CN109772334A - A kind of big mesoporous nickel cobalt glucose-sensitive material of high-specific surface area and preparation method thereof - Google Patents
A kind of big mesoporous nickel cobalt glucose-sensitive material of high-specific surface area and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of high specific surface area ordered big mesoporous nickel cobalt non-enzymatic biological sensor sensing material for glucose detection, especially a kind of big mesoporous nickel cobalt glucose-sensitive materials of high-specific surface area and preparation method thereof.Its main feature is that: the material is arranged by cobalt acid nickel spiral nanometer line cubic periodic, and wherein the diameter of nano wire is 4-6nm, is formed by big mesoporous, the specific surface area 132-185m that meso-hole structure is 11nm2·g‑1.High specific surface area ordered big mesoporous nickel cobalt non-enzymatic glucose biological sensor sensing material provided by the invention shows to show glucose excellent detection performance, it may be implemented to the quick of glucose molecule, highly sensitive detection has good stability and anti-interference ability and good to the selectivity of glucose.
Description
Technical field
The present invention relates to a kind of high specific surface area ordered big mesoporous nickel cobalt non-enzymatic biologies for glucose detection to pass
Sensor sensitive material, especially a kind of big mesoporous nickel cobalt glucose-sensitive material of high-specific surface area and preparation method thereof.
Background technique
Glucose analyzes the content with detection glucose, in clinic as one of necessary compound of life fast and reliablely
Many fields such as detection, food production, biotechnology are all of great significance.In terms of medical diagnosis, diabetes are worldwide
Frequently-occurring disease and common disease, increase with the improvement of people ' s living standards with elderly population, disease incidence becomes in obvious rise
Gesture.Fast and reliable detection blood-sugar content is conducive to the treatment and control of diabetic condition；In terms of food industry, usually need
Detect the glucose content in the food additives such as beverage, fruit juice；Furthermore the glucose content in industrial wastewater also usually needs
Detect etc..
The method of detection glucose content mainly has chromatography, fluorescent spectrometry, spectrophotometry etc. at present.But these sides
Method equipment is expensive and pretreatment process is complicated.And electrochemical sensing method especially non-enzymatic glucose sensor, rely on its Gao Ling
Sensitivity, easy to operate, low cost, the advantages such as response quickly get more and more people's extensive concerning.Mesoporous material has high ratio table because of it
The characteristics such as area, uniform aperture, regulatable pore size, pore wall thickness make it have high activity site, excellent transmission
Performance has very big potentiality in fields such as electrochemical sensors.Have more researcher so far to report based on expensive
Pt metal, Au and its composite material, the nickel oxide (NiO) based on transition metal, cobaltosic oxide (Co3O4), copper oxide (CuO)
The research achievement in equal non-noble metallic materials modification non-enzymatic glucose sensor field.Nugraha et al. is using mesoporous Au as non-
Enzymatic glucose sensitive material, 0.1-10mM of the range of linearity, sensitivity are 291.6 μ AmM-1·cm-2(NugrahaA.S.,et
al.,Block-Copolymer-Assisted Electrochemical Synthesis of Mesoporous Gold
Electrodes:Towards a Non-Enzymatic Glucose Sensor,ChemElectroChem,4(2017)
2571–2576)；Ma et al. uses Cu2O is as non-enzymatic glucose sensitive material, under+0.6V operating voltage, the range of linearity
0.003-7.8mM, sensitivity are 2116.9 μ AmM-1·cm-2(Ma J.,Wang J.,Wang M.,Zhang G.,Peng
W.,Li Y.,Fan X.,Zhang F.,Preparation of Cuprous Oxide Mesoporous Spheres with
Different Pore Sizes for Non-Enzymatic Glucose Detection,Nanomaterials,8
(2018)73)；Huang et al. is using NiO hollow sphere/graphene composite material as non-enzymatic glucose sensitive material, linear model
0.009-0.129mM is enclosed, sensitivity is 2040 μ AmM-1·cm-2(Huang W.,Ding S.,Chen Y.,Hao W.,Lai
X.,Peng J.,Tu J.,Cao Y.,Li X.,3D NiO hollow sphere/reduced graphene oxide
composite for high-performance glucose biosensor,J.Sci.Rep,7(2017))；It is clever based on this
The non-enzymatic glucose sensitive material that sensitivity is high, response is fast, stability is good still needs further to be developed.
