CN106676569B - A kind of preparation method based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly - Google Patents

A kind of preparation method based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly Download PDF

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CN106676569B
CN106676569B CN201710042204.5A CN201710042204A CN106676569B CN 106676569 B CN106676569 B CN 106676569B CN 201710042204 A CN201710042204 A CN 201710042204A CN 106676569 B CN106676569 B CN 106676569B
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nio
photocathodes
temperature
znthpp
bpy
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CN106676569A (en
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那永
韦沛成
周丽
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Harbin Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • C25B1/55—Photoelectrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

A kind of preparation method based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly, it is related to a kind of method for preparing NiO photocathodes.The invention aims to solve the existing method complexity for preparing photocathode and time polar decomghtion water efficiency it is low, produce the slow-footed problem of hydrogen.Preparation method：First, NiO compacted zone precursor liquids are prepared；2nd, NiO compacted zones are prepared；3rd, slurry is prepared；4th, NiO blank is prepared；5th, the NiO photocathodes of ZnTHPP sensitizations are prepared；6th, the NiO photocathodes of ZnTHPP bpy sensitizations are prepared；7th, the NiO photocathodes of ZnTHPP bpy Codmg self assemblies sensitization are prepared；8th, the NiO photocathodes of ZnTPPC sensitizations are prepared；9th, the NiO photocathodes of ZnTPPC bpy sensitizations are prepared；Tenth, it impregnates, clean.The present invention can obtain a kind of preparation method based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly.

Description

A kind of preparation based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly Method
Technical field
The present invention relates to a kind of methods for preparing NiO photocathodes.
Background technology
How a great challenge that sustainable clean energy resource be 21 century scientific circles to be produced, and solar energy conduct A kind of inexhaustible green energy resource, is utilized too by building the photocathode of dye-sensitized solar cells structure Sun can decompose water and generate hydrogen, realize conversion of the solar energy to Hydrogen Energy, can perfectly solve the energy that the mankind are faced at present Crisis and environmental problem.The photosensitizer for decomposing water photocathode currently used for structure has：Compound, porphyrin containing noble ruthenium and its Derivative and pure organic dye etc.；Releasing hydrogen catalyst has：The compound of the elements such as iron content, cobalt, nickel.And to realize photocathode point Solution water efficiency reaches maximization, needs that photosensitizer and catalyst will combine, and acts synergistically.Therefore it is rational Photocathode assembly method is particularly important for structure photocathode.
Invention content
The invention aims to solve the existing method complexity for preparing photocathode and time polar decomghtion water efficiency it is low, produce hydrogen Slow-footed problem, and a kind of preparation method based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly is provided.
A kind of preparation method based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly, specifically by following step Suddenly it completes：
First, NiO compacted zone precursor liquids are prepared：By NiCl2·6H2O, P123, deionized water and absolute ethyl alcohol mixing, stirring It is put into centrifuge and centrifuges after uniformly, removal precipitation, obtained supernatant is NiO compacted zone precursor liquids；
NiCl described in step 12·6H2The mass ratio of O and P123 is 1:(0.5~0.8)；
NiCl described in step 12·6H2O and the mass ratio of deionized water are 1:(1.3~1.66)；
NiCl described in step 12·6H2The mass ratio of O and absolute ethyl alcohol is 1:(3~3.3)；
The centrifugal speed of centrifuge described in step 1 be 7000r/min~9000r/min, centrifugation time for 3min~ 7min；
2nd, NiO compacted zones are prepared：
1., the NiO compacted zone precursor liquids obtained in step 1 are spun to leading for FTO electro-conductive glass by way of spin coating On electric face, it is then placed in dry 3min~7min in the baking oven that temperature is 65 DEG C~80 DEG C again；
2., repeat step 2 1. 1 time~4 times, then 30min~60min is sintered at being 300 DEG C~350 DEG C in temperature, obtain Contain the FTO electro-conductive glass of NiO compacted zones in surface；
Step 2 2. described in surface contain NiO compacted zones on the FTO electro-conductive glass of NiO compacted zones thickness be 50nm ~100nm；
3rd, slurry is prepared：
NiO powders, terpinol and ethyl cellulose are distributed in absolute ethyl alcohol, are aged 2 after stirring evenly at room temperature ~3 days, obtain slurry；
The mass ratio of NiO powders and terpinol described in step 3 is 1:(3.5~4)；
The mass ratio of NiO powders and ethyl cellulose described in step 3 is 1:(0.1~0.2)；
The mass ratio of NiO powders and absolute ethyl alcohol described in step 3 is 1:(3~5)；
NiO powders described in step 3 are the spherical nickel oxide that grain size is 30nm；
The 4th, the slurry obtained in step 3 is printed onto to the surface obtained in step 2 contain using the method for silk-screen printing On the NiO compacted zones of the FTO electro-conductive glass of NiO compacted zones, the thickness of slurry printing is 1 μm~2 μm, and it is 65 to be subsequently placed in temperature DEG C~80 DEG C of baking oven in dry 3min~7min, then be sintered 30min~60min at being 400 DEG C~500 DEG C in temperature, it is natural NiO blank is obtained after cooling；
5th, the NiO photocathodes of ZnTHPP sensitizations are prepared：
1., the NiO blank obtained in step 4 is placed in the baking oven that temperature is 80 DEG C and heats 5min~10min, then soak Bubble 8h~10h in the methanol solution of four (p-hydroxybenzene) zinc porphyrins of a concentration of 10mmol/L~15mmol/L；
2., NiO blank taken out, washed 1 time using absolute ethyl alcohol first, reuse deionized water and wash 1 time；
3., repeat step 5 it is 2. secondary~tetra- times, then be dried at room temperature for 4h, obtain the NiO photocathodes of ZnTHPP sensitizations；
Four (p-hydroxybenzene) zinc porphyrins are in the methanol solution of four (p-hydroxybenzene) zinc porphyrins described in step 5 It is prepared according to following steps：
(1), 6.5g parahydroxyben-zaldehydes are dissolved into 240mL propionic acid, then are heated to reflux at being 140 DEG C in temperature, then 4.3mL pyrroles is added drop-wise in 5min in propionic acid, then 1.5h is heated to reflux at being 140 DEG C in temperature, is cooled to room temperature, then add Enter 100mL methanol, then the cooling and standings 0.5h under ice bath, have violet solid precipitation, then filtered, filter cake is cleaned using methanol It is colourless to cleaning solution, obtain solid matter；Solid matter is dissolved into the mixed liquor of dichloromethane and methanol, stands 12h, then It is filtered, obtains purple crystals, as tetrahydroxy phenyl porphyrin；Dichloromethane in the dichloromethane and the mixed liquor of methanol The volume ratio of alkane and methanol is 1:1；
(2), 0.1064g tetrahydroxy phenyl porphyrins and 0.5054g zinc acetates are mixed, reuses agate mortar and be ground 30min obtains mixed-powder A；Mixed-powder A is distributed in 50mL dimethylformamides, then is heated at being 150 DEG C in temperature Flow back 45min, then pours into 100mL ice water, then stands 12h, then filtered at being -4 DEG C in temperature, obtains four (to hydroxyl Phenyl) zinc porphyrin；
6th, the NiO photocathodes of ZnTHPP-bpy sensitizations are prepared：
1., the ZnTHPP NiO photocathodes being sensitized are placed in temperature is that 3min~7min is heated in 65 DEG C~80 DEG C of baking oven, It is immersed in 8h~10h in the methanol solution of the 4,4- bipyridyls of a concentration of 10mmol/L~15mmol/L again；
2., by ZnTHPP sensitization NiO photocathodes take out, first using absolute ethyl alcohol wash 1 time, reuse deionized water Washing 1 time；
3., repeat step 6 it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain ZnTHPP-bpy sensitizations NiO photocathodes；
7th, the NiO photocathodes of ZnTHPP-bpy-Codmg self assemblies sensitization are prepared：
1., the ZnTHPP-bpy NiO photocathodes being sensitized are placed in temperature be heating 3min in 65 DEG C~80 DEG C of baking oven~ 7min, then it is immersed in the Co of a concentration of 10mmol/L~15mmol/LII(dmgH)2Cl2In methanol solution, triethylamine is added, Impregnate 8h~10h；
