CN105181773B - A kind of precious metal composition and its application - Google Patents
A kind of precious metal composition and its application Download PDFInfo
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- CN105181773B CN105181773B CN201510567167.0A CN201510567167A CN105181773B CN 105181773 B CN105181773 B CN 105181773B CN 201510567167 A CN201510567167 A CN 201510567167A CN 105181773 B CN105181773 B CN 105181773B
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Abstract
The present invention discloses a kind of precious metal composition and its application.The present invention forms a kind of precious metal composition, and applied to the preparation of electrode using nano-noble metal, polylactic acid modified Copolycarbonate (PPC/PLA), graphene oxide as main component.Advantages, the precision to further increase electrochemical sensor such as nano-noble metal is combined by precious metal composition of the present invention and the electrode prepared based on it with the advantages of graphene, and conductive energy is good, resistance is low provide developing direction.
Description
Technical field
The present invention relates to a kind of precious metal composition and its applications, can be used for preparing electrochemical sensing further to one kind
The precious metal composition of device electrode, belongs to electrochemical field.
Background technology
It is apparent to the electrocatalytic oxidation of organic molecule on the precious metal materials electrode such as gold, silver, platinum, therefore, noble metal electricity
Pole is commonly used for the detection of organic molecule.It is organic in detection trace for the electrochemical sensor of working electrode to noble metal electrode
When small molecule, have detection speed fast, detection limits the features such as low, more much more convenient than liquid chromatography, but testing result is one
It causes.
Xu Minmin exists《Noble metal nano structure and the research of the surface nature and SERS of electrode》Point out nano-noble metal due to
Skin effect, and there is prodigious specific surface area, quickening chemical reaction can be catalyzed.Therefore when nano-noble metal is used as electrode,
Reaction efficiency meeting higher, but substantially reduced by the precious metal atom cluster fusing point that small size limits, it cannot even stablize sometimes and deposit
.
Nano-noble metal during being coated to carrier and making electrode, cannot it is accurate, be evenly coated with, to cause
The huge waste of noble metal can not preferably play its effect for reducing resistance, improving electrochemical sensor efficiency.
Invention content
Defect based on the prior art, the first object of the present invention are to provide a kind of precious metal composition.
A kind of precious metal composition, including noble metal, polylactic acid modified Copolycarbonate (PPC/PLA), oxidation
Graphene.
The noble metal is Au Ag Pt Pd, osmium, one kind in iridium or its a variety of alloy.
The grain size of the noble metal is 10~500nm, preferably 50~250nm, more preferable 100nm, it is therefore an objective to increase electrode
Electrical efficiency, grain size is too small can be so that nano level metallic particles fusing point reduces, to during redox graphene
Fusing, cannot keep its original grain size.
The weight average molecular weight of the PPC/PLA is：Mw=10,000~800,000；Preferably, Mw=60,000~500,
000；It is highly preferred that Mw=300,000.The purpose of PPC/PLA is added is by pyrolytic that noble metal is evenly dispersed, to obtain
Obtain the low electrode of resistivity.
Measuring PPC/PLA heat decomposition temperatures is：90~320 DEG C.
Graphene oxide is added in composition, it is therefore an objective to be reduced to graphene, by increase conductive specific surface area and with portion
Divide nano-noble metal to combine enhancing conductive effect, while promoting the PPC/PLA not decomposed completely to decompose completely by reduction reaction.
The present invention also provides the degree of each ingredient in precious metal composition, various composition weight percentages
For：Noble metal 10~20%, polylactic acid modified Copolycarbonate (PPC/PLA) 40~60%, graphene oxide 20~
50%.
Preferably, various composition weight percentage is：Noble metal 12~18%, polylactic acid modified makrolon
Copolymer (PPC/PLA) 45~55%, graphene oxide 27~43%.