Summary of the invention
An object of the present invention is to provide a kind of big mesoporous nickel cobalt glucose-sensitive material of high-specific surface area, by the material
Expect that glucose can be shown excellent detection performance in the application of electrode and glucose non-enzymatic electrochemical sensor of modification,
Have high sensitivity, low-response time, good stability and anti-interference ability.
The second object of the present invention is to provide a kind of preparation method of above-mentioned glucose-sensitive material.
A kind of big mesoporous nickel cobalt glucose-sensitive material of high-specific surface area, its special feature is that: the material is by cobalt
Sour nickel spiral nanometer line cubic periodic arranges, and wherein the diameter of nano wire is 4-6nm, and being formed by meso-hole structure is
11nm's big mesoporous, specific surface area 132-185m2·g-1。
A kind of preparation method of the big mesoporous nickel cobalt glucose-sensitive material of high-specific surface area, its special feature is that,
Preparation method includes the following steps:
A), the 37wt% concentrated hydrochloric acid of 72.0g surfactant P123,2.6L deionized water and 120mL is taken to mix at 35 DEG C
It closes, stirs 1-12 hours, 72g n-butanol is then added, after stirring 2 hours, 154.8g tetraethyl orthosilicate TEOS, stirring is added
It after 24 hours, is transferred in polytetrafluoroethylene (PTFE) bottle, then 35-80 DEG C of hydro-thermal reaction for 24 hours, is filtered, deionization after natural cooling
Water washing arrives the mesopore silicon oxide containing surfactant to neutral, natural drying at room temperature；
B), the mesopore silicon oxide of the obtained P123 containing surfactant is calcined 6 hours for 550 DEG C in air, is obtained not
Mesopore silicon oxide containing surfactant；
C), by 0.2984g Ni (NO3)2·6H2O、0.5972g Co(NO3)2·6H2O, wherein before nickel nitrate and cobalt nitrate
Drive body molar ratio is 1:2, is distributed in 5mL ethanol solution, and the mesoporous oxygen that 1g step b) is obtained is added in Xiang Shangshu solution
SiClx adds 5ml ethanol solution as hard template, and 40 DEG C of stirring dippings continue stirring until ethyl alcohol volatilization and finish, then
It is calcined 5 hours in tube furnace air atmosphere in 300 DEG C, control calcining heating rate is 2 DEG C/min；
D), 2M NaOH solution is added into calcined product, centrifugal filtration is after stirring to remove mesopore silicon oxide mould
Plate, deionization are washed to neutrality, and 65 DEG C are dried overnight to get the big mesoporous nickel cobalt sensitive material of high-specific surface area is arrived.
Step c) the intermediary hole silica, ethyl alcohol, nitric acid object presoma, that is, nickel nitrate and cobalt nitrate three mass ratio
For 1:10:0.8-2.3, nickel nitrate and cobalt nitrate molar ratio are 1:1.6-2.6.