Step 7 1. described in CoII(dmgH)2Cl2Co in methanol solutionII(dmgH)2Cl2It is to prepare according to the following steps 's：
8.40mmol CoCL2 6H2Os are dissolved into 60mL acetone, add 16.81mmol dimethylglyoximes, then stirring Speed is to be stirred to react 10min, then be filtered under 300r/min~500r/min, filters out unreacted sediment, obtains Filtrate；Filtrate is stood into 12h, obtains green crystal；Green crystal is cleaned using acetone 3 times~5 times, obtains CoII(dmgH)2Cl2；
Step 7 1. described in a concentration of 10mmol/L~15mmol/L CoII(dmgH)2Cl2Methanol solution and three second The volume ratio of amine is 100:1；
2., by ZnTHPP-bpy sensitization NiO photocathodes take out, using absolute ethyl alcohol wash 1 time, reuse deionized water Washing 1 time；
3., repeat step 7 it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain ZnTHPP-bpy-Codmg from Assemble the NiO photocathodes of sensitization；
8th, the NiO photocathodes of ZnTPPC sensitizations are prepared：
1., the NiO photocathodes that ZnTHPP-bpy-Codmg self assemblies are sensitized are placed in the baking oven that temperature is 80 DEG C and heated 5min~10min, then be immersed in the methanol solution of four (carboxyl phenyl) zinc porphyrins of a concentration of 10mmol/L~15mmol/L Impregnate 8h~10h；
Step 8 1. described in four (carboxyl phenyl) zinc porphyrins methanol solution in four (carboxyl phenyl) zinc porphyrins it is specific It prepares according to the following steps：
(1), 3.11g p formylbenzoic acid methyl esters is dissolved into 50mL propionic acid, adds 3mL dimethyl sulfoxide (DMSO)s, obtain To mixed liquor；Mixed liquor is heated to 130 DEG C, then 1.3mL pyrroles is added drop-wise in 5min in mixed liquor, then be in temperature 40min is heated to reflux at 130 DEG C, then is filtered under diminished pressure, obtains filter cake；Filter cake is cleaned 3 times~5 times, then make using propionic acid It is dried with washes of absolute alcohol 3 times~5 times, then by filter cake, obtains purple crystals, as four ester group phenyl porphyrins；
(2), tetra- ester group phenyl porphyrins of 250mg and 400mg acetic acid dihydrates zinc are mixed, adds 30mL chloroforms and 10mL Methanol obtains reaction solution；4h is heated to reflux at being 65 DEG C in temperature by reaction solution, is evaporated under reduced pressure, removed after reaction Solvent adds 25mL tetrahydrofurans and 5mL mass fractions as 4% potassium hydroxide aqueous solution, then adds at being 60 DEG C in temperature Heat reflux for 24 hours, then is evaporated under reduced pressure, and removes solvent；Obtain solid matter；25mL deionizations are added in into 0.2g solid matters Water obtains solid matter mixed liquor；Reuse HCl that mass fraction is 37% adjust solid matter mixed liquor to pH value be 1~ 2, then centrifuged, centrifugate is removed, obtains purple precipitation；Using distilled water to purple precipitation cleaning 3 times~5 times, then carry out It is dry, obtain four (carboxyl phenyl) zinc porphyrins；
2., the NiO photocathodes that are sensitized ZnTHPP-bpy-Codmg self assemblies take out, washed 1 time using absolute ethyl alcohol, then Make to be washed with deionized 1 time；
3., repeat step 8 it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain the NiO light of ZnTPPC sensitizations Cathode；
9th, the NiO photocathodes of ZnTPPC-bpy sensitizations are prepared：
1., the ZnTPPC NiO photocathodes being sensitized are placed in temperature is that 3min~7min is heated in 65 DEG C~80 DEG C of baking oven, It is immersed in 8h~10h in the methanol solution of the 4,4- bipyridyls of a concentration of 10mmol/L~15mmol/L again；
2., by ZnTPPC sensitization NiO photocathodes take out, wash 1 time with absolute ethyl alcohol, reuse deionized water wash 1 It is secondary；
3., repeat step 9 it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain ZnTPPC-bpy sensitizations NiO photocathodes；
Tenth, it impregnates, clean：
1., the ZnTPPC-bpy NiO photocathodes being sensitized are placed in temperature be heating 3min in 65 DEG C~80 DEG C of baking oven~ 7min, then it is immersed in the Co of a concentration of 10mmol/L~15mmol/LII(dmgH)2Cl2In methanol solution, triethylamine is added, Impregnate 8h~10h；
Step 10 1. described in CoII(dmgH)2Cl2Co in methanol solutionII(dmgH)2Cl2It is to prepare according to the following steps 's：8.40mmol CoCL2 6H2Os are dissolved into 60mL acetone, add 16.81mmol dimethylglyoximes, then low whipping speed To be stirred to react 10min under 300r/min~500r/min, then be filtered, unreacted sediment is filtered out, obtains filtrate； Filtrate is stood into 12h, obtains green crystal；Green crystal is cleaned using acetone 3 times~5 times, obtains CoII(dmgH)2Cl2；
Step 10 1. described in a concentration of 10mmol/L~15mmol/L CoII(dmgH)2Cl2Methanol solution and three second The volume ratio of amine is 100:1；
2., by ZnTPPC-bpy sensitization NiO photocathodes take out, using absolute ethyl alcohol wash 1 time, reuse deionized water Washing 1 time；
3., the operation that repeats step 10 it is secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain based on zinc porphyrin and fourth The NiO photocathodes of two ketoxime cobalt self assemblies.
With existing Technical comparing, the present invention has the following advantages：
First, have been reported release hydrogen photocathode generally using more complicated assembling mode come build photocathode and stability compared with Difference, the present invention use a kind of simple and practicable method by two kinds of photosensitizer four (p-hydroxybenzene) zinc porphyrins (ZnTHPP) and four (carboxyl phenyl) zinc porphyrin (ZnTPPC) and catalyst CoII(dmgH)2Cl2(Codmg) by being coordinated with 4,4- bipyridyls (bpy) Self assembly releases hydrogen photocathode to build, and the raising hydrogen generation efficiency that can stablize, because light excitation porphyrin directly shifts electronics Hydrogen ion in feedwater, such catalytic effect is low, in addition CoII(dmgH)2Cl2(Codmg) after catalyst, photoelectric current improves, Illustrate that electronics is transferred to Co from porphyrin under illumination conditionII(dmgH)2Cl2(Codmg) on catalyst, and then the hydrogen in catalytic water Ion becomes hydrogen, and catalytic effect improves；
2nd, the NiO photocathodes that ZnTHPP-bpy-Codmg self assemblies are sensitized in the present invention are relative to simple absorption ZnTHPP NiO photocathode photocurrent responses be significantly improved, efficiency improves 50%~55%, and electric current is stablized；
3rd, the NiO photocathodes based on zinc porphyrin and dimethylglyoxime cobalt self assembly prepared by the present invention are relative to simple absorption The NiO photocathode photocurrent responses of ZnTPPC are significantly improved, and efficiency improves 75%~80%, and electric current is stablized.
The present invention can obtain a kind of preparation method based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly.
Description of the drawings
Fig. 1 is photoelectric current comparison diagram, the 1 NiO photocathodes of ZnTHPP sensitizations to be obtained in one step 5 of embodiment in Fig. 1 Photocurrent curve, 2 be the NiO photocathodes of ZnTHPP-bpy-Codmg self assemblies sensitization that obtain in one step 7 of embodiment Photocurrent curve；
Fig. 2 is solid ultraviolet-ray visible absorbing figure comparison diagram, and 1 is quick for the ZnTHPP that is obtained in one step 5 of embodiment in Fig. 2 The solid ultraviolet-ray visible absorbing curve of the NiO photocathodes of change, 2 ZnTHPP-bpy- to be obtained in one step 7 of embodiment The solid ultraviolet-ray visible absorbing curve of the NiO photocathodes of Codmg self assemblies sensitization；
Fig. 3 is photoelectric current comparison diagram, the 1 NiO photocathodes of ZnTPPC sensitizations to be obtained in one step 8 of embodiment in Fig. 3 Photocurrent curve, the 2 NiO photocathodes based on zinc porphyrin and dimethylglyoxime cobalt self assembly obtained for one step 10 of embodiment Photocurrent curve；
Fig. 4 is solid ultraviolet-ray visible absorbing figure comparison diagram, and 1 is quick for the ZnTPPC that is obtained in one step 8 of embodiment in Fig. 4 The solid ultraviolet-ray visible absorbing curve of the NiO photocathodes of change, 2 for one step 10 of embodiment obtain based on zinc porphyrin and fourth two The solid ultraviolet-ray visible absorbing curve of the NiO photocathodes of ketoxime cobalt self assembly；
Fig. 5 is flow diagram of one step 5 of embodiment to step 7；
Fig. 6 is flow diagram of one step 8 of embodiment to step 10.
