CN109518207B - A kind of efficient oxygen evolution reaction elctro-catalyst and preparation method thereof - Google Patents
A kind of efficient oxygen evolution reaction elctro-catalyst and preparation method thereof Download PDFInfo
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- CN109518207B CN109518207B CN201811564746.XA CN201811564746A CN109518207B CN 109518207 B CN109518207 B CN 109518207B CN 201811564746 A CN201811564746 A CN 201811564746A CN 109518207 B CN109518207 B CN 109518207B
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Abstract
The invention belongs to natural biologies, the combination that conventional metals are corroded and Modern electrochemistry energy technology is multi-field, more particularly, to a kind of efficient oxygen evolution reaction elctro-catalyst and preparation method thereof.Efficient oxygen is prepared using microbiologic(al) corrosion engineering, electrode is precipitated, on the one hand chemical attack is carried out to corrosion substrate using culture medium solution, on the other hand using microorganism itself there is the metabolite of oxygen evolution reaction (OER) catalytic activity to be coupled with corrosion substrate, to be modified to substrate material surface, generate the corrosive biological film with efficient OER catalytic activity, as oxygen evolution reaction catalyst, oxygen precipitation efficiency is greatly promoted, and is suitable for industrial applications.
Description
Technical field
The invention belongs to natural biologies, the combination that conventional metals are corroded and Modern electrochemistry energy technology is multi-field, more
In particular it relates to a kind of efficient oxygen evolution reaction elctro-catalyst and preparation method thereof.
Background technique
With being continuously increased to clean energy resource demand, the fungible energy source that development efficiency is high, at low cost and environmental-friendly
Conversion and storage system receive significant attention.Oxygen evolution reaction (OER) elctro-catalyst is undoubtedly the key of various renewable energy
Technology, including metal-air battery and electrolysis water technology etc..To solve noble metal (Pt, Pd, Au, Ru, Ir etc.) catalyst
Cost and its problem of unsustainable development, Metal Substrate oxide/hydroxide has abundant, cheap, easily preparation, pattern can
Control, higher OER catalytic activity the advantages that and cause the extensive research interest of people.
Currently, the preparation method of Metal Substrate oxide/hydroxide OER elctro-catalyst mainly passes through electro-deposition or hydro-thermal
Method, however, these bottom-to-top methods need complicated precursor solution or stringent synthesis condition (such as high temperature, pressure or
Additional electric power input), to hinder the large-scale application of such elctro-catalyst.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of microbiologic(al) corrosion engineerings to be prepared into
Efficient oxygen evolution reaction elctro-catalyst arrived and preparation method thereof uses microbiologic(al) corrosion engineering to prepare efficient oxygen precipitation electricity and urges
On the one hand agent carries out chemical attack to corrosion substrate using culture medium solution, on the other hand has oxygen using microorganism itself
The metabolite of evolution reaction (OER) catalytic activity is coupled with corrosion substrate, so that substrate material surface is modified,
The corrosive biological film with efficient OER catalytic activity is generated, oxygen evolution reaction elctro-catalyst is obtained, thus solves the prior art
Metal Substrate oxide/hydroxide OER elctro-catalyst preparation method is complicated, technical problem of synthesis condition harshness.
To achieve the above object, according to one aspect of the present invention, it provides a kind of microbiologic(al) corrosion engineering and prepares oxygen analysis
The method for reacting elctro-catalyst out, in the culture medium solution containing sulfate reducing bacteria, sulfate radical and metal ion, to corrosion
Base material carries out chemical attack and microbiologic(al) corrosion；Wherein:
The own metabolism product of the sulfate reducing bacteria generates gold in conjunction with the metal ion in the culture medium solution
Belong to sulfide；
Metal sulfide doping enters in the base material through chemical attack, generates in corrosion substrate material surface
The corrosive biological film of metal sulfide doping, obtains the oxygen evolution reaction elctro-catalyst.
Preferably, the corrosion base material is in nickel foam, nickel particle, nickel nano wire, stainless steel, carbon steel and carbon cloth
It is one or more.
Preferably, the corrosion base material is gone using preceding using the one or more of hydrochloric acid, nitric acid, ethyl alcohol and acetone
Except the oxidation film or impurity on its surface.
Preferably, the metal ion in the culture medium solution is Ni2+、Fe2+、Fe3+、Co2+And Mn2+One of or it is more
Kind, the concentration of the metal ion is not higher than 0.01mol/L.