The present invention has following effect:
1) high specific surface area ordered big mesoporous nickel cobalt non-enzymatic glucose biological sensor sensing material provided by the invention
It shows to show glucose excellent detection performance, may be implemented to the quick of glucose molecule, highly sensitive detection has
Good stability and anti-interference ability and good to the selectivity of glucose；
2) orderly big mesoporous nickel cobalt provided by the invention is arranged by cobalt acid nickel spiral nanometer line cubic periodic, is received
The diameter of rice noodles is 4-6nm, high-specific surface area 132-185m2·g-1, more work can be provided for the catalysis oxidation of glucose
Property site, so that detection sensitivity is promoted, and the big mesoporous diffusion for being conducive to effects of ion and glucose molecule of 11nm,
Active site is more effectively utilized, enhances sensitivity, accelerates the response time；
3) specific surface area of material and mesoporous size can be by adjusting the loading of nitrate precursors and mesoporous
The aperture of silica controls, and can change its glucose catalyticing oxidation performance accordingly；
4) using the material as glucose sensor made of sensing material, in 0.1M NaOH solution ,+0.55V work electricity
Under the conditions of pressure, glucose concentration range is that 0.01-0.638mM is and when 0.638-3.360mM, sensitivity respectively reaches 4368.8
μA·mM-1·cm-2With 3301.6 μ AmM-1·cm-2, the response time is less than 2s.Uric acid, anti-bad is added in glucose detection
The interfering substances such as hematic acid, sodium chloride and dopamine, are nearly free from any influence, show that the selectivity of the glucose sensor is good
It is good.Therefore the non-enzyme sensor based on material building can be used for the highly sensitive detection of glucose.
Detailed description of the invention
Fig. 1 is 1 gained of embodiment orderly big mesoporous NiCo2O4HRTEM picture；
Fig. 2 is 1 gained of embodiment orderly big mesoporous NiCo2O4Graph of pore diameter distribution；
Fig. 3 is the EIS curve graph of the glass-carbon electrode of 1 gained sensitive material of embodiment modification, in which: (a) Bare GCE；
(b)NiCo2O4/GCE；
Fig. 4 is 1 gained of embodiment orderly big mesoporous NiCo2O4The glass-carbon electrode of sensitive material modification is with and without containing
CV curve in the 0.1M NaOH solution of 0.1mM glucose；
Fig. 5 is 1 gained of embodiment orderly big mesoporous NiCo2O4The glass-carbon electrode of sensitive material modification is in 0.1mM glucose
Difference sweeps the CV curve (fitted figure that illustration is peak current and sweep speed) under speed；
Fig. 6 is 1 gained of embodiment orderly big mesoporous NiCo2O4The glass-carbon electrode of sensitive material modification is in 0.1M NaOH solution
In chrono-amperometric detection (+0.55V) (illustration be corresponding matched curve and response time)；
Fig. 7 is 1 gained of embodiment orderly big mesoporous NiCo2O4The interference--free experiments of the glass-carbon electrode of sensitive material modification.
Specific embodiment:
The present invention relates to a kind of preparation methods of high specific surface area ordered big mesoporous nickel cobalt non-enzymatic glucose sensitive material.
The non-enzymatic glucose biological sensor sensing material is arranged by the spiral nanometer line cubic periodic of cobalt acid nickel, nano wire
Diameter be 4-6nm, be formed by meso-hole structure be 11nm it is mesoporous greatly, specific surface area 132-185m2·g-1。
The present invention relates to a kind of high specific surface area ordered big mesoporous nickel cobalt non-enzymatic glucose sensitive materials, with material work
For glucose sensor made of sensing material, under the conditions of 0.1M NaOH solution ,+0.55V operating voltage, concentration of glucose
Range is that 0.01-0.638mM is and when 0.638-3.360mM, sensitivity respectively reaches 4368.8 μ AmM-1·cm-2With
3301.6μA·mM-1·cm-2, the response time is less than 2s.Uric acid, ascorbic acid, sodium chloride and more are added in glucose detection
The interfering substances such as bar amine, are nearly free from any influence, show that the selectivity of the glucose sensor is good.Therefore it is based on the material
The non-enzyme sensor of material building can be used for the highly sensitive detection of glucose.