Specific embodiment
Technical scheme of the present invention is further described with reference to the accompanying drawings and examples, but is not so limited, It is every that technical solution of the present invention is modified or replaced equivalently, without departing from the spirit and scope of technical solution of the present invention, It should all cover in protection scope of the present invention.
Specific embodiment one：Present embodiment is a kind of NiO time based on zinc porphyrin Yu dimethylglyoxime cobalt self assembly The preparation method of pole, it is characterised in that this method was specifically realized by the following steps：
First, NiO compacted zone precursor liquids are prepared：By NiCl2·6H2O, P123, deionized water and absolute ethyl alcohol mixing, stirring It is put into centrifuge and centrifuges after uniformly, removal precipitation, obtained supernatant is NiO compacted zone precursor liquids；
NiCl described in step 12·6H2The mass ratio of O and P123 is 1:(0.5~0.8)；
NiCl described in step 12·6H2O and the mass ratio of deionized water are 1:(1.3~1.66)；
NiCl described in step 12·6H2The mass ratio of O and absolute ethyl alcohol is 1:(3~3.3)；
The centrifugal speed of centrifuge described in step 1 be 7000r/min~9000r/min, centrifugation time for 3min~ 7min；
2nd, NiO compacted zones are prepared：
1., the NiO compacted zone precursor liquids obtained in step 1 are spun to leading for FTO electro-conductive glass by way of spin coating On electric face, it is then placed in dry 3min~7min in the baking oven that temperature is 65 DEG C~80 DEG C again；
2., repeat step 2 1. 1 time~4 times, then 30min~60min is sintered at being 300 DEG C~350 DEG C in temperature, obtain Contain the FTO electro-conductive glass of NiO compacted zones in surface；
Step 2 2. described in surface contain NiO compacted zones on the FTO electro-conductive glass of NiO compacted zones thickness be 50nm ~100nm；
3rd, slurry is prepared：
NiO powders, terpinol and ethyl cellulose are distributed in absolute ethyl alcohol, are aged 2 after stirring evenly at room temperature ~3 days, obtain slurry；
The mass ratio of NiO powders and terpinol described in step 3 is 1:(3.5~4)；
The mass ratio of NiO powders and ethyl cellulose described in step 3 is 1:(0.1~0.2)；
The mass ratio of NiO powders and absolute ethyl alcohol described in step 3 is 1:(3~5)；
NiO powders described in step 3 are the spherical nickel oxide that grain size is 30nm；
The 4th, the slurry obtained in step 3 is printed onto to the surface obtained in step 2 contain using the method for silk-screen printing On the NiO compacted zones of the FTO electro-conductive glass of NiO compacted zones, the thickness of slurry printing is 1 μm~2 μm, and it is 65 to be subsequently placed in temperature DEG C~80 DEG C of baking oven in dry 3min~7min, then be sintered 30min~60min at being 400 DEG C~500 DEG C in temperature, it is natural NiO blank is obtained after cooling；
5th, the NiO photocathodes of ZnTHPP sensitizations are prepared：
1., the NiO blank obtained in step 4 is placed in the baking oven that temperature is 80 DEG C and heats 5min~10min, then soak Bubble 8h~10h in the methanol solution of four (p-hydroxybenzene) zinc porphyrins of a concentration of 10mmol/L~15mmol/L；
2., NiO blank taken out, washed 1 time using absolute ethyl alcohol first, reuse deionized water and wash 1 time；
3., repeat step 5 it is 2. secondary~tetra- times, then be dried at room temperature for 4h, obtain the NiO photocathodes of ZnTHPP sensitizations；
Four (p-hydroxybenzene) zinc porphyrins are in the methanol solution of four (p-hydroxybenzene) zinc porphyrins described in step 5 It is prepared according to following steps：
(1), 6.5g parahydroxyben-zaldehydes are dissolved into 240mL propionic acid, then are heated to reflux at being 140 DEG C in temperature, then 4.3mL pyrroles is added drop-wise in 5min in propionic acid, then 1.5h is heated to reflux at being 140 DEG C in temperature, is cooled to room temperature, then add Enter 100mL methanol, then the cooling and standings 0.5h under ice bath, have violet solid precipitation, then filtered, filter cake is cleaned using methanol It is colourless to cleaning solution, obtain solid matter；Solid matter is dissolved into the mixed liquor of dichloromethane and methanol, stands 12h, then It is filtered, obtains purple crystals, as tetrahydroxy phenyl porphyrin；Dichloromethane in the dichloromethane and the mixed liquor of methanol The volume ratio of alkane and methanol is 1:1；
(2), 0.1064g tetrahydroxy phenyl porphyrins and 0.5054g zinc acetates are mixed, reuses agate mortar and be ground 30min obtains mixed-powder A；Mixed-powder A is distributed in 50mL dimethylformamides, then is heated at being 150 DEG C in temperature Flow back 45min, then pours into 100mL ice water, then stands 12h, then filtered at being -4 DEG C in temperature, obtains four (to hydroxyl Phenyl) zinc porphyrin；
6th, the NiO photocathodes of ZnTHPP-bpy sensitizations are prepared：
1., the ZnTHPP NiO photocathodes being sensitized are placed in temperature is that 3min~7min is heated in 65 DEG C~80 DEG C of baking oven, It is immersed in 8h~10h in the methanol solution of the 4,4- bipyridyls of a concentration of 10mmol/L~15mmol/L again；
2., by ZnTHPP sensitization NiO photocathodes take out, first using absolute ethyl alcohol wash 1 time, reuse deionized water Washing 1 time；
3., repeat step 6 it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain ZnTHPP-bpy sensitizations NiO photocathodes；
7th, the NiO photocathodes of ZnTHPP-bpy-Codmg self assemblies sensitization are prepared：
1., the ZnTHPP-bpy NiO photocathodes being sensitized are placed in temperature be heating 3min in 65 DEG C~80 DEG C of baking oven~ 7min, then it is immersed in the Co of a concentration of 10mmol/L~15mmol/LII(dmgH)2Cl2In methanol solution, triethylamine is added, Impregnate 8h~10h；
Step 7 1. described in CoII(dmgH)2Cl2Co in methanol solutionII(dmgH)2Cl2It is to prepare according to the following steps 's：
8.40mmol CoCL2 6H2Os are dissolved into 60mL acetone, add 16.81mmol dimethylglyoximes, then stirring Speed is to be stirred to react 10min, then be filtered under 300r/min~500r/min, filters out unreacted sediment, obtains Filtrate；Filtrate is stood into 12h, obtains green crystal；Green crystal is cleaned using acetone 3 times~5 times, obtains CoII(dmgH)2Cl2；
Step 7 1. described in a concentration of 10mmol/L~15mmol/L CoII(dmgH)2Cl2Methanol solution and three second The volume ratio of amine is 100:1；
2., by ZnTHPP-bpy sensitization NiO photocathodes take out, using absolute ethyl alcohol wash 1 time, reuse deionized water Washing 1 time；
3., repeat step 7 it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain ZnTHPP-bpy-Codmg from Assemble the NiO photocathodes of sensitization；
8th, the NiO photocathodes of ZnTPPC sensitizations are prepared：
1., the NiO photocathodes that ZnTHPP-bpy-Codmg self assemblies are sensitized are placed in the baking oven that temperature is 80 DEG C and heated 5min~10min, then be immersed in the methanol solution of four (carboxyl phenyl) zinc porphyrins of a concentration of 10mmol/L~15mmol/L Impregnate 8h~10h；
Step 8 1. described in four (carboxyl phenyl) zinc porphyrins methanol solution in four (carboxyl phenyl) zinc porphyrins it is specific It prepares according to the following steps：
(1), 3.11g p formylbenzoic acid methyl esters is dissolved into 50mL propionic acid, adds 3mL dimethyl sulfoxide (DMSO)s, obtain To mixed liquor；Mixed liquor is heated to 130 DEG C, then 1.3mL pyrroles is added drop-wise in 5min in mixed liquor, then be in temperature 40min is heated to reflux at 130 DEG C, then is filtered under diminished pressure, obtains filter cake；Filter cake is cleaned 3 times~5 times, then make using propionic acid It is dried with washes of absolute alcohol 3 times~5 times, then by filter cake, obtains purple crystals, as four ester group phenyl porphyrins；