Preferably for the corrosion base material every square centimeter, contain volume fraction in the culture medium solution
For the sulfate reduction bacterium stoste no more than 80%, in the sulfate reduction bacterium stoste concentration of sulfate reducing bacteria be 8 ×
104cell/mL。
Preferably, the concentration of the sulfate radical in the culture medium solution is not higher than 0.01mol/L.
Preferably, the chemical attack and microbiologic(al) corrosion condition are as follows: rotten under the sealing oxygen-free environment not higher than 37 DEG C
Erosion is no more than 21 days.
Other side according to the invention provides a kind of oxygen evolution reaction that microbiologic(al) corrosion engineering is prepared electricity
Catalyst comprising corrosion base material and the corrosive biological film formed in the corrosion substrate material surface, in which:
The corrosion base material be one of nickel foam, nickel particle, nickel nano wire, stainless steel, carbon steel and carbon cloth or
It is a variety of；
The corrosive biological film includes the corrosion base material through chemical attack, further includes itself of sulfate reducing bacteria
The metal sulfide that metabolite generates in conjunction with metal ion, and metal sulfide doping enters through described through chemical attack
Corrosion base material in；
The metal ion is Ni2+、Fe2+、Fe3+、Co2+And Mn2+One of or it is a variety of；
The corrosive biological film thickness is 50-300nm.
Preferably, the corrosion base material is nickel foam or stainless steel.
Preferably, the corrosion base material through chemical attack is metal based hybroxide.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) oxygen precipitation elctro-catalyst is prepared using microbiologic(al) corrosion engineering the invention proposes a kind of, using microorganism corruption
Erosion engineering prepares efficient oxygen and electrode is precipitated, and on the one hand carries out chemical attack to corrosion substrate using culture medium solution, on the other hand
Using microorganism itself there is the metabolite of OER catalytic activity to be coupled with corrosion substrate, which enters chemistry
In the lattice of substrate surface material after corrosion, to be modified to substrate material surface, generating, there is efficient OER catalysis to live
Property corrosive biological film, elctro-catalyst, which is precipitated, as oxygen uses, oxygen precipitation efficiency is greatly improved, suitable for industrial applications.
(2) when the present invention is using different corrosion base materials, SRB is to the extent of corrosion of base material and elctro-catalyst
It is related to analyse oxygen efficiency.Extent of corrosion is bigger, and analysis oxygen efficiency is increased more significant.Elctro-catalyst made from method of the invention is preferred
Using foam nickel base and contain Fe2+Culture medium, corrosive biological film group obtained become Ni (Fe) (OH)2-FeS。
(3) oxygen precipitation elctro-catalyst preparation method proposed by the present invention is simple, easy to operate, environmental-friendly, realizes the energy
Reproducible utilization.
Detailed description of the invention
Fig. 1 be embodiment 1 in sulfate reducing bacteria corrosion foam nickel electrode surface corrosion biomembrane pattern and
Mapping figure；Wherein Fig. 1 (a) is the scanning electron microscope (SEM) photograph of electrode surface erosion biomembrane；Fig. 1 (b) is electrode surface erosion
The TEM of biomembrane schemes；Fig. 1 (c) and (d) are that the HRTEM of electrode surface erosion biomembrane schemes；Fig. 1 (e) is corrosive biological film
The mapping of Ni, O, Fe, S element on surface is distributed；
Curve 1,2,3,4 in Fig. 2 is respectively commercial iridium dioxide in embodiment 1, and blank nickel foam, nickel foam-is without SRB
The linear polarisation curves of corrosion and nickel foam-SRB corroding electrode；
Fig. 3 is nickel foam-SRB corroding electrode in embodiment 1 respectively in 10mA/cm2And 100mA/cm2Under current density
Time-measuring electric potential curve；
Fig. 4 is that nickel foam corrosion in the SRB (0%, 23%, 33%, 65%) of different volumes score is different in embodiment 2
The linear polarisation curves of time；Wherein Fig. 4 (a), Fig. 4 (b), Fig. 4 (c), Fig. 4 (d) and Fig. 4 (e) be respectively corrode 3 days, 7 days,
10 days, 14 days and 17 days linear polarisation curves；Fig. 4 (f) is that nickel foam corrodes different time in the SRB of different volumes score
Linear polarisation curves in 10mA/cm2Corresponding overpotential under current density；
Fig. 5 is the surface SEM that foam nickel electrode corrodes different time in the SRB that volume fraction is 33% in embodiment 3