It is further preferred that various composition weight percentage is：Noble metal 16%, polylactic acid modified poly- carbon
Acid ester copolymer (PPC/PLA) 50%, graphene oxide 34%.
The second object of the present invention is to provide a kind of application process of precious metal composition, and the composition is in specified conditions
Under, it can be attached on electrode holder, to modification and modified electrode.
By the noble metal granule of 10~500nm of average grain diameter and weight average molecular weight (Mw) it is 10,000 using V-Mixer
~800,000 polylactic acid modified Copolycarbonate (PPC/PLA) is uniformly mixed, which is utilized high frequency sense
It answers heat plasma body device to be discarded in plasma atmosphere under argon atmosphere, generated micro mist is recycled using filter,
Obtain compound particle.Graphene oxide is added into compound particle, is sufficiently mixed using planetary mill, and mixed powder is obtained
End.It after mixed-powder is dried, is heated 0.5~2.5 hour at 500~950 DEG C, concrete mode is：Muffle furnace is first to heat to
950 DEG C or more, then set temperature is cooled to, graphene oxide is added under the protection of argon gas, during which pours argon gas incessantly,
In reaction process, can electrode holder be placed in exit in due course as needed, the electrode of different size is made.
The noble metal, PPC/PLA, the dosage of graphene oxide are next by the weight percentage of above-mentioned precious metal composition
Proportioning.
The preferred reaction temperature is 700~920 DEG C, and temperature still more preferably is 850 DEG C.
The preferred heating time is 1~2h, and heating time still more preferably is 1.5h.
The third object of the present invention be to provide it is a kind of be made of precious metal composition of the present invention electrode structure
Electrochemical sensor.
The grain size that precious metal composition according to the present invention controls nano-noble metal prevents it from melting at high temperature
Melt, maintains its nano-meter characteristic.The present invention reduces the dosage of noble metal in electrode production process, improves the profit of noble metal
With efficiency, the polylactic acid modified Copolycarbonate (PPC/PLA) for being mixed with nano-noble metal and graphene oxide passes through
A part of noble metal is uniformly coated on electrode holder by pyrolytic, and another part noble metal is uniformly coated on reduction
On graphene oxide (graphene) afterwards, the advantages that giving full play to the high-specific surface area and satisfactory electrical conductivity of graphene.
Nano-noble metal is combined by the present invention with the advantages of graphene, is prepared for the electricity that electric conductivity is good, resistance is low
Pole, the precision to further increase electrochemical sensor provide developing direction.
Specific implementation mode
Below by specific embodiment, further technical scheme of the present invention is specifically described.It should be understood that below
Embodiment be intended only as illustrating, and do not limit the scope of the invention, while those skilled in the art is according to the present invention
The obvious change and modification made are also contained within the scope of the invention.
Embodiment 1
By the nanogold particle 10% and weight average molecular weight (Mw) of average grain diameter 10nm it is 10,000 using V-Mixer
Polylactic acid modified Copolycarbonate (PPC/PLA) 40% is uniformly mixed, which is utilized high frequency induction thermal etc.
Ion body device is discarded under argon atmosphere in plasma atmosphere, using filter recycle caused by micro mist to get to
Compound particle.Graphene oxide 50% is added into compound particle, is sufficiently mixed using planetary mill, is obtained mixed-powder.
It after mixed-powder is dried, is heated 0.8 hour at 900 DEG C, concrete mode is：Muffle furnace is first to heat to 950 DEG C or more, then drops
Precious metal composition is added under the protection of argon gas, during which pours argon gas incessantly, electrode holder is placed in 900 DEG C for temperature
In reactor, the electrode is obtained.
Embodiment 2
By the nanoparticle palladium 12% and weight average molecular weight (Mw) of average grain diameter 50nm it is 60,000 using V-Mixer
Polylactic acid modified Copolycarbonate (PPC/PLA) 45% is uniformly mixed, which is utilized high frequency induction thermal etc.