(2), tetra- ester group phenyl porphyrins of 250mg and 400mg acetic acid dihydrates zinc are mixed, adds 30mL chloroforms and 10mL Methanol obtains reaction solution；4h is heated to reflux at being 65 DEG C in temperature by reaction solution, is evaporated under reduced pressure, removed after reaction Solvent adds 25mL tetrahydrofurans and 5mL mass fractions as 4% potassium hydroxide aqueous solution, then adds at being 60 DEG C in temperature Heat reflux for 24 hours, then is evaporated under reduced pressure, and removes solvent；Obtain solid matter；25mL deionizations are added in into 0.2g solid matters Water obtains solid matter mixed liquor；Reuse HCl that mass fraction is 37% adjust solid matter mixed liquor to pH value be 1~ 2, then centrifuged, centrifugate is removed, obtains purple precipitation；Using distilled water to purple precipitation cleaning 3 times~5 times, then carry out It is dry, obtain four (carboxyl phenyl) zinc porphyrins；
2., the NiO photocathodes that are sensitized ZnTHPP-bpy-Codmg self assemblies take out, washed 1 time using absolute ethyl alcohol, then Make to be washed with deionized 1 time；
3., repeat step 8 it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain the NiO light of ZnTPPC sensitizations Cathode；
9th, the NiO photocathodes of ZnTPPC-bpy sensitizations are prepared：
1., the ZnTPPC NiO photocathodes being sensitized are placed in temperature is that 3min~7min is heated in 65 DEG C~80 DEG C of baking oven, It is immersed in 8h~10h in the methanol solution of the 4,4- bipyridyls of a concentration of 10mmol/L~15mmol/L again；
2., by ZnTPPC sensitization NiO photocathodes take out, wash 1 time with absolute ethyl alcohol, reuse deionized water wash 1 It is secondary；
3., repeat step 9 it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain ZnTPPC-bpy sensitizations NiO photocathodes；
Tenth, it impregnates, clean：
1., the ZnTPPC-bpy NiO photocathodes being sensitized are placed in temperature be heating 3min in 65 DEG C~80 DEG C of baking oven~ 7min, then it is immersed in the Co of a concentration of 10mmol/L~15mmol/LII(dmgH)2Cl2In methanol solution, triethylamine is added, Impregnate 8h~10h；
Step 10 1. described in CoII(dmgH)2Cl2Co in methanol solutionII(dmgH)2Cl2It is to prepare according to the following steps 's：8.40mmol CoCL2 6H2Os are dissolved into 60mL acetone, add 16.81mmol dimethylglyoximes, then low whipping speed To be stirred to react 10min under 300r/min~500r/min, then be filtered, unreacted sediment is filtered out, obtains filtrate； Filtrate is stood into 12h, obtains green crystal；Green crystal is cleaned using acetone 3 times~5 times, obtains CoII(dmgH)2Cl2；
Step 10 1. described in a concentration of 10mmol/L~15mmol/L CoII(dmgH)2Cl2Methanol solution and three second The volume ratio of amine is 100:1；
2., by ZnTPPC-bpy sensitization NiO photocathodes take out, using absolute ethyl alcohol wash 1 time, reuse deionized water Washing 1 time；
3., the operation that repeats step 10 it is secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain based on zinc porphyrin and fourth The NiO photocathodes of two ketoxime cobalt self assemblies.
Present embodiment is suitable for ZnTHPP and ZnTPPC as sensitizer, dimethylglyoxime cobalt complex CoII(dmgH)2Cl2As catalyst, and with 4,4- bipyridyls hydrogen photocathode is released by what self assembly mode was built as linking group.
With existing Technical comparing, this embodiment presents the advantage that：
First, have been reported release hydrogen photocathode generally using more complicated assembling mode come build photocathode and stability compared with Difference, present embodiment using a kind of simple and practicable method by two kinds of photosensitizer four (p-hydroxybenzene) zinc porphyrins (ZnTHPP) and Four (carboxyl phenyl) zinc porphyrins (ZnTPPC) and catalyst CoII(dmgH)2Cl2(Codmg) by matching with 4,4- bipyridyls (bpy) Position self assembly releases hydrogen photocathode, and the raising hydrogen generation efficiency that can stablize to build, because light excitation porphyrin directly turns electronics The hydrogen ion in feedwater is moved, such catalytic effect is low, in addition CoII(dmgH)2Cl2(Codmg) after catalyst, photoelectric current carries Height illustrates that electronics is transferred to Co from porphyrin under illumination conditionII(dmgH)2Cl2(Codmg) on catalyst, and then in catalytic water Hydrogen ion become hydrogen, catalytic effect improves；
2nd, the NiO photocathodes that ZnTHPP-bpy-Codmg self assemblies are sensitized in present embodiment are relative to simple absorption The NiO photocathode photocurrent responses of ZnTHPP are significantly improved, and efficiency improves 50%~55%, and electric current is stablized；
3rd, present embodiment prepare based on the NiO photocathodes of zinc porphyrin and dimethylglyoxime cobalt self assembly relative to simple The NiO photocathode photocurrent responses of absorption ZnTPPC are significantly improved, and efficiency improves 75%~80%, and electric current is steady It is fixed.
Present embodiment can obtain a kind of preparation side based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly Method.
Specific embodiment two：Present embodiment is with one difference of specific embodiment：Described in step 1 NiCl2·6H2The mass ratio of O and P123 is 1:(0.5~0.65)；NiCl described in step 12·6H2O and deionized water Mass ratio is 1:(1.3~1.45)；NiCl described in step 12·6H2The mass ratio of O and absolute ethyl alcohol is 1:(3~ 3.15).Other steps are same as the specific embodiment one.
Specific embodiment three：One of present embodiment and specific embodiment one or two difference are：Step 2 1. in The NiO compacted zone precursor liquids obtained in step 1 are spun to by way of spin coating on the conducting surface of FTO electro-conductive glass, then It is placed in dry 3min~5min in the baking oven that temperature is 65 DEG C~75 DEG C again；Step 2 is 2. middle to repeat step 2 1. 1 time~2 times, 30min~40min is sintered at being again 300 DEG C~350 DEG C in temperature, obtains the FTO electro-conductive glass that NiO compacted zones are contained on surface. Other steps are the same as one or two specific embodiments.
Specific embodiment four：One of present embodiment and specific embodiment one to three difference are：Institute in step 3 The NiO powders and the mass ratio of terpinol stated are 1:(3.5~3.8)；NiO powders and ethyl cellulose described in step 3 Mass ratio is 1:(0.1~0.15)；The mass ratio of NiO powders and absolute ethyl alcohol described in step 3 is 1:(3~4).Other Step is identical with specific embodiment one to three.
Specific embodiment five：One of present embodiment and specific embodiment one to four difference are：It is adopted in step 4 The slurry obtained in step 3 with the method for silk-screen printing is printed onto to the surface obtained in step 2 and contains NiO compacted zones On the NiO compacted zones of FTO electro-conductive glass, the thickness of slurry printing is 1 μm~2 μm, and it is 65 DEG C~75 DEG C to be subsequently placed in temperature Dry 3min~5min in baking oven, then 30min~40min is sintered at being 400 DEG C~450 DEG C in temperature, it is obtained after natural cooling NiO blank.Other steps are identical with specific embodiment one to four.
Specific embodiment six：One of present embodiment and specific embodiment one to five difference are：Step 5 1. in The NiO blank obtained in step 4 is placed in the baking oven that temperature is 80 DEG C and heats 5min~8min, then be immersed in a concentration of 8h~9h in the methanol solution of four (p-hydroxybenzene) zinc porphyrins of 10mmol/L~13mmol/L.Other steps and specific implementation Mode one to five is identical.
Specific embodiment seven：One of present embodiment and specific embodiment one to six difference are：Step 6 1. in The ZnTHPP NiO photocathodes being sensitized are placed in the baking oven that temperature is 65 DEG C~70 DEG C and heat 3min~5min, then be immersed in dense Spend 8h~9h in the methanol solution for the 4,4- bipyridyls of 10mmol/L~13mmol/L.Other steps and specific embodiment one It is identical to six.