Figure；Wherein blank nickel foam, SRB corrode 3 days, 7 respectively by Fig. 5 (a), Fig. 5 (b), Fig. 5 (c), Fig. 5 (d), Fig. 5 (e) and Fig. 5 (f)
It, 10 days, the electrode surface SEM figures of 14 days and 17 days；
Fig. 6 is the linear polarisation curves that different base material corrodes front and back using SRB in embodiment 4；Wherein in Fig. 6 (a)
Curve 1 and 2 is respectively the linear polarisation curves of the stainless steel after blank stainless steel and SRB corrosion；Curve 1 and 2 point in Fig. 6 (b)
Not Wei blank carbon steel and SRB corrosion after carbon steel linear polarisation curves；In Fig. 6 (c) curve 1 and 2 be respectively blank carbon cloth and
The linear polarisation curves of carbon cloth after SRB corrosion.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The method that microbiologic(al) corrosion engineering provided by the invention prepares oxygen evolution reaction elctro-catalyst are as follows: containing sulfate
In the culture medium solution of reducing bacteria, sulfate radical and metal ion, chemical attack and microbiologic(al) corrosion are carried out to corrosion base material,
The own metabolism product of the sulfate reducing bacteria generates metal sulfide in conjunction with the metal ion in culture medium solution, mixes
It is miscellaneous into the base material through chemical attack, it is raw in the corrosivity that corrosion substrate material surface generates metal sulfide doping
Object film obtains the oxygen evolution reaction elctro-catalyst.
In some embodiments, the corrosion base material is nickel foam, nickel particle, nickel nano wire, stainless steel, carbon steel and carbon
One of cloth is a variety of.
In some embodiments, the corrosion base material using preceding one kind using hydrochloric acid, nitric acid, ethyl alcohol and acetone or
A variety of oxidation films or impurity for removing its surface.
In some embodiments, the metal ion in the culture medium solution is Ni2+、Fe2+、Fe3+、Co2+And Mn2+In one
Kind is a variety of.The concentration of the metal ion is not higher than 0.01mol/L, preferably 0.002mol/L.
In some embodiments, sulfate radical increases for the metabolism of SRB in the culture medium solution, and SRB can be by sulfate radical also
It originally is S2-.The concentration of sulfate radical is not higher than 0.01mol/L, preferably 0.006mol/L.
In some embodiments, for the corrosion base material every square centimeter, contain body in the culture medium solution
Fraction is the sulfate reduction bacterium stoste no more than 80%, the concentration of sulfate reducing bacteria in the sulfate reduction bacterium stoste
It is 8 × 104cell/mL。
Any sulfate reducing bacteria can be selected in sulfate reducing bacteria SRB of the present invention, for example it can be from oil field dirt
It is separated in water or soil, belongs to the SRB bacterial strain of Desulfotomaculum.
In some embodiments, the Latin literary fame of the SRB bacterium is Desulfotomaculum nigrificans, deposit number
It in ingredient is K to the bacterium for ATCC 135412HPO40.01g/L, MgSO40.2g/L, (NH4)2Fe(SO4)20.2g/L,
NaCl 10g/L, yeast extract 1g/L, Victoria C 0.1g/L are cultivated in the culture medium of sodium lactate 4g/L, until concentration reaches 8
×104Cell/mL (according to MPN method carry out cell count), then according to the present invention claims volume ratio be added to the training
It supports in based sols.
In some embodiments, chemistry and microbiologic(al) corrosion condition are as follows: corrode under the sealing oxygen-free environment not higher than 37 DEG C
No more than 21 days.This is mainly due to SRB to belong to anaerobic type microorganism, and it entirely grows week in the environment not higher than 37 DEG C
Phase is 21 days.
Present invention provides a kind of oxygen evolution reaction elctro-catalysts that microbiologic(al) corrosion engineering is prepared comprising rotten
The corrosive biological film for losing base material and being formed in the corrosion substrate material surface, in which:
The corrosion base material be one of nickel foam, nickel particle, nickel nano wire, stainless steel, carbon steel and carbon cloth or
It is a variety of；The corrosive biological film thickness is 50-300nm；The corrosive biological film includes the corrosion substrate material through chemical attack
Material, the metal sulfide that also the own metabolism product including sulfate reducing bacteria generates in conjunction with metal ion, and the metal sulphur
Compound doping enters through in the corrosion base material through chemical attack；The metal ion is Ni2+、Fe2+、Fe3+、Co2+With
Mn2+One of or it is a variety of.