A kind of preparation method of new high specific surface area ordered big mesoporous nickel cobalt non-enzymatic glucose bio-sensing, including such as
Lower step:
(a), 72.0g surfactant P123,2.6L deionized water and 120mL concentrated hydrochloric acid (37wt%) are mixed at 35 DEG C
It closes, stirs 1-12 hours until surfactant is all dissolved and is uniformly dispersed, then addition 72g n-butanol, is stirred 2 hours
Afterwards, 154.8g tetraethyl orthosilicate TEOS is added to be transferred in a polytetrafluoroethylene (PTFE) bottle, then 40 DEG C of water after stirring 24 hours
Thermal response for 24 hours, is filtered, deionized water is washed to neutral, natural drying at room temperature to get to containing surface after cooled to room temperature
The mesopore silicon oxide of activating agent；
B), above-mentioned gained sample surfaces activating agent P123 is obtained after being removed within calcining 6 hours by 550 DEG C in air and is free of table
The mesopore silicon oxide of face activating agent；
C), by 0.2984g Ni (NO3)2·6H2O、0.5972g Co(NO3)2·6H2O (nickel nitrate and nitric acid cobalt precursor
Molar ratio is 1:2) it is distributed in 5mL ethanol solution, mesopore silicon oxide obtained by 1g step b) is added in Xiang Shangshu solution and makees
For hard template, 5ml dehydrated alcohol, 40 DEG C of stirrings dippings are added, so that nickel, cobalt salt solution be made to enter the duct of mesopore silicon oxide
In, continue stirring until ethyl alcohol volatilization finish, by the sample powder of acquisition after being fully ground in tube furnace air atmosphere in 300
DEG C calcining 5 hours, calcining heating rate be 2 DEG C/min；
D), 2M NaOH solution is added into calcined product, centrifugal filtration is after stirring to remove mesopore silicon oxide mould
Plate.Deionization is washed to neutrality, and 65 DEG C are dried overnight to get high specific surface area ordered big mesoporous nickel cobalt non-enzymatic of the invention is arrived
Biological sensor sensing material.
40 DEG C of hydrothermal temperature in the step a), the excessively high gained mesopore silicon oxide of hydrothermal temperature cannot be with it
Template prepares big meso-hole structure；
Nickel nitrate and cobalt nitrate molar ratio are 1:1.6-2.6, the dosage and nitrate of mesopore silicon oxide in the step c)
The ratio between dosage be 0.8-2.3, the ratio between dosage of the dosage of mesopore silicon oxide and nitrate is too big or too small cannot to obtain height
Large specific surface area mesoporous nickel cobalt, calcination temperature are 150-600 DEG C, and heating rate is 0.5-3 DEG C/min, calcination time 2-
10h。
The concentration of sodium hydroxide solution in the step d) is 2-10M.
Below by embodiment, the invention will be further elaborated:
Embodiment 1:
One, the preparation of high specific surface area ordered big mesoporous nickel cobalt non-enzymatic biological sensor sensing material:
72.0g surfactant P123,2.6L deionized water is taken to mix at 35 DEG C with 120mL concentrated hydrochloric acid (37wt%),
It all dissolves and is uniformly dispersed until surfactant within stirring 1-12 hour, 72g n-butanol is then added, after stirring 2 hours,
154.8g tetraethyl orthosilicate TEOS is added to be transferred in polytetrafluoroethylene (PTFE) bottle, then 40 DEG C of hydro-thermal reactions after stirring 24 hours
For 24 hours, it is filtered after cooled to room temperature, deionized water is washed to neutral, natural drying at room temperature to get to containing surfactant
Mesopore silicon oxide；After activating agent P123 on gained sample surfaces is removed for calcining 6 hours by 550 DEG C in air, obtain
Mesopore silicon oxide without surfactant；Resulting ordered meso-porous silicon oxide specific surface area 819m2·g-1, pore volume
0.73cm3·g-1, pore size is about 5.7nm.
By 0.2984g Ni (NO3)2·6H2O、0.5972g Co(NO3)2·6H2O (rub by nickel nitrate and nitric acid cobalt precursor
You are than being 1:2) it is distributed in 5mL ethanol solution, the above-mentioned mesopore silicon oxide of 1g is added in Xiang Shangshu solution as hard template,
5ml ethanol solution is added, 40 DEG C of stirring dippings so that nickel, cobalt salt solution be made to enter in the duct of mesopore silicon oxide, are held
Continuous stirring to ethyl alcohol volatilization finishes.