Ion body device is discarded under argon atmosphere in plasma atmosphere, using filter recycle caused by micro mist to get to
Compound particle.Graphene oxide 43% is added into compound particle, is sufficiently mixed using planetary mill, is obtained mixed-powder.
It after mixed-powder is dried, is heated 0.5 hour at 950 DEG C, concrete mode is：Muffle furnace is first to heat to 950 DEG C or more, then drops
Temperature returns 950 DEG C, and precious metal composition is added under the protection of argon gas, during which pours argon gas incessantly, obtains the electrode.
Embodiment 3
Using V-Mixer by the nano-Ag particles 15% and weight average molecular weight (Mw) of average grain diameter 170nm be 100,000
Polylactic acid modified Copolycarbonate (PPC/PLA) 52% be uniformly mixed, by the mixed-powder utilize high frequency induction thermal
Plasma device is discarded under argon atmosphere in plasma atmosphere, using filter recycle caused by micro mist to get
To compound particle.Graphene oxide 33% is added into compound particle, is sufficiently mixed using planetary mill, is obtained mixed powder
End.It after mixed-powder is dried, is heated 2.5 hours at 500 DEG C, concrete mode is：Muffle furnace is first to heat to 950 DEG C or more,
Cool down back again 500 DEG C, precious metal composition is added under the protection of argon gas, during which pours argon gas incessantly, obtains described
Electrode.
Embodiment 4
Using V-Mixer by the nano-platinum particle 16% and weight average molecular weight (Mw) of average grain diameter 100nm be 300,
0000 polylactic acid modified Copolycarbonate (PPC/PLA) 50% is uniformly mixed, which is utilized high frequency sense
It answers heat plasma body device to be discarded in plasma atmosphere under argon atmosphere, generated micro mist is recycled using filter,
Obtain compound particle.Graphene oxide 34% is added into compound particle, is sufficiently mixed, is mixed using planetary mill
Powder.It after mixed-powder is dried, is heated 1.5 hours at 850 DEG C, concrete mode is：Muffle furnace be first to heat to 950 DEG C with
On, then 850 DEG C are cooled to, precious metal composition is added under the protection of argon gas, during which pours argon gas, reaction knot incessantly
Beam obtains electrode.
Embodiment 5
It is by the nanogold of average grain diameter 250nm/iridium alloy particle 18% and weight average molecular weight (Mw) using V-Mixer
500,000 polylactic acid modified Copolycarbonate (PPC/PLA) 55% is uniformly mixed, which is utilized high frequency
Induction heat plasma device is discarded under argon atmosphere in plasma atmosphere, is recycled using filter generated micro-
Powder is to get to compound particle.Graphene oxide 27% is added into compound particle, is sufficiently mixed, is obtained using planetary mill
Mixed-powder.It after mixed-powder is dried, is heated 1 hour at 920 DEG C, concrete mode is：Muffle furnace be first to heat to 950 DEG C with
On, then 920 DEG C are cooled to, precious metal composition is added under the protection of argon gas, during which pours argon gas incessantly, obtains described
Electrode.
Embodiment 6
Using V-Mixer by the nano-platinum particle 19% and weight average molecular weight (Mw) of average grain diameter 200nm be 200,000
Polylactic acid modified Copolycarbonate (PPC/PLA) 47% be uniformly mixed, by the mixed-powder utilize high frequency induction thermal
Plasma device is discarded under argon atmosphere in plasma atmosphere, using filter recycle caused by micro mist to get
To compound particle.Graphene oxide 34% is added into compound particle, is sufficiently mixed using planetary mill, is obtained mixed powder
End.It after mixed-powder is dried, is heated 2.3 hours at 700 DEG C, concrete mode is：Muffle furnace is first to heat to 950 DEG C or more,
700 DEG C are cooled to again, precious metal composition is added under the protection of argon gas, during which pours argon gas incessantly, are obtained described
Electrode.