Specific embodiment eight：One of present embodiment and specific embodiment one to seven difference are：Step 7 1. in The ZnTHPP-bpy NiO photocathodes being sensitized are placed in the baking oven that temperature is 65 DEG C~70 DEG C and heat 3min~5min, then impregnate In the Co of a concentration of 10mmol/L~15mmol/LII(dmgH)2Cl2In methanol solution, triethylamine is added, impregnates 8h~9h. Other steps are identical with specific embodiment one to seven.
Specific embodiment nine：One of present embodiment and specific embodiment one to eight difference are：Step 8 1. in The NiO photocathodes that ZnTHPP-bpy-Codmg self assemblies are sensitized are placed in the baking oven that temperature is 80 DEG C and heat 5min~8min, It is immersed in immersion 8h~9h in the methanol solution of four (carboxyl phenyl) zinc porphyrins of a concentration of 10mmol/L~13mmol/L again.Its His step is identical with specific embodiment one to eight.
Specific embodiment ten：One of present embodiment and specific embodiment one to nine difference are：Step 9 1. in The ZnTPPC NiO photocathodes being sensitized are placed in the baking oven that temperature is 65 DEG C~70 DEG C and heat 3min~5min, then be immersed in dense Spend 8h~9h in the methanol solution for the 4,4- bipyridyls of 10mmol/L~13mmol/L.Other steps and specific embodiment one It is identical to nine.
Advantages of the present invention is verified using following embodiment：
Embodiment one：A kind of preparation method based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly, specifically It completes according to the following steps：
First, NiO compacted zone precursor liquids are prepared：By NiCl2·6H2O, P123, deionized water and absolute ethyl alcohol mixing, stirring It is put into centrifuge and centrifuges after uniformly, removal precipitation, obtained supernatant is NiO compacted zone precursor liquids；
NiCl described in step 12·6H2The mass ratio of O and P123 is 1:0.8；
NiCl described in step 12·6H2O and the mass ratio of deionized water are 1:1.66；
NiCl described in step 12·6H2The mass ratio of O and absolute ethyl alcohol is 1:3.3；
The centrifugal speed of centrifuge described in step 1 is 8000r/min, centrifugation time 5min；
2nd, NiO compacted zones are prepared：
1., the NiO compacted zone precursor liquids obtained in step 1 are spun to leading for FTO electro-conductive glass by way of spin coating On electric face, it is then placed in dry 5min in the baking oven that temperature is 80 DEG C again；
2., repeat step 2 1. 1 time, then 30min is sintered at being 350 DEG C in temperature, obtain surface and contain NiO compacted zones FTO electro-conductive glass；
Step 2 2. described in surface contain NiO compacted zones FTO electro-conductive glass on the thickness of NiO compacted zones be 100nm；
3rd, slurry is prepared：
NiO powders, terpinol and ethyl cellulose are distributed in absolute ethyl alcohol, are aged 2 after stirring evenly at room temperature ~3 days, obtain slurry；
The mass ratio of NiO powders and terpinol described in step 3 is 1:3.5；
The mass ratio of NiO powders and ethyl cellulose described in step 3 is 1:0.15；
The mass ratio of NiO powders and absolute ethyl alcohol described in step 3 is 1:3；
NiO powders described in step 3 are the spherical nickel oxide that grain size is 30nm；
The 4th, the slurry obtained in step 3 is printed onto to the surface obtained in step 2 contain using the method for silk-screen printing On the NiO compacted zones of the FTO electro-conductive glass of NiO compacted zones, the thickness of slurry printing is 1 μm~2 μm, and it is 80 to be subsequently placed in temperature DEG C baking oven in dry 5min, then be sintered 30min at being 450 DEG C in temperature, NiO blank obtained after natural cooling；
5th, the NiO photocathodes of ZnTHPP sensitizations are prepared：
1., the NiO blank obtained in step 4 is placed in the baking oven that temperature is 80 DEG C and heats 10min, then be immersed in dense Spend 8h in the methanol solution for four (p-hydroxybenzene) zinc porphyrins of 10mmol/L；
2., NiO blank taken out, washed 1 time using absolute ethyl alcohol first, reuse deionized water and wash 1 time；
3., repeat step 5 2. three times, then be dried at room temperature for 4h, obtain ZnTHPP sensitization NiO photocathodes；
Four (p-hydroxybenzene) zinc porphyrins are in the methanol solution of four (p-hydroxybenzene) zinc porphyrins described in step 5 It is prepared according to following steps：
(1), 6.5g parahydroxyben-zaldehydes are dissolved into 240mL propionic acid, then are heated to reflux at being 140 DEG C in temperature, then 4.3mL pyrroles is added drop-wise in 5min in propionic acid, then 1.5h is heated to reflux at being 140 DEG C in temperature, is cooled to room temperature, then add Enter 100mL methanol, then the cooling and standings 0.5h under ice bath, have violet solid precipitation, then filtered, filter cake is cleaned using methanol It is colourless to cleaning solution, obtain solid matter；Solid matter is dissolved into the mixed liquor of dichloromethane and methanol, stands 12h, then It is filtered, obtains purple crystals, as tetrahydroxy phenyl porphyrin；Dichloromethane in the dichloromethane and the mixed liquor of methanol The volume ratio of alkane and methanol is 1:1；
(2), 0.1064g tetrahydroxy phenyl porphyrins and 0.5054g zinc acetates are mixed, reuses agate mortar and be ground 30min obtains mixed-powder A；Mixed-powder A is distributed in 50mL dimethylformamides, then is heated at being 150 DEG C in temperature Flow back 45min, then pours into 100mL ice water, then stands 12h, then filtered at being -4 DEG C in temperature, obtains four (to hydroxyl Phenyl) zinc porphyrin；
6th, the NiO photocathodes of ZnTHPP-bpy sensitizations are prepared：
1., the ZnTHPP NiO photocathodes being sensitized are placed in temperature is to heat 5min, then be immersed in concentration in 80 DEG C of baking oven For 8h in the methanol solution of the 4,4- bipyridyls of 10mmol/L；
2., by ZnTHPP sensitization NiO photocathodes take out, first using absolute ethyl alcohol wash 1 time, reuse deionized water Washing 1 time；
3., repeat step 6 2. three times, then be dried at room temperature for 4h, obtain ZnTHPP-bpy sensitization NiO photocathodes；
7th, the NiO photocathodes of ZnTHPP-bpy-Codmg self assemblies sensitization are prepared：
1., the ZnTHPP-bpy NiO photocathodes being sensitized are placed in temperature is to heat 5min, then be immersed in 80 DEG C of baking oven The Co of a concentration of 10mmol/LII(dmgH)2Cl2In methanol solution, triethylamine is added, impregnates 8h；
Step 7 1. described in CoII(dmgH)2Cl2Co in methanol solutionII(dmgH)2Cl2It is to prepare according to the following steps 's：
8.40mmol CoCL2 6H2Os are dissolved into 60mL acetone, add 16.81mmol dimethylglyoximes, then stirring Speed is to be stirred to react 10min, then be filtered under 400r/min, filters out unreacted sediment, obtains filtrate；By filtrate 12h is stood, obtains green crystal；Green crystal is cleaned using acetone 5 times, obtains CoII(dmgH)2Cl2；
Step 7 1. described in a concentration of 10mmol/L CoII(dmgH)2Cl2The volume ratio of methanol solution and triethylamine It is 100:1；
2., by ZnTHPP-bpy sensitization NiO photocathodes take out, using absolute ethyl alcohol wash 1 time, reuse deionized water Washing 1 time；
3., repeat step 7 2. three times, then be dried at room temperature for 4h, obtain ZnTHPP-bpy-Codmg self assemblies sensitization NiO photocathodes；
8th, the NiO photocathodes of ZnTPPC sensitizations are prepared：
1., the NiO photocathodes that ZnTHPP-bpy-Codmg self assemblies are sensitized are placed in the baking oven that temperature is 80 DEG C and heated 5min, then be immersed in a concentration of 10mmol/L four (carboxyl phenyl) zinc porphyrins methanol solution in impregnate 8h；
Step 8 1. described in four (carboxyl phenyl) zinc porphyrins methanol solution in four (carboxyl phenyl) zinc porphyrins it is specific It prepares according to the following steps：
(1), 3.11g p formylbenzoic acid methyl esters is dissolved into 50mL propionic acid, adds 3mL dimethyl sulfoxide (DMSO)s, obtain To mixed liquor；Mixed liquor is heated to 130 DEG C, then 1.3mL pyrroles is added drop-wise in 5min in mixed liquor, then be in temperature 40min is heated to reflux at 130 DEG C, then is filtered under diminished pressure, obtains filter cake；Filter cake is cleaned 5 times using propionic acid, is reused anhydrous Ethyl alcohol cleans 5 times, then filter cake is dried, and obtains purple crystals, as four ester group phenyl porphyrins；
