure 7, distinct peaks of pyridine nitrogen at 398.0 eV, Fe-N at 398.9 eV, pyrrolic nitrogen at 400.3 eV, and oxidized nitrogen at 402.9 eV can be seen, in addition to further confirming the obtained gold/iron carbide In addition to the nitrogen element contained in the carbon-based composites, the Fe-N-C bond structure is also indicated, which is beneficial to improve the ability to catalyze the oxygen reduction reaction.
实施例2Example 2
本实施例使用实施例1制备的核壳结构的Au/Fe2C纳米颗粒制备金/碳化铁碳基复合材料，具体为：This example uses the core-shell structure Au/Fe 2 C nanoparticles prepared in Example 1 to prepare a gold/iron carbide carbon-based composite material, specifically:
将15mg实施例1制备的核壳结构Au/Fe2C的纳米颗粒溶于2mL三氯甲烷中，将该溶液加入盛有10mL 0.2M的十六烷基三甲基溴化铵与600mg二氰二胺溶液的烧杯中，搅拌3h。随后将该烧杯放入真空干燥箱内，并于70℃下进行干燥。Dissolve 15mg of nanoparticles of core-shell structure Au/Fe 2 C prepared in Example 1 in 2mL of chloroform, add the solution to 10mL of 0.2M hexadecyltrimethylammonium bromide and 600mg of dicyano In a beaker of diamine solution, stir for 3h. The beaker was then placed in a vacuum drying oven and dried at 70°C.
收集干燥后的材料，在氮气气氛以及750℃的条件下，保温处理2h，得到金/碳化铁碳基复合材料。The dried material was collected, and the gold/iron carbide carbon matrix composite material was obtained under the condition of nitrogen atmosphere and 750 ℃ for 2 hours.
对得到的金/碳化铁碳基复合材料进行TEM和SEM表征，结果与实施例1相同。此外，采用X射线光电子能谱进行分析表明，制备得到的金/碳化铁碳基复合材料表面有且只含有碳、氮、氧、铁元素，几乎不含其他杂质。The obtained gold/iron carbide carbon matrix composites were characterized by TEM and SEM, and the results were the same as those in Example 1. In addition, the analysis by X-ray photoelectron spectroscopy showed that the surface of the prepared gold/iron carbide carbon-based composite material only contained carbon, nitrogen, oxygen, and iron elements, and almost no other impurities.
实施例3Example 3
将实施例1制备的金/碳化铁碳基复合材料应用于燃料电池阴极的氧还原反应中，具体为：The gold/iron carbide carbon-based composite material prepared in Example 1 was applied to the oxygen reduction reaction of the fuel cell cathode, specifically:
使用实施例1中制备的金/碳化铁碳基复合材料用于催化燃料电池阴极的氧还原反应，其中氧还原反应是在碱性条件下进行(0.1M KOH水溶液)，使用循环扫描伏安法和线性扫描伏安法对金/碳化铁碳基复合材料催化氧还原反应的作用进行研究，扫描速率为200mVs-1。The gold/iron carbide carbon-based composite prepared in Example 1 was used to catalyze the oxygen reduction reaction of the fuel cell cathode, wherein the oxygen reduction reaction was carried out under alkaline conditions (0.1M KOH aqueous solution), using cyclic scanning voltammetry The effect of gold/iron carbide carbon matrix composites on the catalytic oxygen reduction reaction was investigated by linear sweep voltammetry with a scan rate of 200mVs -1 .
上述氧还原反应的反应式为：The reaction formula of the above-mentioned oxygen reduction reaction is:
O2+4e-+2H2O→4OH-。O 2 +4e − +2H 2 O→4OH − .
图8是实施例1制备的金/碳化铁碳基复合材料的循环伏安曲线。如图8可知，比较溶液中充满N2和O2时的曲线，该复合材料在-0.19V电位处表现出明显氧还原峰，说明其作为氧还原反应的催化剂材料表现出良好的性能。8 is the cyclic voltammetry curve of the gold/iron carbide carbon-based composite material prepared in Example 1. As can be seen in Figure 8, comparing the curves when the solution is full of N2 and O2 , the composite material exhibits an obvious oxygen reduction peak at -0.19V potential, indicating that it has good performance as a catalyst material for oxygen reduction reaction.
图9是实施例1制备的金/碳化铁碳基复合材料的线性扫描伏安图。由图9可以看出，相对于Ag/AgCl参比电极，该复合材料氧还原反应的起始电压为-0.01V，在负载量为0.1mg/cm2时，该复合材料的极限电流为5mA/cm2。FIG. 9 is a linear sweep voltammogram of the gold/iron carbide carbon-based composite material prepared in Example 1. FIG. It can be seen from Figure 9 that, relative to the Ag/AgCl reference electrode, the onset voltage of the oxygen reduction reaction of the composite material is -0.01V, and when the loading amount is 0.1 mg/cm 2 , the limiting current of the composite material is 5mA. /cm 2 .
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features thereof can be equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention. scope.
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