The sample powder of acquisition is calcined 5 hours in air atmosphere in 300 DEG C in tube furnace after being fully ground, calcining
Heating rate is 2 DEG C/min；The stirring of 2M NaOH solution is added into calcined product, centrifugal filtration is situated between after stirring to remove
Hole silica template.Deionization is washed to neutrality, and 65 DEG C are dried overnight to get raw to order mesoporous cobalt acid nickel non-enzymatic of the invention
Object sensor sensing material.The specific surface area of the material is 181m2·g-1, pore volume 0.72cm3·g-1, aperture size is
11nm。
Two, the preparation of working electrode and electrochemical property test:
All electrochemical measurements be PARSTAT4000 electrochemical workstation (PrincetonApplied Research,
USA it is carried out on), using three-electrode system；Glass-carbon electrode (diameter 3mm) is working electrode, and saturated calomel electrode is reference electrode,
Pt electrodes are to electrode.Glass-carbon electrode 1.0 μm, 0.3 μm, 0.05 μm of alumina powder successively polishing grinding, every time after polishing
It is cleaned by ultrasonic with ethyl alcohol and deionized water, it is spare after dry.By the orderly big mesoporous NiCo of preparation2O4It is dispersed in dehydrated alcohol
(3mg/mL) takes a certain amount of gained dispersant liquid drop to be coated in the glassy carbon electrode surface handled well, the certain density sodium hydroxide of 10mL
It is spare as electrolyte solution.
Fig. 1 is the HRTEM picture of mesoporous nickel cobalt obtained by the present embodiment, show its cellular structure with high-sequential and
The large aperture of 11nm, lattice fringe pitch measurements are NiCo in 0.245nm, with XRD2O4(311) indices of crystallographic plane are consistent, bone
Frame dimensional measurements are 4.6nm, show that synthesized mesoporous nickel cobalt replicates Jie's sight of mesoporous KIT-6-40 orderly well
Structure；
Fig. 2 is the pore size distribution map of orderly big mesoporous nickel cobalt obtained by the present embodiment, it was demonstrated that it is with orderly 11nm's
Big meso-hole structure；
What Fig. 3 was provided is ordered into big mesoporous nickel cobalt modified electrode and glass-carbon electrode in 0.1M KCl, 5mM K3Fe(CN)6/
K4Fe(CN)6Middle EIS map.It is shown in figure, compare glass-carbon electrode, modified electrode has lesser high frequency region semi arch, and explanation has
The big mesoporous nickel cobalt modified electrode of sequence its with smaller charge transfer resistance, embody its excellent conductive performance, be more advantageous to
The catalytic oxidation of glucose.
Fig. 4 is that orderly big mesoporous nickel cobalt modified electrode and the electrode of bare glassy carbon electrode follow in 0.1mM glucose solution
Ring volt-ampere curve.It can be seen from the figure that modifying suitable mesoporous NiCo in glassy carbon electrode surface under alkaline condition2O4After material,
There is apparent oxidation peak in 0.53V or so, apparent reduction peak occurs in 0.31V or so, and its electric current all accordingly enhances, and says
Bright mesoporous NiCo2O4Material has good electrochemical catalysis activity to glucose, i.e. modified electrode has the energy for detecting glucose
Power, redox peak current are remarkably reinforced this and are attributed to the fact that mesoporous NiCo2O4Bigger serface (181m2·g-1) it is urging for glucose
Change oxidation and more active sites are provided.
The rate-determining steps for further studying the modified electrode interfacial reaction are illustrated in figure 5 orderly big mesoporous NiCo2O4It is quick
It is the CV curve under 5-100mV/s that the glass-carbon electrode of sense material modification sweeps fast range in 0.1mM glucose, corresponding scanning speed
Degree and peak current intensity fitting result show that the two has good linear relationship, therefore the rate-determining steps of electrode process are surface
Reaction controlling shows the big mesoporous diffusion for being conducive to effects of ion and glucose molecule of 11nm, can more effectively utilize
Active site.