(2), tetra- ester group phenyl porphyrins of 250mg and 400mg acetic acid dihydrates zinc are mixed, adds 30mL chloroforms and 10mL Methanol obtains reaction solution；4h is heated to reflux at being 65 DEG C in temperature by reaction solution, is evaporated under reduced pressure, removed after reaction Solvent adds 25mL tetrahydrofurans and 5mL mass fractions as 4% potassium hydroxide aqueous solution, then adds at being 60 DEG C in temperature Heat reflux for 24 hours, then is evaporated under reduced pressure, and removes solvent；Obtain solid matter；25mL deionizations are added in into 0.2g solid matters Water obtains solid matter mixed liquor；Reuse HCl that mass fraction is 37% adjust solid matter mixed liquor to pH value be 1~ 2, then centrifuged, centrifugate is removed, obtains purple precipitation；Using distilled water to purple precipitation cleaning 3 times~5 times, then carry out It is dry, obtain four (carboxyl phenyl) zinc porphyrins；
2., the NiO photocathodes that are sensitized ZnTHPP-bpy-Codmg self assemblies take out, washed 1 time using absolute ethyl alcohol, then Make to be washed with deionized 1 time；
3., repeat step 8 2. three times, then be dried at room temperature for 4h, obtain ZnTPPC sensitization NiO photocathodes；
9th, the NiO photocathodes of ZnTPPC-bpy sensitizations are prepared：
1., the ZnTPPC NiO photocathodes being sensitized are placed in temperature is to heat 5min, then be immersed in concentration in 80 DEG C of baking oven For 8h in the methanol solution of the 4,4- bipyridyls of 10mmol/L；
2., by ZnTPPC sensitization NiO photocathodes take out, wash 1 time with absolute ethyl alcohol, reuse deionized water wash 1 It is secondary；
3., repeat step 9 2. three times, then be dried at room temperature for 4h, obtain ZnTPPC-bpy sensitization NiO photocathodes；
Tenth, it impregnates, clean：
1., the ZnTPPC-bpy NiO photocathodes being sensitized are placed in temperature is to heat 5min, then be immersed in 80 DEG C of baking oven The Co of a concentration of 10mmol/LII(dmgH)2Cl2In methanol solution, triethylamine is added, impregnates 8h；
Step 10 1. described in CoII(dmgH)2Cl2Co in methanol solutionII(dmgH)2Cl2It is to prepare according to the following steps 's：8.40mmol CoCL2 6H2Os are dissolved into 60mL acetone, add 16.81mmol dimethylglyoximes, then low whipping speed To be stirred to react 10min under 400r/min, then be filtered, unreacted sediment is filtered out, obtains filtrate；Filtrate is stood 12h obtains green crystal；Green crystal is cleaned using acetone 5 times, obtains CoII(dmgH)2Cl2；
Step 10 1. described in a concentration of 10mmol/L CoII(dmgH)2Cl2The volume ratio of methanol solution and triethylamine It is 100:1；
2., by ZnTPPC-bpy sensitization NiO photocathodes take out, using absolute ethyl alcohol wash 1 time, reuse deionized water Washing 1 time；
3., the operation that repeats step 10 three times, then be dried at room temperature for 3h, obtain based on zinc porphyrin and dimethylglyoxime cobalt from The NiO photocathodes of assembling.
Using CHI 660E electrochemical workstations as platform, tested using three electrode standards systems, with Ag/AgCl electrodes For reference electrode, Pt be to electrode, prepared time extremely working electrode, the aqueous sodium persulfate solution of 0.1mol/L is as electricity Solve liquid, the bias voltage of application -0.2V；Light source is simulated visible light (300W xenon lamps, illumination density 300mW/cm2, it is subject to 400nm long pass filters are filtering off ultraviolet light)；It assembles photoelectrochemistrpool pool and I-T curve tests is carried out to photocurrent response.In order to It needs to carry out bubbling argon 15min to electrolyte before removing the oxygen electro-chemical test in electrolyte.All tests are at 25 DEG C Lower progress, such as Fig. 1 and as indicated at 3.
It will be obtained in one step 7 of NiO photocathodes and embodiment of the ZnTHPP obtained in one step 5 of embodiment sensitizations respectively The NiO photocathodes of ZnTHPP-bpy-Codmg self assemblies sensitization arrived are as working electrode, and assembling photoelectrochemistrpool pool is to photoelectric current Response carries out I-T curve tests, as shown in Figure 1；
Fig. 1 is photoelectric current comparison diagram, the 1 NiO photocathodes of ZnTHPP sensitizations to be obtained in one step 5 of embodiment in Fig. 1 Photocurrent curve, 2 be the NiO photocathodes of ZnTHPP-bpy-Codmg self assemblies sensitization that obtain in one step 7 of embodiment Photocurrent curve；
From fig. 1, it can be seen that the NiO photocathodes of ZnTHPP-bpy-Codmg self assemblies sensitization obtained in one step 7 of embodiment It being significantly improved relative to the NiO photocathode photocurrent responses of simple absorption ZnTHPP, efficiency improves 50% or so, And electric current is stablized.
The NiO photocathodes of the ZnTPPC obtained in one step 8 of embodiment sensitizations and one step 10 of embodiment are obtained respectively Based on the NiO photocathodes of zinc porphyrin and dimethylglyoxime cobalt self assembly as working electrode, assemble photoelectrochemistrpool pool to photoelectric current Response carries out I-T curve tests, as shown in Figure 3；
Fig. 3 is photoelectric current comparison diagram, the 1 NiO photocathodes of ZnTPPC sensitizations to be obtained in one step 8 of embodiment in Fig. 3 Photocurrent curve, the 2 NiO photocathodes based on zinc porphyrin and dimethylglyoxime cobalt self assembly obtained for one step 10 of embodiment Photocurrent curve；
As can be seen from Figure 3, the NiO photocathodes based on zinc porphyrin Yu dimethylglyoxime cobalt self assembly that one step 10 of embodiment obtains It being significantly improved relative to the NiO photocathode photocurrent responses of simple absorption ZnTPPC, efficiency improves 75% or so, And electric current is stablized.
Fig. 2 is solid ultraviolet-ray visible absorbing figure comparison diagram, and 1 is quick for the ZnTHPP that is obtained in one step 5 of embodiment in Fig. 2 The solid ultraviolet-ray visible absorbing curve of the NiO photocathodes of change, 2 ZnTHPP-bpy- to be obtained in one step 7 of embodiment The solid ultraviolet-ray visible absorbing curve of the NiO photocathodes of Codmg self assemblies sensitization；
As can be seen from Figure 2, the NiO photocathodes of ZnTHPP sensitizations obtained in one step 5 of embodiment are left for 440nm in wavelength The absorption peak of right appearance is the characteristic absorption of ZnTHPP, and the ZnTHPP- by being obtained in one step 7 of embodiment after self assembly Absorption of the NiO photocathodes of bpy-Codmg self assemblies sensitization at this decreases, this is because the NiO light of ZnTHPP sensitizations Cathode repeatedly impregnates in methanol solution causes dye moiety desorption to cause.And the absorption after 450nm increased be by It is caused in catalyst Codmg absorption.
Fig. 4 is solid ultraviolet-ray visible absorbing figure comparison diagram, and 1 is quick for the ZnTPPC that is obtained in one step 8 of embodiment in Fig. 4 The solid ultraviolet-ray visible absorbing curve of the NiO photocathodes of change, 2 for one step 10 of embodiment obtain based on zinc porphyrin and fourth two The solid ultraviolet-ray visible absorbing curve of the NiO photocathodes of ketoxime cobalt self assembly；
As can be seen from Figure 4, the NiO photocathodes of ZnTPPC sensitizations obtained in one step 8 of embodiment are left for 435nm in wavelength The absorption peak of right appearance be ZnTPPC characteristic absorption, and by one step 10 of embodiment after independently filling obtain based on porphyrin Absorption of the NiO photocathodes of zinc and dimethylglyoxime cobalt self assembly at this decreases, this is because the NiO light of ZnTPPC sensitizations Cathode repeatedly impregnates in methanol solution causes dye moiety desorption to cause.And the absorption after 450nm increased be by It is caused in catalyst Codmg absorption.
