CN114689668A - Copper-iron nano composite material prepared by microbial corrosion method and application thereof - Google Patents
Copper-iron nano composite material prepared by microbial corrosion method and application thereof Download PDFInfo
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- CN114689668A CN114689668A CN202011621990.2A CN202011621990A CN114689668A CN 114689668 A CN114689668 A CN 114689668A CN 202011621990 A CN202011621990 A CN 202011621990A CN 114689668 A CN114689668 A CN 114689668A
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 49
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000005260 corrosion Methods 0.000 title claims abstract description 31
- 230000007797 corrosion Effects 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 26
- 230000000813 microbial effect Effects 0.000 title claims abstract description 15
- 229920000728 polyester Polymers 0.000 claims abstract description 61
- 239000004744 fabric Substances 0.000 claims abstract description 59
- 239000000835 fiber Substances 0.000 claims abstract description 57
- 229910017827 Cu—Fe Inorganic materials 0.000 claims abstract description 31
- 238000002791 soaking Methods 0.000 claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 230000008021 deposition Effects 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 241000894006 Bacteria Species 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000002135 nanosheet Substances 0.000 claims abstract description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims abstract description 6
- 229910002666 PdCl2 Inorganic materials 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims abstract description 6
- 229910052927 chalcanthite Inorganic materials 0.000 claims abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000001509 sodium citrate Substances 0.000 claims abstract description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000012258 culturing Methods 0.000 claims abstract description 5
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 5
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 16
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- 239000002086 nanomaterial Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 4
- 229930003268 Vitamin C Natural products 0.000 description 4
- 229940041514 candida albicans extract Drugs 0.000 description 4
- DXKGMXNZSJMWAF-UHFFFAOYSA-N copper;oxido(oxo)iron Chemical compound [Cu+2].[O-][Fe]=O.[O-][Fe]=O DXKGMXNZSJMWAF-UHFFFAOYSA-N 0.000 description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 4
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000001963 growth medium Substances 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- NGSFWBMYFKHRBD-UHFFFAOYSA-M sodium lactate Chemical compound [Na+].CC(O)C([O-])=O NGSFWBMYFKHRBD-UHFFFAOYSA-M 0.000 description 4
- 239000001540 sodium lactate Substances 0.000 description 4
- 235000019154 vitamin C Nutrition 0.000 description 4
- 239000011718 vitamin C Substances 0.000 description 4
- 239000012138 yeast extract Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 208000003174 Brain Neoplasms Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/285—Sensitising or activating with tin based compound or composition
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
Abstract
The invention discloses a copper-iron nano composite material prepared by a microbial corrosion method, which is a copper-iron nano composite material containing a composite Cu-Fe (OH)2-a nanosheet structure of FeS. The preparation method comprises the following steps: cleaning the polyester fiber cloth; disposing polyester fibers to SnCl2·2H2Sensitizing the surface of the mixture of O and HCl; soaking in PdCl2Completing surface activation in a mixed solution of HCl and HCl; with deionized waterRinsing and keeping under nitrogen flow for drying; the activated polyester fiber is coated on CuSO4·5H2O、Na3C6H5O7、NH4Cl, 10% NaOH and NaH2PO2·H2Soaking in DI water mixed solution of O to obtain polyester fiber cloth with Cu deposition; then immersing the copper-iron nano composite material into a reagent bottle containing 33 percent of Sulfate Reducing Bacteria (SRB), and culturing for 5-14 days in an oxygen-free atmosphere to obtain the copper-iron nano composite material.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a copper-iron nano composite material prepared by a microbial corrosion method and application thereof.
Technical Field
The precious metal-based nano material has excellent electrocatalytic efficiency, but the practical application of the precious metal-based nano material is greatly limited by the defects of high cost, scarcity and the like. In comparison, metal oxides, hydroxides and sulfides also have quite high electrocatalytic activity, can be used as a substitute of noble metal materials, and have wide application prospects in the field of electrochemical sensing detection. Particularly, the composite material is compounded by metal oxide/hydroxide and sulfide, and the composite material can show excellent electrocatalytic performance. Layered nanostructured copper-iron oxide/hydroxide and sulfide composites have been demonstrated to have excellent electrocatalytic activity, and current synthetic methods include electrodeposition and hydrothermal methods. However, these bottom-up processes require very stringent synthesis conditions, such as high temperatures and pressures. Therefore, the development of a simple and efficient method for preparing the copper-iron oxide/hydroxide composite material with the layered nano structure is still a great challenge for realizing the application of the copper-iron oxide/hydroxide composite material in the direction of electrochemical sensors, even in other fields.