Measure the relationship between concentration of glucose and electric current by chrono-amperometric, as shown in fig. 6,0.1MNaOH solution ,+
Under 0.55V operating voltage, orderly big mesoporous NiCo2O4The glass-carbon electrode of sensitive material modification realizes the quick height to glucose
The response of effect.Illustration 1 shows that the detection of modified electrode is limited to 1.33 μM (S/N=3), and the range of linearity is 0.01-0.638mM, spirit
Sensitivity is up to 4368.8 μ AmM-1·cm-2, when the range of linearity is 0.638-3.360mM, sensitivity is 3301.6 μ AmM-1·
cm-2.Illustration 2 shows modified electrode to the response quickly of glucose, and the response time is less than 2s.
Fig. 7 shows chaff interferent (0.01mM uric acid, 0.01mM ascorbic acid, 0.01mM sodium chloride and 0.01mM dopamine)
Addition is smaller on the influence of the response current of glucose, illustrates that modified electrode has preferable anti-interference ability therefore the sound to glucose
There should be certain selectivity.And the electrode after modifying also has preferable stability, reproducibility and long-time stability.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Embodiment 2:
72.0g surfactant P123,2.6L deionized water is taken to mix at 35 DEG C with 120mL concentrated hydrochloric acid (37wt%),
It all dissolves and is uniformly dispersed until surfactant within stirring 1-12 hour, 72g n-butanol is then added, after stirring 2 hours,
154.8g tetraethyl orthosilicate TEOS is added to be transferred in polytetrafluoroethylene (PTFE) bottle, then 40 DEG C of hydro-thermal reactions after stirring 24 hours
For 24 hours, it is filtered after cooled to room temperature, deionized water is washed to neutral, natural drying at room temperature to get to containing surfactant
Mesopore silicon oxide；After activating agent P123 on gained sample surfaces is removed for calcining 6 hours by 550 DEG C in air, obtain
Mesopore silicon oxide without surfactant；Resulting ordered meso-porous silicon oxide specific surface area 829m2·g-1, pore volume
0.90cm3·g-1, pore size is about 6.5nm.
By 0.4792g Ni (NO3)2·6H2O、0.9592g Co(NO3)2·6H2O (rub by nickel nitrate and nitric acid cobalt precursor
You are than being 1:2) it is distributed in 5mL ethanol solution, the above-mentioned mesopore silicon oxide of 1g is added in Xiang Shangshu solution as hard template,
5ml ethanol solution is added, is impregnated in 40 DEG C of stirrings, thus enter nickel, cobalt salt solution in the duct of mesopore silicon oxide,
Continue stirring until ethyl alcohol volatilization finish, by the sample powder of acquisition after being fully ground in tube furnace air atmosphere in 300 DEG C
Calcining 5 hours, calcining heating rate are 2 DEG C/min；2M NaOH solution is added into calcined product, was centrifuged after stirring
Filter is to remove mesopore silicon oxide template.Deionization is washed to neutrality, and 65 DEG C are dried overnight to get order mesoporous cobalt of the invention is arrived
Sour nickel non-enzymatic biological sensor sensing material.The specific surface area of the material is 135m2·g-1, pore volume 0.37cm3·g-1, hole
Diameter is having a size of 11 (3.5) nm.
Embodiment 3:
72.0g surfactant P123,2.6L deionized water mixes at 35 DEG C with 120mL concentrated hydrochloric acid (37wt%), stirs
1-12 hours are mixed until surfactant is all dissolved and is uniformly dispersed, then addition 72g n-butanol adds after stirring 2 hours
Enter 154.8g tetraethyl orthosilicate TEOS to be transferred in a polytetrafluoroethylene (PTFE) bottle, then 40 DEG C of hydro-thermal reactions after stirring 24 hours
For 24 hours, it is filtered after cooled to room temperature, deionized water is washed to neutral, natural drying at room temperature to get to containing surfactant
Mesopore silicon oxide；After gained sample surfaces activating agent P123 is removed for calcining 6 hours by 550 DEG C in air, it must be free of
The mesopore silicon oxide of surfactant；Resulting ordered meso-porous silicon oxide specific surface area 819m2·g-1, pore volume 0.73cm3·g-1, pore size is about 5.7nm.