Embodiment 7
Using V-Mixer by the nanoparticle palladium 20% and weight average molecular weight (Mw) of average grain diameter 500nm be 800,000
Polylactic acid modified Copolycarbonate (PPC/PLA) 60% be uniformly mixed, by the mixed-powder utilize high frequency induction thermal
Plasma device is discarded under argon atmosphere in plasma atmosphere, using filter recycle caused by micro mist to get
To compound particle.Graphene oxide 20% is added into compound particle, is sufficiently mixed using planetary mill, is obtained mixed powder
End.It after mixed-powder is dried, is heated 2 hours at 620 DEG C, concrete mode is：Muffle furnace is first to heat to 950 DEG C or more, then
620 DEG C are cooled to, precious metal composition is added under the protection of argon gas, during which pours argon gas incessantly, reaction terminates to obtain
Electrode.
Volume resistivity measurement is carried out to Examples 1 to 7, as a result such as【Table one】It is shown.
【Table one】
Claims (9)
1. a kind of precious metal composition, it is characterised in that：Including noble metal, polylactic acid modified Copolycarbonate, oxidation
Graphene；
Wherein, each ingredient weight percentage in the precious metal composition：Noble metal 10~20%, it is polylactic acid modified
Copolycarbonate 40~60%, graphene oxide 20~50%；
The noble metal is Au Ag Pt Pd, osmium, one kind in iridium or its a variety of alloy；
The grain size of the noble metal is 10~500nm, and the weight average molecular weight of the polylactic acid modified Copolycarbonate is：
Mw=10,000~800,000.
2. precious metal composition according to claim 1, it is characterised in that：Each ingredient is by weight in the precious metal composition
Measure percentage composition meter：Noble metal 12~18%, polylactic acid modified Copolycarbonate 45~55%, graphene oxide 27~
43%.
3. precious metal composition according to claim 1, it is characterised in that：Each ingredient is by weight in the precious metal composition
Measure percentage composition meter：Noble metal 16%, polylactic acid modified Copolycarbonate 50%, graphene oxide 34%.
4. precious metal composition according to claim 1, it is characterised in that：The grain size of the noble metal is 50~250nm,
The weight average molecular weight of the polylactic acid modified Copolycarbonate is：Mw=60,000~500,000.
5. precious metal composition according to claim 1, it is characterised in that：The grain size of the noble metal is 100nm, described
The weight average molecular weight of polylactic acid modified Copolycarbonate is：Mw=300,000.
6. a kind of preparation method of electrode, the electrode is based on any one of the Claims 1 to 5 precious metal composition, system
It is standby that steps are as follows：
(1) it is 10,000~800 by the noble metal granule of 10~500nm of average grain diameter and weight average molecular weight using V-Mixer,
000 polylactic acid modified Copolycarbonate is uniformly mixed, which is filled using high frequency induction thermal plasma
Set and be discarded in plasma atmosphere under argon atmosphere, using filter recycle caused by micro mist to get to compound particle；
(2) graphene oxide is added into compound particle, is sufficiently mixed using planetary mill, and mixed-powder is obtained；
(3) it after drying mixed-powder, and is heated 0.5~2.5 hour at 500~950 DEG C, concrete mode is：Muffle furnace is first
950 DEG C or more are heated to, then cools to set temperature, graphene oxide is added under the protection of argon gas, during which rushes incessantly
Enter argon gas, in reaction process, electrode holder is placed in exit, the electrode is made.
7. the preparation method of electrode according to claim 6, it is characterised in that：The reaction temperature is 700~920 DEG C, institute
It is 1~2h to state heating time.
8. the preparation method of electrode according to claim 7, it is characterised in that：The reaction temperature is 850 DEG C, the heating
Time is 1.5h.
9. a kind of electrochemical sensor, it is characterised in that：The electrochemical sensor is based on any one of Claims 1 to 5 institute
What the precious metal composition stated was prepared.
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