Fig. 5 is flow diagram of one step 5 of embodiment to step 7；
As can be seen from Figure 5, photosensitizer ZnTHPP forms Hydrogen Binding Adsorption by the hydroxy groups of its band and the hydroxyl on NiO surfaces On NiO surfaces, the N on the Zn ions of ZnTHPP and one of pyridine of 4,4- bipyridyl forms coordination, last Codmg later Coordination completion self assembly, which is formed, with the N on another pyridine of 4,4- bipyridyls obtains ZnTHPP-bpy-Codmg self assembly light Cathode.
Fig. 6 is flow diagram of one step 8 of embodiment to step 10；
It is adsorbed it will be appreciated from fig. 6 that photosensitizer ZnTPPC forms ester bond by the carboxyl group of its band with the hydroxyl on NiO surfaces On NiO surfaces, the N on the Zn ions of ZnTPPC and one of pyridine of 4,4- bipyridyl forms coordination, last Codmg later Coordination completion self assembly, which is formed, with the N on another pyridine of 4,4- bipyridyls obtains ZnTHPC-bpy-Codmg self assembly light Cathode, i.e., the NiO photocathodes based on zinc porphyrin Yu dimethylglyoxime cobalt self assembly.

Claims (10)

  1. A kind of 1. preparation method based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly, it is characterised in that this method It is specifically realized by the following steps：
    First, NiO compacted zone precursor liquids are prepared：By NiCl2·6H2O, P123, deionized water and absolute ethyl alcohol mixing, stir evenly After be put into centrifuge and centrifuge, removal precipitation, obtained supernatant is NiO compacted zone precursor liquids；
    NiCl described in step 12·6H2The mass ratio of O and P123 is 1:(0.5~0.8)；
    NiCl described in step 12·6H2O and the mass ratio of deionized water are 1:(1.3~1.66)；
    NiCl described in step 12·6H2The mass ratio of O and absolute ethyl alcohol is 1:(3~3.3)；
    The centrifugal speed of centrifuge described in step 1 be 7000r/min~9000r/min, centrifugation time for 3min~ 7min；
    2nd, NiO compacted zones are prepared：
    1., the NiO compacted zone precursor liquids obtained in step 1 are spun to the conducting surface of FTO electro-conductive glass by way of spin coating On, it is then placed in dry 3min~7min in the baking oven that temperature is 65 DEG C~80 DEG C again；
    2., repeat step 2 1. 1 time~4 times, then 30min~60min is sintered at being 300 DEG C~350 DEG C in temperature, obtain surface FTO electro-conductive glass containing NiO compacted zones；
    Step 2 2. described in surface contain the thickness of NiO compacted zones on the FTO electro-conductive glass of NiO compacted zones for 50nm~ 100nm；
    3rd, slurry is prepared：
    NiO powders, terpinol and ethyl cellulose are distributed in absolute ethyl alcohol, are aged 2~3 after stirring evenly at room temperature My god, obtain slurry；
    The mass ratio of NiO powders and terpinol described in step 3 is 1:(3.5~4)；
    The mass ratio of NiO powders and ethyl cellulose described in step 3 is 1:(0.1~0.2)；
    The mass ratio of NiO powders and absolute ethyl alcohol described in step 3 is 1:(3~5)；
    NiO powders described in step 3 are the spherical nickel oxide that grain size is 30nm；
    The 4th, the slurry obtained in step 3 using the method for silk-screen printing is printed onto to the surface obtained in step 2 contain NiO On the NiO compacted zones of the FTO electro-conductive glass of compacted zone, the thickness of slurry printing is 1 μm~2 μm, and it is 65 DEG C to be subsequently placed in temperature Dry 3min~7min in~80 DEG C of baking oven, then 30min~60min is sintered at being 400 DEG C~500 DEG C in temperature, it is naturally cold But NiO blank is obtained afterwards；
    5th, the NiO photocathodes of ZnTHPP sensitizations are prepared：
    1., the NiO blank obtained in step 4 is placed in the baking oven that temperature is 80 DEG C and heats 5min~10min, then be immersed in 8h~10h in the methanol solution of four (p-hydroxybenzene) zinc porphyrins of a concentration of 10mmol/L~15mmol/L；
    2., NiO blank taken out, washed 1 time using absolute ethyl alcohol first, reuse deionized water and wash 1 time；
    3., repeat step 5 it is 2. secondary~tetra- times, then be dried at room temperature for 4h, obtain the NiO photocathodes of ZnTHPP sensitizations；
    In the methanol solution of four (p-hydroxybenzene) zinc porphyrins described in step 5 four (p-hydroxybenzene) zinc porphyrins be according to Prepared by following steps：
    (1), 6.5g parahydroxyben-zaldehydes are dissolved into 240mL propionic acid, then are heated to reflux at being 140 DEG C in temperature, then will 4.3mL pyrroles is added drop-wise in 5min in propionic acid, then is heated to reflux 1.5h at being 140 DEG C in temperature, is cooled to room temperature, is added 100mL methanol, then the cooling and standings 0.5h under ice bath, have violet solid precipitation, then filtered, using methanol cleaning filter cake extremely Cleaning solution is colourless, obtains solid matter；Solid matter is dissolved into the mixed liquor of dichloromethane and methanol, standing 12h, then into Row filters, and obtains purple crystals, as tetrahydroxy phenyl porphyrin；Dichloromethane in the dichloromethane and the mixed liquor of methanol Volume ratio with methanol is 1:1；
    (2), 0.1064g tetrahydroxy phenyl porphyrins and 0.5054g zinc acetates are mixed, reuses agate mortar and be ground 30min obtains mixed-powder A；Mixed-powder A is distributed in 50mL dimethylformamides, then is heated at being 150 DEG C in temperature Flow back 45min, then pours into 100mL ice water, then stands 12h, then filtered at being -4 DEG C in temperature, obtains four (to hydroxyl Phenyl) zinc porphyrin；
    6th, the NiO photocathodes of ZnTHPP-bpy sensitizations are prepared：
    1., the ZnTHPP NiO photocathodes being sensitized are placed in temperature is 3min~7min to be heated in 65 DEG C~80 DEG C of baking oven, then soak Bubble 8h~10h in the methanol solution of the 4,4- bipyridyls of a concentration of 10mmol/L~15mmol/L；
    2., by ZnTHPP sensitization NiO photocathodes take out, first using absolute ethyl alcohol wash 1 time, reuse deionized water washing 1 time；
    3., repeat step 6 it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain the NiO light of ZnTHPP-bpy sensitizations Cathode；
    7th, the NiO photocathodes of ZnTHPP-bpy-Codmg self assemblies sensitization are prepared：
    1., the ZnTHPP-bpy NiO photocathodes being sensitized are placed in temperature is that 3min~7min is heated in 65 DEG C~80 DEG C of baking oven, It is immersed in the Co of a concentration of 10mmol/L~15mmol/L againII(dmgH)2Cl2In methanol solution, triethylamine is added, impregnates 8h ~10h；
    Step 7 1. described in CoII(dmgH)2Cl2Co in methanol solutionII(dmgH)2Cl2It prepares according to the following steps：
    8.40mmol CoCL2 6H2Os are dissolved into 60mL acetone, add 16.81mmol dimethylglyoximes, then low whipping speed To be stirred to react 10min under 300r/min~500r/min, then be filtered, unreacted sediment is filtered out, obtains filtrate； Filtrate is stood into 12h, obtains green crystal；Green crystal is cleaned using acetone 3 times~5 times, obtains CoII(dmgH)2Cl2；
    Step 7 1. described in a concentration of 10mmol/L~15mmol/L CoII(dmgH)2Cl2Methanol solution and triethylamine Volume ratio is 100:1；
    2., by ZnTHPP-bpy sensitization NiO photocathodes take out, using absolute ethyl alcohol wash 1 time, reuse deionized water washing 1 time；
    3., repeat step 7 it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain ZnTHPP-bpy-Codmg self assemblies The NiO photocathodes of sensitization；
    8th, the NiO photocathodes of ZnTPPC sensitizations are prepared：
    1., the NiO photocathodes that ZnTHPP-bpy-Codmg self assemblies are sensitized are placed in the baking oven that temperature is 80 DEG C and heat 5min ~10min, then be immersed in a concentration of 10mmol/L~15mmol/L four (carboxyl phenyl) zinc porphyrins methanol solution in impregnate 8h~10h；
    Step 8 1. described in four (carboxyl phenyl) zinc porphyrins methanol solution in four (carboxyl phenyl) zinc porphyrins be specifically press Prepared by following steps：