By 0.3458g Ni (NO3)2·6H2O、0.5537g Co(NO3)2·6H2O (rub by nickel nitrate and nitric acid cobalt precursor
You are than being 1:1.6) it is distributed in 5mL ethanol solution, the above-mentioned mesopore silicon oxide of 1g is added in Xiang Shangshu solution as hard mold
Plate adds 5ml ethanol solution, impregnates in 40 DEG C of stirrings, so that nickel, cobalt salt solution be made to enter the duct of mesopore silicon oxide
In, continue stirring until ethyl alcohol volatilization finish, by the sample powder of acquisition after being fully ground in tube furnace air atmosphere in 300
DEG C calcining 5 hours, calcining heating rate be 2 DEG C/min；2M NaOH solution is added into calcined product, is centrifuged after stirring
Filtering is to remove mesopore silicon oxide template.Deionization is washed to neutrality, and 65 DEG C are dried overnight to get to of the invention order mesoporous
Cobalt acid nickel non-enzymatic biological sensor sensing material.The specific surface area of the material is 147m2·g-1, pore volume 0.49cm3·g-1,
Aperture size is 11 (5.8) nm.
Embodiment 4:
72.0g surfactant P123,2.6L deionized water mixes at 35 DEG C with 120mL concentrated hydrochloric acid (37wt%), stirs
1-12 hours are mixed until surfactant is all dissolved and is uniformly dispersed, then addition 72g n-butanol adds after stirring 2 hours
Enter 154.8g tetraethyl orthosilicate TEOS to be transferred in a polytetrafluoroethylene (PTFE) bottle, then 40 DEG C of hydro-thermal reactions after stirring 24 hours
For 24 hours, it is filtered after cooled to room temperature, deionized water is washed to neutral, natural drying at room temperature to get to containing surfactant
Mesopore silicon oxide；After gained sample surfaces activating agent P123 is removed for calcining 6 hours by 550 DEG C in air, it must be free of
The mesopore silicon oxide of surfactant；Resulting ordered meso-porous silicon oxide specific surface area 819m2·g-1, pore volume 0.73cm3·g-1, pore size is about 5.7nm.
By 0.2475g Ni (NO3)2·6H2O、0.6439g Co(NO3)2·6H2O (rub by nickel nitrate and nitric acid cobalt precursor
You are than being 1:2.6) it is distributed in 5mL ethanol solution, the above-mentioned mesopore silicon oxide of 1g is added in Xiang Shangshu solution as hard
Template adds 5ml ethanol solution, impregnates in 40 DEG C of stirrings, so that nickel, cobalt salt solution be made to enter the hole of mesopore silicon oxide
In road, continue stirring until ethyl alcohol volatilization finish, by the sample powder of acquisition after being fully ground in tube furnace air atmosphere in
300 DEG C are calcined 5 hours, and calcining heating rate is 2 DEG C/min；The stirring of 2M NaOH solution, stirring are added into calcined product
Centrifugal filtration is afterwards to remove mesopore silicon oxide template.Deionization is washed to neutrality, and 65 DEG C are dried overnight and have to get to of the invention
Sequence mesoporous nickel cobalt non-enzymatic biological sensor sensing material.The specific surface area of the material is 132m2·g-1, pore volume is
0.54cm3·g-1, aperture size is 11 (5.8) nm.