In corrosion engineering, metal corrosion is usually performed at normal temperature and pressure. Therefore, this top-down metal corrosion strategy provides a new approach to building integrated nanomaterials under mild environmental conditions. In addition, many microorganisms in nature are generally capable of accelerating the corrosion process and ultimately producing corrosion products on the substrate. It is worth mentioning that Sulfate Reducing Bacteria (SRB) are the main corrosive microorganisms present in oil field produced water, offshore sediments, etc. and energy is obtained by reducing sulfates to sulfides by enzymes. Generally, corrosion of carbon steel by SRB produces integral corrosion products of iron sulfide and iron (oxy) hydroxide. Therefore, the corrosion method of the SRB can solve the problems of complicated preparation process, danger, high cost and the like, and a new way is provided for constructing an ideal high-efficiency composite electrode material.
Disclosure of Invention
The invention aims to provide a copper-iron nano composite material prepared by a microbial corrosion method, simultaneously provide application of the copper-iron nano composite material, and solve the technical problems that in the prior art, a copper-iron oxide/hydroxide and sulfide composite material needs high temperature and high pressure, a complex process, a precursor solution is finely treated, the nano material is expensive to prepare and the like. The invention provides a method for preparing a copper-iron nano composite material by a microbial corrosion method, which generates a composite corrosion product of iron sulfide and iron (oxygen) hydroxide by the corrosion of SRB on iron. These SRBs produce corrosion products with excellent electrocatalytic properties. The SRB corrosion method overcomes the problems of high temperature and high pressure, complex and complicated process, high cost and the like.
In order to achieve the above object, the present invention firstly provides a method for preparing a copper-iron nanocomposite by a microbial corrosion method, comprising the following steps:
(1) adopting polyester fiber cloth as a supporting substrate, and cleaning the polyester fiber cloth by using neutral deionized water;
(2) configuration of SnCl2·2H2O and HCl mixed solution, polyester fiber in the step (1) is arranged in the solution, and the solution is stirred at room temperature and the surface of the solution is sensitized;
(3) soaking the sensitized polyester fiber cloth obtained in the step (2) in PdCl2And HCl to complete surface activation;
(4) rinsing the activated polyester fiber cloth obtained in the step (3) by using deionized water, and keeping the activated polyester fiber cloth dry under nitrogen flow, thereby avoiding pollution;
(5) the activated polyester fiber cloth obtained in the step (4) is coated on CuSO4·5H2O、Na3C6H5O7、NH4Cl, 10% NaOH and NaH2PO2·H2Soaking the mixture of DI water and O at room temperature to obtain polyester fiber cloth with Cu deposition;
(6) soaking the polyester fiber cloth with the Cu deposition obtained in the step (5) into a reagent bottle containing 33% of Sulfate Reducing Bacteria (SRB), and culturing for 5-14 days at 37 ℃ in an oxygen-free atmosphere to obtain the copper-iron nano composite material, wherein the culture medium component of the sulfate reducing bacteria comprises K2HPO4,MgSO4NaCl, vitamin C, yeast extract, (NH)4)2Fe(SO4)2Sodium lactate.
Preferably, the mechanical strength of the polyester fiber cloth is 4 to 7 cN/dex.
Preferably, the SnCl of step (2)2·2H2The concentrations of O and HCl are 5-20mg/mL and 0.05-0.15M respectively, and the stirring time is 10-20 min. .
Preferably, the PdCl of step (3)2And HCl concentrations of 0.05-0.15mg/mL and 0.01-0.05M, respectively; the soaking time is 5-15 min.
Preferably, the soaking time in the step (5) is 10-30 min.
The invention discloses a copper-iron nano composite material prepared by the microbial corrosion method,
preferably, the composite material comprises a supporting substrate and a copper-iron nano composite, wherein the supporting substrate is polyester fiber cloth; the copper-iron nano composite is Cu-Fe (OH)2-FeS, nanosheet morphology.
Preferably, the copper-iron nanocomposite is deposited on the surface of the supporting substrate in an amount ranging from 10 to 100mg cm-2。
The invention also provides application of the copper-iron nano composite material prepared by the method as an electrode material.
Preferably, the copper-iron nanocomposite acts as H2O2Use of an electrochemical sensor.