    (1), 3.11g p formylbenzoic acid methyl esters is dissolved into 50mL propionic acid, adds 3mL dimethyl sulfoxide (DMSO)s, mixed Close liquid；Mixed liquor is heated to 130 DEG C, then 1.3mL pyrroles is added drop-wise in 5min in mixed liquor, then temperature be 130 DEG C Under be heated to reflux 40min, then be filtered under diminished pressure, obtain filter cake；Filter cake is cleaned 3 times~5 times using propionic acid, is reused anhydrous Ethyl alcohol cleans 3 times~5 times, then filter cake is dried, and obtains purple crystals, as four ester group phenyl porphyrins；
    (2), tetra- ester group phenyl porphyrins of 250mg and 400mg acetic acid dihydrates zinc are mixed, adds 30mL chloroforms and 10mL first Alcohol obtains reaction solution；4h is heated to reflux at being 65 DEG C in temperature by reaction solution, is evaporated under reduced pressure after reaction, removal is molten Agent adds 25mL tetrahydrofurans and 5mL mass fractions as 4% potassium hydroxide aqueous solution, then is heated at being 60 DEG C in temperature Reflux for 24 hours, then is evaporated under reduced pressure, and removes solvent；Obtain solid matter；25mL deionizations are added in into 0.2g solid matters Water obtains solid matter mixed liquor；Reuse HCl that mass fraction is 37% adjust solid matter mixed liquor to pH value be 1~ 2, then centrifuged, centrifugate is removed, obtains purple precipitation；Using distilled water to purple precipitation cleaning 3 times~5 times, then carry out It is dry, obtain four (carboxyl phenyl) zinc porphyrins；
    2., the NiO photocathodes that are sensitized ZnTHPP-bpy-Codmg self assemblies take out, washed 1 time, reused using absolute ethyl alcohol Deionized water is washed 1 time；
    3., repeat step 8 it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain the NiO photocathodes of ZnTPPC sensitizations；
    9th, the NiO photocathodes of ZnTPPC-bpy sensitizations are prepared：
    1., the ZnTPPC NiO photocathodes being sensitized are placed in temperature is 3min~7min to be heated in 65 DEG C~80 DEG C of baking oven, then soak Bubble 8h~10h in the methanol solution of the 4,4- bipyridyls of a concentration of 10mmol/L~15mmol/L；
    2., by ZnTPPC sensitization NiO photocathodes take out, wash 1 time with absolute ethyl alcohol, reuse deionized water washing 1 time；
    3., repeat step 9 it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain the NiO light of ZnTPPC-bpy sensitizations Cathode；
    Tenth, it impregnates, clean：
    1., the ZnTPPC-bpy NiO photocathodes being sensitized are placed in temperature is that 3min~7min is heated in 65 DEG C~80 DEG C of baking oven, It is immersed in the Co of a concentration of 10mmol/L~15mmol/L againII(dmgH)2Cl2In methanol solution, triethylamine is added, impregnates 8h ~10h；
    Step 10 1. described in CoII(dmgH)2Cl2Co in methanol solutionII(dmgH)2Cl2It prepares according to the following steps：It will 8.40mmol CoCL2 6H2Os are dissolved into 60mL acetone, add 16.81mmol dimethylglyoximes, then low whipping speed is 10min is stirred to react under 300r/min~500r/min, then is filtered, unreacted sediment is filtered out, obtains filtrate；It will Filtrate stands 12h, obtains green crystal；Green crystal is cleaned using acetone 3 times~5 times, obtains CoII(dmgH)2Cl2；
    Step 10 1. described in a concentration of 10mmol/L~15mmol/L CoII(dmgH)2Cl2Methanol solution and triethylamine Volume ratio is 100:1；
    2., by ZnTPPC-bpy sensitization NiO photocathodes take out, using absolute ethyl alcohol wash 1 time, reuse deionized water washing 1 time；
    3., the operation that repeats step 10 it is secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain based on zinc porphyrin and diacetyl The NiO photocathodes of oxime cobalt self assembly.
  2. 2. a kind of preparation side based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly according to claim 1 Method, it is characterised in that the NiCl described in step 12·6H2The mass ratio of O and P123 is 1:(0.5~0.65)；Institute in step 1 The NiCl stated2·6H2O and the mass ratio of deionized water are 1:(1.3~1.45)；NiCl described in step 12·6H2O and nothing The mass ratio of water-ethanol is 1:(3~3.15).
  3. 3. a kind of preparation side based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly according to claim 1 Method, it is characterised in that step 2 1. in the NiO compacted zone precursor liquids obtained in step 1 are spun to FTO by way of spin coating On the conducting surface of electro-conductive glass, it is then placed in dry 3min~5min in the baking oven that temperature is 65 DEG C~75 DEG C again；Step 2 is 2. It is middle to repeat step 2 1. 1 time~2 times, then 30min~40min is sintered at being 300 DEG C~350 DEG C in temperature, it obtains surface and contains The FTO electro-conductive glass of NiO compacted zones.
  4. 4. a kind of preparation side based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly according to claim 1 Method, it is characterised in that the mass ratio of NiO powders and terpinol described in step 3 is 1:(3.5~3.8)；Described in step 3 NiO powders and ethyl cellulose mass ratio be 1:(0.1~0.15)；NiO powders and absolute ethyl alcohol described in step 3 Mass ratio be 1:(3~4).
  5. 5. a kind of preparation side based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly according to claim 1 Method, it is characterised in that the slurry obtained in step 3 is printed onto in step 2 using the method for silk-screen printing in step 4 and is obtained Surface contain NiO compacted zones the NiO compacted zones of FTO electro-conductive glass on, then the thickness of slurry printing is put for 1 μm~2 μm In temperature be dry 3min~5min in 65 DEG C~75 DEG C of baking oven, then sintering 30min at being 400 DEG C~450 DEG C in temperature~ 40min obtains NiO blank after natural cooling.
  6. 6. a kind of preparation side based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly according to claim 1 Method, it is characterised in that step 5 1. in the NiO blank obtained in step 4 is placed in temperature is to heat 5min in 80 DEG C of baking oven ~8min, then be immersed in a concentration of 10mmol/L~13mmol/L four (p-hydroxybenzene) zinc porphyrins methanol solution in 8h~ 9h。
  7. 7. a kind of preparation side based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly according to claim 1 Method, it is characterised in that step 6 1. in by the NiO photocathodes of ZnTHPP sensitizations be placed in temperature be in 65 DEG C~70 DEG C of baking oven plus Hot 3min~5min, then be immersed in a concentration of 10mmol/L~13mmol/L 4,4- bipyridyls methanol solution in 8h~9h.
  8. 8. a kind of preparation side based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly according to claim 1 Method, it is characterised in that step 7 1. in the NiO photocathodes of ZnTHPP-bpy sensitizations are placed in temperature is 65 DEG C~70 DEG C of baking oven Middle heating 3min~5min, then it is immersed in the Co of a concentration of 10mmol/L~15mmol/LII(dmgH)2Cl2In methanol solution, then Triethylamine is added in, impregnates 8h~9h.
  9. 9. a kind of preparation side based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly according to claim 1 Method, it is characterised in that step 8 1. in the NiO photocathodes that ZnTHPP-bpy-Codmg self assemblies are sensitized are placed in temperature as 80 DEG C Baking oven in heat 5min~8min, then be immersed in four (carboxyl phenyl) zinc porphyrins of a concentration of 10mmol/L~13mmol/L 8h~9h is impregnated in methanol solution.
  10. 10. a kind of preparation side based on zinc porphyrin Yu the NiO photocathodes of dimethylglyoxime cobalt self assembly according to claim 1 Method, it is characterised in that step 9 1. in by the NiO photocathodes of ZnTPPC sensitizations be placed in temperature be in 65 DEG C~70 DEG C of baking oven plus Hot 3min~5min, then be immersed in a concentration of 10mmol/L~13mmol/L 4,4- bipyridyls methanol solution in 8h~9h.
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