Claims (3)
1. a kind of big mesoporous nickel cobalt glucose-sensitive material of high-specific surface area, it is characterised in that: the material is by cobalt acid nickel spiral shell
Rotation nano wire cubic periodic arranges, and wherein the diameter of nano wire is 4-6nm, and being formed by meso-hole structure is the big of 11nm
It is mesoporous, specific surface area 132-185m2·g-1。
2. a kind of preparation method of the big mesoporous nickel cobalt glucose-sensitive material of high-specific surface area, which is characterized in that its preparation side
Method includes the following steps:
A), take 72.0g surfactant P123,2.6L deionized water to mix at 35 DEG C with the 37wt% concentrated hydrochloric acid of 120mL, stir
It mixes 1-12 hours, 72g n-butanol is then added, after stirring 2 hours, 154.8g tetraethyl orthosilicate TEOS is added, stirring 24 is small
Shi Hou is transferred in polytetrafluoroethylene (PTFE) bottle, and then 35-80 DEG C of hydro-thermal reaction for 24 hours, is filtered, deionization is washed after natural cooling
It washs to neutral, natural drying at room temperature to get the mesopore silicon oxide containing surfactant is arrived；
B), the mesopore silicon oxide of the obtained P123 containing surfactant is calcined 6 hours for 550 DEG C in air, is obtained without table
The mesopore silicon oxide of face activating agent；
C), by 0.2984g Ni (NO3)2·6H2O、0.5972g Co(NO3)2·6H2O, wherein nickel nitrate and nitric acid cobalt precursor
Molar ratio is 1:2, is distributed in 5mL ethanol solution, and the mesopore silicon oxide that 1g step b) is obtained is added in Xiang Shangshu solution
As hard template, 5ml ethanol solution is added, 40 DEG C of stirring dippings continue stirring until ethyl alcohol volatilization and finish, then in pipe
It is calcined 5 hours in formula stove air atmosphere in 300 DEG C, control calcining heating rate is 2 DEG C/min；
D), 2M NaOH solution is added into calcined product, after stirring centrifugal filtration to removing mesopore silicon oxide template,
Deionization is washed to neutrality, and 65 DEG C are dried overnight to get the big mesoporous nickel cobalt sensitive material of high-specific surface area is arrived.
3. a kind of preparation method of the big mesoporous nickel cobalt glucose-sensitive material of high-specific surface area as claimed in claim 2,
It is characterized in that: step c) the intermediary hole silica, ethyl alcohol, nitric acid object presoma, that is, nickel nitrate and cobalt nitrate three mass ratio
For 1:10:0.8-2.3, nickel nitrate and cobalt nitrate molar ratio are 1:1.6-2.6.
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| CN201811625031.0A CN109772334A (en) | 2018-12-28 | 2018-12-28 | A kind of big mesoporous nickel cobalt glucose-sensitive material of high-specific surface area and preparation method thereof |
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| CN110606510A (en) * | 2019-09-18 | 2019-12-24 | 宁夏大学 | High-specific-surface-area ordered large-mesoporous zinc manganate material and preparation method thereof |
| CN110665506A (en) * | 2019-09-18 | 2020-01-10 | 宁夏大学 | Tetracycline photocatalytic degradation material and preparation method thereof |
| CN110950387A (en) * | 2019-09-18 | 2020-04-03 | 宁夏大学 | Spinel manganate material with ordered mesostructure and preparation method thereof |
| CN111620366A (en) * | 2020-04-15 | 2020-09-04 | 宁夏大学 | High specific surface area ordered large mesoporous spinel zinc gallate and preparation method thereof |
| CN114620763A (en) * | 2021-11-26 | 2022-06-14 | 宁夏大学 | High-specific-surface-area ordered large-mesoporous copper gallate gas-sensitive material and preparation method thereof |
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| CN110665506A (en) * | 2019-09-18 | 2020-01-10 | 宁夏大学 | Tetracycline photocatalytic degradation material and preparation method thereof |
| CN110950387A (en) * | 2019-09-18 | 2020-04-03 | 宁夏大学 | Spinel manganate material with ordered mesostructure and preparation method thereof |
| CN111620366A (en) * | 2020-04-15 | 2020-09-04 | 宁夏大学 | High specific surface area ordered large mesoporous spinel zinc gallate and preparation method thereof |
| CN114620763A (en) * | 2021-11-26 | 2022-06-14 | 宁夏大学 | High-specific-surface-area ordered large-mesoporous copper gallate gas-sensitive material and preparation method thereof |
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