Generally, compared with the prior art, the technical scheme of the invention mainly has the following beneficial effects:
(1) Cu-Fe (OH) in the present invention2The FeS composite material is of a nanosheet structure, the specific surface area of the two-dimensional micro-nano structure is large, and a large number of active sites can be exposed on a two-dimensional plane. And Cu-Fe (O)H)2Has certain synergistic effect with FeS, and the factors cause Cu-Fe (OH)2the-FeS nanosheet composite electrode material shows excellent electrocatalytic performance. Cu-Fe (OH)2FeS has excellent H2O2The electrochemical sensing performance is wide in linear range (5nM-8.2mM), low in detection limit (2nM) and good in selectivity, and can be used as a detection sensing platform for monitoring H of different human brain cancer cells in real time2O2And (4) releasing the situation.
(2) The corrosion method caused by SRB provided by the invention provides a mild, natural and simple-operation preparation process of the copper-iron nano composite material. Compared with the existing hydrothermal method, diffusion method and electrodeposition method for preparing copper-iron composite materials on substrates, the method adopts the process of combining microorganism-assisted corrosion and chemical plating to prepare two-dimensional Cu-Fe (OH) on polyester fiber cloth for the first time2The FeS nanosheet overcomes the problems of high temperature, high pressure, complexity and the like in the existing nano synthesis technology, and provides a brand new visual angle and approach for constructing an ideal high-efficiency copper-iron composite electrode material.
(3) From the perspective of preparation idea, the invention builds a bridge, skillfully connects the traditional corrosion engineering with the emerging electrochemical sensing technology, and makes up for the gap between the two technologies. The preparation process has wide prospect in the fields of corrosion engineering technology, nanotechnology, electrochemical sensors and the like.
Drawings
Fig. 1A and 1B are planar Scanning Electron Microscope (SEM) images of the surface-deposited copper polyester fiber cloth at magnifications of 1 ten thousand and 10 ten thousand in example 1, respectively.
Fig. 1C and 1D are 10 ten thousand times and 20 ten thousand times magnified polyester fiber cloth supported Cu-fe (oh)2-FeS nanoplates of example 1, respectively.
FIG. 2 shows a blank polyester cloth and Cu-Fe (OH) supported by the polyester cloth in example 12-X-ray diffraction spectrum (XRD) of FeS, with peak intensity on the ordinate and diffraction angle on the abscissa twice.
FIG. 3 is Cu-Fe (OH) supported by polyester cloth prepared in example 12-FeS gold composite electrode in PBS (pH 8.0) buffer solutionChronoamperometric response curves for different concentrations of hydrogen peroxide.
FIG. 4 is Cu-Fe (OH) prepared from example 12Linear range fit plots from timed current response plots of FeS gold composite electrodes to different concentrations of hydrogen peroxide in PBS (pH 8.0) buffer solution.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The copper-iron nano composite material prepared by the microbial corrosion method comprises a copper-iron nano composite, wherein the copper-iron nano composite is Cu-Fe (OH)2-FeS; the copper-iron nano composite is in a nano sheet shape; the Cu-Fe (OH)2FeS is deposited on the surface of the polyester fiber cloth with the deposition amount of 10mg cm-2。
The method for preparing the copper-iron nano composite material by the microbial corrosion method comprises the following steps:
taking polyester fiber cloth as a supporting substrate, cleaning the polyester fiber cloth by using neutral deionized water, and then placing the polyester fiber cloth in SnCl2·2H2In a mixed solution of O and HCl (concentration 10mg/mL and 0.1M, respectively), the mixture was gently stirred at room temperature and sensitized for 15 min. Then soaking the polyester fiber cloth after surface sensitization in PdCl2Soaking in mixed solution of HCl (concentration of 0.1mg/mL and 0.02M) for 10min to complete activation; rinsing the surface-activated polyester fiber cloth with deionized water, drying under nitrogen flow while avoiding contamination, and then washing with CuSO4·5H2O、Na3C6H5O7、NH4Cl、10％NaOH、NaH2PO2·H2Soaking in DI water mixed solution of O for 30min to obtain polyester fiber cloth with Cu deposition, as shown in FIGS. 1A and 1B.