Oxygen evolution reaction elctro-catalyst that the present invention is prepared using microbiologic(al) corrosion engineering is compared with the existing technology
Metal Substrate oxide/hydroxide OER elctro-catalyst has higher oxygen evolution reaction efficiency.For oxygen evolution reaction, reacted
Shown in journey following (1)-(4):
Wherein * represents an active site of catalyst surface, and * OH, * O and * OOH respectively represent the chemistry of OH, O and OOH
Absorption.
For the oxygen evolution reaction elctro-catalyst that the present invention obtains, why there is higher oxygen evolution reaction efficiency, be
Because forming the rate controlling step that * OOH is OER reaction on catalyst in reaction process (3), on the one hand, the gold in culture medium
Belong to the corresponding metallic atom of ion and S atom bonding will increase the amount of electrostatic charge of the metallic atom, while enhancing the metallic atom
And the combination of * OOH causes catalyst to have lower overpotential for oxygen evolution；On the other hand, metallicity corrosion substrate chemical attack produces
Raw OH-And S2-Adjustable transition metal d orbital electron promotes elctro-catalyst that can complete electro-catalysis under lower current potential
Process.
Metallic nickel or stainless steel itself are used as OER elctro-catalyst or electrode, compared with carbon steel or carbon cloth, have higher oxygen
Precipitation efficiency, therefore, after carrying out corrosion to corrosion base material using microbial corrosion method of the present invention and being modified, electricity is urged
It is different to change the increased amplitude of efficiency.For the stainless steel base containing Fe and Ni element, its overpotential for oxygen evolution after SRB corrosion
Reduce 20mV；For the carbon steel substrates containing Fe and C element, its overpotential for oxygen evolution reduces 60mV after SRB corrosion；And for containing only
The carbon cloth substrate of C element, its overpotential for oxygen evolution reduces 95mV after SRB corrosion, shows SRB to the extent of corrosion of base material and electricity
The analysis oxygen efficiency of catalyst is related.Extent of corrosion is bigger, and analysis oxygen efficiency is increased more significant.Therefore, method of the invention is made
Elctro-catalyst preferably use foam nickel base and contain Fe2+Culture medium, corrosive biological film group obtained become Ni (Fe)
(OH)2-FeS.When as elctro-catalyst, since Fe atom and FeS are doped into the lattice of Ni, to have nickel foam more excellent for it
Different OER electrocatalysis characteristic.
The oxygen evolution reaction elctro-catalyst that the present invention is prepared according to the method described above uses nickel foam, stainless steel, carbon steel
Or carbon cloth as substrate when, can be directly used as the use of oxygen evolution reaction electrode, and when using nickel particle, nickel nano wire as rotten
When losing base material, the elctro-catalyst being prepared is coated on glass-carbon electrode, is used as oxygen evolution reaction electrode.
The following are embodiments:
Embodiment 1
A kind of efficient oxygen precipitation electrode comprising corrosion base material and the corrosivity formed in corrosion substrate material surface
Biomembrane, wherein corrosion base material is nickel foam, the group of corrosive biological film becomes Ni (Fe) (OH)2- FeS, wherein Ni
(Fe)(OH)2For the product of base material chemical attack, the own metabolism product S of sulfate reducing bacteria2-With metal cations Fe2+Knot
At metal sulfide, sulphur atom and iron atom doping in the metal sulfide enter through the corrosion through chemical attack for symphysis
In base material, the two couples to obtain the corrosive biological film.
The method that electrode is precipitated in the efficient oxygen is prepared using microbiologic(al) corrosion engineering, comprising the following steps:
(1) for corrosion base material every square centimeter, it is added into the culture of the microorganism containing volume fraction 33%
In based sols；
The corrosion base material is nickel foam；The microorganism is sulfate reduction bacterium stoste, the sulfate reduction
The concentration of sulfate reducing bacteria is 8 × 10 in bacterium stoste4cell/mL；Contain Fe in culture medium solution2+, Fe2+Concentration be
0.002mol/L, sulfate concentration 0.006mol/L.
(2) the corrosion base material of the culture medium containing microorganism in step (1) is put into the reagent bottle of 250mL, by it
10day is cultivated in 37 DEG C of constant temperature and humidity incubator obtains the material of microbiologic(al) corrosion；
The reagent bottle is in the oxygen-free environment of sealing.
The Latin literary fame for the SRB bacterium that the present embodiment uses is Desulfotomaculum nigrificans, deposit number
It in ingredient is K to the bacterium for ATCC 135412HPO40.01g/L, MgSO40.2g/L, (NH4)2Fe(SO4)20.2g/L,
NaCl 10g/L, yeast extract 1g/L, Victoria C 0.1g/L are cultivated in the culture medium of sodium lactate 4g/L, until concentration reaches 8
×104Cell/mL (according to MPN method carry out cell count), then according to the present invention claims volume ratio be added to the training
It supports in based sols.
Fig. 1 is that the SEM of nickel foam-SRB corroding electrode surface corrosion biomembrane provided in this embodiment schemes, TEM,
HRTEM and corresponding element mapping figure.Wherein Fig. 1 (a) is the scanning electron microscope (SEM) photograph of electrode surface erosion biomembrane；Fig. 1
(b) scheme for the TEM of electrode surface erosion biomembrane；Fig. 1 (c) and (d) are that the HRTEM of electrode surface erosion biomembrane schemes；
Fig. 1 (e) is the mapping distribution of Ni, O, Fe, S element of corrosive biological film surface；It can be seen that bubble provided in this embodiment
The corrosive biological film on foam nickel-SRB corroding electrode surface is that uniform nano-layer structure is deposited on the skeleton of nickel foam,
HRTEM shows that the corrosive biological film corresponds to α-Ni (OH)2Lattice information, element mapping figure shows that Fe and S element is uniform
Be distributed on the corrosive biological film, show Fe and S element doping into α-Ni (OH)2Lattice in.
Linear polarisation curves are carried out on electrochemical workstation using three-electrode system, test solution is 1mol/L KOH,
Its potential value is relative to standard hydrogen electrode (RHE).Different electrodes (commercial iridium dioxide, blank nickel foam, nickel foam-nothing
SRB corrosion and nickel foam-SRB corroding electrode provided in this embodiment) linear polarisation curves such as Fig. 2 in curve 1,2,3,4
Shown, Different electrodes are in 10mA/cm2The overpotential size order at place are as follows: blank nickel foam (400mV) > commercialization iridium dioxide
(370mV) > nickel foam-corrodes (300mV) > nickel foam provided in this embodiment-SRB corroding electrode (190mV) without SRB, as a result
Illustrate the overpotential for oxygen evolution of electrode after SRB corrodes nickel foam than commercial iridium dioxide and blank nickel foam and the bubble corroded without SRB
Foam nickel is lower, and nickel foam of the analysis oxygen electric current relative to commercial iridium dioxide and blank nickel foam and without SRB corrosion significantly increases.
Nickel foam-SRB corroding electrode provided in this embodiment is surveyed in 1mol/LKOH solution using time-measuring electric potential curve
It is tried respectively in 10mA/cm2And 100mA/cm2Stability under current density, stability curve is as shown in figure 3, can see
Out, the foam nickel electrode after being corroded using SRB is in 10mA/cm2(oxygen evolution potential~1.42V) and 100mA/cm2(oxygen evolution potential~
Under current density 1.53V) can at least stable 16h, show that the electrode can industrially be used for high current electrolysis water.
Embodiment 2
A kind of efficient oxygen precipitation electrode comprising corrosion base material and the corrosivity formed in corrosion substrate material surface
Biomembrane, wherein corrosion base material is nickel foam, the group of corrosive biological film becomes Ni (Fe) (OH)2-FeS.Wherein Ni
(Fe)(OH)2For the product of base material chemical attack, the own metabolism product S of sulfate reducing bacteria2-With metal cations Fe2+Knot
At metal sulfide, sulphur atom and iron atom doping in the metal sulfide enter through the corrosion through chemical attack for symphysis
In base material, the two couples to obtain the corrosive biological film.
The method that electrode is precipitated in efficient oxygen is prepared using microbiologic(al) corrosion engineering, comprising the following steps:
(1) for corrosion base material every square centimeter, it is added into the microorganism of the 0%-65% containing volume fraction
In culture medium solution；
The corrosion base material is nickel foam；The microorganism is sulfate reduction bacterium stoste, the sulfate reduction
The concentration of sulfate reducing bacteria is 8 × 10 in bacterium stoste4cell/mL；Contain Fe in culture medium solution2+, Fe2+Concentration be 0-
0.01mol/L, sulfate concentration 0-0.01mol/L.
(2) the corrosion base material of the culture medium containing microorganism in step (1) is put into the reagent bottle of 250mL, by it
0day-17day is cultivated in 37 DEG C of constant temperature and humidity incubator obtains the material of microbiologic(al) corrosion；
The reagent bottle is in the oxygen-free environment of sealing.