Immersing the polyester fiber cloth with Cu deposition into a reagent bottle containing 33% of Sulfate Reducing Bacteria (SRB)Culturing at 37 deg.C under oxygen-free atmosphere for 10 days to obtain Cu-Fe (OH) supported by polyester fiber cloth2-a FeS nanocomposite. Sulfate Reducing Bacteria (SRB) are derived from oil field, wherein the culture medium of the SRB comprises K2HPO4,MgSO4NaCl, vitamin C, yeast extract, (NH)4)2Fe(SO4)2Sodium lactate. As shown in FIG. 1C and FIG. 1D, Cu-Fe (OH)2-FeS exhibits a nanosheet structure. Measurement of Cu-Fe (OH)2The deposition amount of the FeS material on the surface of the polyester fiber cloth of the supporting substrate is 10mg cm-2。
FIG. 2 shows Cu-Fe (OH) prepared in this example2XRD spectrum of FeS, it can be seen that the samples have obvious Cu-Fe (OH)2-characteristic peaks of FeS.
Example 2
Preparation of copper-iron nanocomposite by microbial corrosion process, said copper-iron nanocomposite being Cu-Fe (OH)2-FeS; the copper-iron nano composite is of a nano-sheet structure; the Cu-Fe (OH)2The FeS material is deposited on the surface of the polyester fiber cloth of the substrate, and the deposition amount is 25mg cm-2。
The method for preparing the copper-iron nano composite material by the microbial corrosion method comprises the following steps:
the polyester fiber cloth is used as a supporting substrate, washed by neutral deionized water and then placed in a SnCl preparation2·2H2In a mixed solution of O and HCl (concentration 10mg/mL and 0.1M, respectively), the mixture was gently stirred at room temperature and sensitized for 15 min. Then soaking the polyester fiber cloth after surface sensitization in PdCl2Soaking in mixed solution of HCl (concentration of 0.1mg/mL and 0.02M) for 10min to complete activation; rinsing the surface-activated polyester fiber cloth with deionized water, drying under nitrogen flow while avoiding contamination, and subjecting the rinsed surface-activated polyester fiber cloth to CuSO4·5H2O、Na3C6H5O7、NH4Cl、10％NaOH、NaH2PO2·H2And D, soaking the cloth in a DI water mixed solution of O for 20min to obtain the polyester fiber cloth with Cu deposition.
Soaking a polyester fiber cloth with Cu deposition into a solution containing 33 percent of Cu depositionCulturing Sulfate Reducing Bacteria (SRB) in a reagent bottle at 37 deg.C under oxygen-free atmosphere for 12 days to obtain Cu-Fe (OH) supported by polyester fiber cloth2-a FeS nanocomposite. Sulfate Reducing Bacteria (SRB) are derived from oil field, wherein the culture medium of the SRB comprises K2HPO4,MgSO4NaCl, vitamin C, yeast extract, (NH)4)2Fe(SO4)2Sodium lactate. Cu-Fe (OH)2FeS exhibits a nanosheet structure, Cu-Fe (OH) being detected2The deposition amount of the FeS material on the surface of the polyester fiber cloth of the supporting substrate is 25mg cm-2. Example 3
Preparation of copper-iron nanocomposite by microbial corrosion process, said copper-iron nanocomposite being Cu-Fe (OH)2-FeS; the copper-iron nano composite is of a nano-sheet structure; the Cu-Fe (OH)2The FeS material is deposited on the surface of the polyester fiber cloth of the supporting substrate, and the deposition amount is 80mg cm-2。
The method for preparing the copper-iron nano composite material by the microbial corrosion method comprises the following steps:
taking polyester fiber cloth as a supporting substrate, cleaning the supporting substrate by using neutral deionized water, and then placing the supporting substrate in SnCl2·2H2In a mixed solution of O and HCl (concentration 10mg/mL and 0.1M, respectively), the mixture was gently stirred at room temperature and sensitized for 15 min. Then soaking the sensitized polyester fiber cloth in PdCl2Soaking in mixed solution of HCl (concentration of 0.1mg/mL and 0.02M) for 10min to complete activation; rinsing the surface-activated polyester fiber cloth with deionized water, drying under nitrogen flow while avoiding contamination, and then washing with CuSO4·5H2O、Na3C6H5O7、NH4Cl、10％NaOH、NaH2PO2·H2And soaking the cloth in the mixed solution of O for 10min to obtain the polyester fiber cloth with Cu deposition.