The Latin literary fame for the SRB bacterium that the present embodiment uses is Desulfotomaculum nigrificans, deposit number
It in ingredient is K to the bacterium for ATCC 135412HPO40.01g/L, MgSO40.2g/L, (NH4)2Fe(SO4)20.2g/L,
NaCl 10g/L, yeast extract 1g/L, Victoria C 0.1g/L are cultivated in the culture medium of sodium lactate 4g/L, until concentration reaches 8
×104Cell/mL (according to MPN method carry out cell count), then according to the present invention claims volume ratio be added to the training
It supports in based sols.
Linear polarisation curves are carried out on electrochemical workstation using three-electrode system, test solution is 1mol/L KOH,
Its potential value is relative to standard hydrogen electrode (RHE).Nickel foam corrodes the line of different time in the SRB of different volumes score
Property polarization curve as shown in the graph in fig. 4, wherein Fig. 4 (a), Fig. 4 (b), Fig. 4 (c), Fig. 4 (d) and Fig. 4 (e) be respectively corrode
3 days, 7 days, 10 days, 14 days and 17 days linear polarisation curves；Fig. 4 (f) is that nickel foam is corroded in the SRB of different volumes score
The linear polarisation curves of different time are in 10mA/cm2Corresponding overpotential under current density；It can be seen that nickel foam is by simple
Chemical attack after its OER performance increase, and its OER performance further increases after SRB corrodes.For different volumes score
SRB corrosion, volume fraction be 33% SRB corrosion after nickel foam have optimal OER electro catalytic activity.For different
SRB etching time, nickel foam OER electro catalytic activity of electrode after SRB corrodes first increases to be reduced afterwards, when etching time is 10
It when, the OER electro catalytic activity of SRB corroding electrode is best.
Embodiment 3
A kind of efficient oxygen precipitation electrode comprising corrosion base material and the corrosivity formed in corrosion substrate material surface
Biomembrane, wherein corrosion base material is nickel foam, the group of corrosive biological film becomes Ni (Fe) (OH)2-FeS.Wherein Ni
(Fe)(OH)2For the product of base material chemical attack, the own metabolism product S of sulfate reducing bacteria2-With metal cations Fe2+Knot
At metal sulfide, sulphur atom and iron atom doping in the metal sulfide enter through the corrosion through chemical attack for symphysis
In base material, the two couples to obtain the corrosive biological film.
The method that electrode is precipitated in efficient oxygen is prepared using microbiologic(al) corrosion engineering, comprising the following steps:
(1) for corrosion base material every square centimeter, it is added into the culture of the microorganism containing volume fraction 33%
In based sols；
The corrosion base material is nickel foam；The microorganism is sulfate reduction bacterium stoste, the sulfate reduction
The concentration of sulfate reducing bacteria is 8 × 10 in bacterium stoste4cell/mL；Contain Fe in culture medium solution2+, Fe2+Concentration be
0.002mol/L, sulfate concentration 0.006mol/L.
(2) the corrosion base material of the culture medium containing microorganism in step (1) is put into the reagent bottle of 250mL, by it
0day-17day is cultivated in 37 DEG C of constant temperature and humidity incubator obtains the material of microbiologic(al) corrosion；
The reagent bottle is in the oxygen-free environment of sealing.
The Latin literary fame for the SRB bacterium that the present embodiment uses is Desulfotomaculum nigrificans, deposit number
It in ingredient is K to the bacterium for ATCC 135412HPO40.01g/L, MgSO40.2g/L, (NH4)2Fe(SO4)20.2g/L,
NaCl 10g/L, yeast extract 1g/L, Victoria C 0.1g/L are cultivated in the culture medium of sodium lactate 4g/L, until concentration reaches 8
×104Cell/mL (according to MPN method carry out cell count), then according to the present invention claims volume ratio be added to the training
It supports in based sols.
Fig. 5 is that nickel foam provided in this embodiment corrodes electrode table after different time in the SRB that volume fraction is 33%
The SEM of face corrosive biological film schemes.Wherein Fig. 5 (a), Fig. 5 (b), Fig. 5 (c), Fig. 5 (d), Fig. 5 (e) and Fig. 5 (f) difference blank
Nickel foam, SRB corrode 3 days, 7 days, 10 days, 14 days and 17 days electrode surface SEM figures；It can be seen that nickel foam is rotten in SRB
Electrode surface generates one layer of corrosive biological film after erosion, and when etching time is 10 days, electrode surface is compared to other corrosion
The corrosive biological film that time generates is more loose.
Embodiment 4
A kind of efficient oxygen precipitation electrode comprising corrosion base material and the corrosivity formed in corrosion substrate material surface
Biomembrane, wherein corrosion base material is stainless steel, carbon steel or carbon cloth, the own metabolism product S of sulfate reducing bacteria2-With metal
Ion Fe2+In conjunction with metal sulfide is generated, the sulphur atom and iron atom doping in the metal sulfide enter through described through chemistry
Coupling obtains the corrosive biological film in the corrosion base material of corrosion.
The method that electrode is precipitated in efficient oxygen is prepared using microbiologic(al) corrosion engineering, comprising the following steps:
(1) for corrosion base material every square centimeter, it is added into the culture of the microorganism containing volume fraction 33%
In based sols；
The corrosion base material is respectively stainless steel, carbon steel and carbon cloth；The microorganism is sulfate reduction bacterium stoste,
The concentration of sulfate reducing bacteria is 8 × 10 in the sulfate reduction bacterium stoste4cell/mL；Contain Fe in culture medium solution2+, Fe2+
Concentration be 0.002mol/L, sulfate concentration 0.006mol/L.
(2) the corrosion base material of the culture medium containing microorganism in step (1) is put into the reagent bottle of 250mL, by it
0day-17day is cultivated in 37 DEG C of constant temperature and humidity incubator obtains the material of microbiologic(al) corrosion；
The reagent bottle is in the oxygen-free environment of sealing.
Linear polarisation curves are carried out on electrochemical workstation using three-electrode system, test solution is 1mol/L KOH,
Its potential value is relative to standard hydrogen electrode (RHE).Different electrodes (blank stainless steel, blank carbon steel, blank carbon cloth, this reality
Stainless steel-SRB the corroding electrode of example offer, carbon steel-SRB corroding electrode and carbon cloth-SRB corroding electrode are provided) linear polarization it is bent
Line as shown in fig. 6, wherein in Fig. 6 (a) Different electrodes in 10mA/cm2The overpotential size order at place are as follows: blank stainless steel
(340mV) > stainless steel provided in this embodiment-SRB corroding electrode (320mV)；Different electrodes are in 10mA/cm in Fig. 6 (b)2Place
Overpotential size order are as follows: blank carbon steel (430mV) > carbon steel provided in this embodiment-SRB corroding electrode (370mV)；Wherein
Different electrodes are in 10mA/cm in Fig. 6 (c)2The overpotential size order at place are as follows: blank carbon cloth (605mV) > provided in this embodiment
Carbon cloth-SRB corroding electrode (510mV) as a result illustrates (stainless steel, carbon steel and carbon cloth) its correspondence electricity after SRB corrosion different base
The overpotential for oxygen evolution of pole is lower, and analysis oxygen electric current increases.
Embodiment 5
A kind of efficient oxygen precipitation electrode comprising corrosion base material and the corrosivity formed in corrosion substrate material surface
Biomembrane, wherein corrosion base material is nickel foam, the group of corrosive biological film becomes Ni (Co) (OH)2-CoS.Wherein Ni
(Co)(OH)2For the product of base material chemical attack, the own metabolism product S of sulfate reducing bacteria2-With metal ion CO 2+Knot
At metal sulfide, sulphur atom and cobalt atom doping in the metal sulfide enter through the corrosion through chemical attack for symphysis
In base material, the two couples to obtain the corrosive biological film.
The method that electrode is precipitated in the efficient oxygen is prepared using microbiologic(al) corrosion engineering, comprising the following steps:
(1) for corrosion base material every square centimeter, it is added into the culture of the microorganism containing volume fraction 33%
In based sols；
The corrosion base material is nickel foam；The microorganism is sulfate reduction bacterium stoste, the sulfate reduction
The concentration of sulfate reducing bacteria is 8 × 10 in bacterium stoste4cell/mL；Contain Co in culture medium solution2+, Co2+Concentration be
0.002mol/L, sulfate concentration 0.006mol/L.
(2) the corrosion base material of the culture medium containing microorganism in step (1) is put into the reagent bottle of 250mL, by it
10day is cultivated in 37 DEG C of constant temperature and humidity incubator obtains the material of microbiologic(al) corrosion；
The reagent bottle is in the oxygen-free environment of sealing.