Soaking the polyester fiber cloth with Cu deposition into a reagent bottle containing 33% Sulfate Reducing Bacteria (SRB), and culturing at 37 deg.C under oxygen-free atmosphere for 14 days to obtain Cu-Fe (OH) supported by the polyester fiber cloth2-a FeS nanocomposite. Sulfate Reducing Bacteria (SRB) are derived from oil field, and sulfate is also contained in the SRBThe culture medium of the original bacteria comprises K2HPO4,MgSO4NaCl, vitamin C, yeast extract, (NH)4)2Fe(SO4)2Sodium lactate. Cu-Fe (OH)2-FeS exhibits a nanosheet structure. Measurement of Cu-Fe (OH)2The deposition amount of the FeS material on the surface of the polyester fiber cloth of the supporting substrate is 80mg cm-2。
Example 4
The polyester cloth prepared in example 1 was supported by Cu-Fe (OH)2the-FeS composite electrode is applied to a hydrogen peroxide electrochemical sensor, and has high sensitivity and low detection limit. Constructing a three-electrode system, wherein the working electrode is a polyester fiber cloth supported Cu-Fe (OH)2The FeS nano composite electrode, the auxiliary electrode, the reference electrode and the test solution are respectively a platinum electrode, a saturated calomel electrode and a PBS buffer solution, and the timing current curve is measured. As shown in fig. 3, as the concentration of hydrogen peroxide increases, the current gradually increases, showing a step-up; as shown in fig. 4, the linear range is good. The above results show that [ Cu-CAT ] of carbon paper supported fractal structure]Metal organic frame polyester fiber cloth support Cu-Fe (OH)2the-FeS nano composite electrode is applied to a hydrogen peroxide electrochemical sensor, and has good electrochemical sensing performance, the linear range is 5nM-8.2mM, and the detection limit is 2 nM.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A method for preparing a copper-iron nano composite material by a microbial corrosion method is characterized by comprising the following steps:
(1) adopting polyester fiber cloth as a supporting substrate, and cleaning the polyester fiber cloth by using neutral deionized water;
(2) configuration of SnCl2·2H2O and HCl mixed solution, polyester fiber in the step (1) is arranged in the solution, and the solution is stirred at room temperature and the surface of the solution is sensitized;
(3) soaking the sensitized polyester fiber cloth obtained in the step (2) in PdCl2And HCl to complete surface activation;
(4) rinsing the activated polyester fiber cloth obtained in the step (3) by using deionized water, and keeping the activated polyester fiber cloth dry under nitrogen flow, thereby avoiding pollution;
(5) the activated polyester fiber cloth obtained in the step (4) is coated on CuSO4·5H2O、Na3C6H5O7、NH4Cl, 10% NaOH and NaH2PO2·H2Soaking the mixture of DI water and O at room temperature to obtain polyester fiber cloth with Cu deposition;
(6) and (3) soaking the polyester fiber cloth with the Cu deposition obtained in the step (5) into a reagent bottle containing 33% of Sulfate Reducing Bacteria (SRB), and culturing for 5-14 days at 37 ℃ in an oxygen-free atmosphere to obtain the copper-iron nano composite material.
2. The method of preparing a copper-iron nanocomposite as claimed in claim 2, wherein: the mechanical strength of the support substrate is 4-7 cN/dex.
3. The method of preparing a copper-iron nanocomposite material according to claim 1, wherein: the SnCl of the step (2)2·2H2The concentrations of O and HCl are 5-20mg/mL and 0.05-0.15M respectively, and the stirring time is 10-20 min.
4. The method of preparing a copper-iron nanocomposite as claimed in claim 1, wherein: PdCl in the step (3)2And HCl concentrations of 0.05-0.15mg/mL and 0.01-0.05M, respectively; the soaking time is 5-15 min.
5. The method of preparing a copper-iron nanocomposite as claimed in claim 1, wherein: the soaking time in the step (5) is 10-30 min.
6. A copper-iron nanocomposite prepared by the process according to any one of claims 1 to 5, wherein: comprising a support liningThe copper-iron nano composite is further included, and the supporting substrate is polyester fiber cloth; the copper-iron nano composite is Cu-Fe (OH)2-FeS in nanosheet morphology.
7. The copper-iron nanocomposite of claim 6 wherein: the copper iron nanocomposite is deposited on the surface of the supporting substrate. The deposition amount is 10-100mg cm-2。
8. A copper-iron nanocomposite as claimed in claim 7 as H2O2Use of an electrochemical sensor.
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| CN101092247A (en) * | 2007-04-28 | 2007-12-26 | 首都师范大学 | Method for preparing non-crystalline Nano composite material of Nano titania of nickel, phosphor, chrome |
| CN110951818A (en) * | 2019-12-30 | 2020-04-03 | 华南理工大学 | Method for efficiently biologically synthesizing nano pyrite SM-FeS material, synthesized nano pyrite SM-FeS material and application |
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