Embodiment 6
A kind of efficient oxygen precipitation electrode comprising corrosion base material and the corrosivity formed in corrosion substrate material surface
Biomembrane, wherein corrosion base material is nickel foam, the group of corrosive biological film becomes Ni (Mn) (OH)2-MnS.Wherein Ni
(Mn)(OH)2- MnS is the product of base material chemical attack, the own metabolism product S of sulfate reducing bacteria2-With metal ion
Mn 2+In conjunction with metal sulfide is generated, the sulphur atom and manganese atom doping in the metal sulfide enter through described through chemical attack
Corrosion base material in, the two couples to obtain the corrosive biological film.
The method that electrode is precipitated in the efficient oxygen is prepared using microbiologic(al) corrosion engineering, comprising the following steps:
(1) for corrosion base material every square centimeter, it is added into the culture of the microorganism containing volume fraction 33%
In based sols；
The corrosion base material is nickel foam；The microorganism is sulfate reduction bacterium stoste, the sulfate reduction
The concentration of sulfate reducing bacteria is 8 × 10 in bacterium stoste4cell/mL；Contain Mn in culture medium solution2+, Mn2+Concentration be
0.002mol/L, sulfate concentration 0.006mol/L.
(2) the corrosion base material of the culture medium containing microorganism in step (1) is put into the reagent bottle of 250mL, by it
10day is cultivated in 37 DEG C of constant temperature and humidity incubator obtains the material of microbiologic(al) corrosion；
The reagent bottle is in the oxygen-free environment of sealing.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (9)
1. a kind of method that microbiologic(al) corrosion engineering prepares oxygen evolution reaction elctro-catalyst, which is characterized in that containing sulfate
In the culture medium solution of reducing bacteria, sulfate radical and metal ion, chemical attack and microbiologic(al) corrosion are carried out to corrosion base material；
Wherein:
The own metabolism product of the sulfate reducing bacteria generates metal sulphur in conjunction with the metal ion in the culture medium solution
Compound；
Metal sulfide doping enters in the base material through chemical attack, generates metal in corrosion substrate material surface
The corrosive biological film of sulfide doping, obtains the oxygen evolution reaction elctro-catalyst；
The corrosion base material is one of nickel foam, nickel particle, nickel nano wire, stainless steel and carbon steel or a variety of.
2. the method as described in claim 1, which is characterized in that the corrosion base material using it is preceding using hydrochloric acid, nitric acid,
The oxidation film or impurity on one or more its surface of removal of ethyl alcohol and acetone.
3. the method as described in claim 1, which is characterized in that the metal ion in the culture medium solution is Ni2+、Fe2+、
Fe3+、Co2+And Mn2+One of or it is a variety of, the concentration of the metal ion is not higher than 0.01mol/L.
4. the method as described in claim 1, which is characterized in that described for the corrosion base material every square centimeter
It containing volume fraction is sulfate reduction bacterium stoste no more than 80% in culture medium solution, in the sulfate reduction bacterium stoste
The concentration of sulfate reducing bacteria is 8 × 104cell/mL。
5. the method as described in claim 1, which is characterized in that the concentration of the sulfate radical in the culture medium solution is not higher than
0.01mol/L。
6. the method as described in claim 1, which is characterized in that the chemical attack and microbiologic(al) corrosion condition are as follows: not high
Corrosion is no more than 21 days under 37 DEG C of sealing oxygen-free environment.
7. a kind of oxygen evolution reaction elctro-catalyst that microbiologic(al) corrosion engineering is prepared, which is characterized in that it includes corrosion base
Bottom material and the corrosive biological film formed in the corrosion substrate material surface, in which:
The corrosion base material is one of nickel foam, nickel particle, nickel nano wire, stainless steel and carbon steel or a variety of；
The corrosive biological film includes the corrosion base material through chemical attack, further includes the own metabolism of sulfate reducing bacteria
The metal sulfide that product generates in conjunction with metal ion, and metal sulfide doping enters through the corruption through chemical attack
It loses in base material；
The metal ion is Ni2+、Fe2+、Fe3+、Co2+And Mn2+One of or it is a variety of；
The corrosive biological film thickness is 50-300nm.
8. oxygen evolution reaction elctro-catalyst as claimed in claim 7, which is characterized in that the corrosion base material is nickel foam
Or stainless steel.
9. oxygen evolution reaction elctro-catalyst as claimed in claim 7, which is characterized in that the corrosion substrate through chemical attack
Material is metal based hybroxide.
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