CN106676569A - Preparation method of NiO photocathode based on self-assembly of zinc porphyrin and cobalt dimethylglyoximate - Google Patents
Preparation method of NiO photocathode based on self-assembly of zinc porphyrin and cobalt dimethylglyoximate Download PDFInfo
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- CN106676569A CN106676569A CN201710042204.5A CN201710042204A CN106676569A CN 106676569 A CN106676569 A CN 106676569A CN 201710042204 A CN201710042204 A CN 201710042204A CN 106676569 A CN106676569 A CN 106676569A
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Abstract
The invention relates to a preparation method of a NiO photocathode based on self-assembly of zinc porphyrin and cobalt dimethylglyoximate. The preparation method aims at solving the problems that existing photocathode preparation methods are complex, photocathodes are low in water decomposition efficiency, and the hydrogen production speed is low. The preparation method comprises the steps of 1, preparing a precursor solution of a NiO compact layer; 2, preparing the NiO compact layer; 3, preparing slurry; 4, preparing a NiO blank piece; 5, preparing a NiO photocathode sensitized by ZnTHPP; 6, preparing a NiO photocathode sensitized by ZnTHPP-bpy; 7, preparing a NiO photocathode sensitized by self-assembly of ZnTHPP-bpy-Codmg; 8, preparing a NiO photocathode sensitized by ZnTPPC; 9, preparing a NiO photocathode sensitized by ZnTPPC-bpy; and 10, conducting soaking and cleaning. By means of the preparation method, the NiO photocathode based on self-assembly of the zinc porphyrin and the cobalt dimethylglyoximate can be obtained.
Description
Technical field
The present invention relates to a kind of method for preparing NiO photocathodes.
Background technology
How a great challenge that continuable 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 DSSC structure
Positive energy decomposition water produces hydrogen, realizes conversion of the solar energy to Hydrogen Energy, can perfectly solve the energy that the mankind are faced at present
Crisis and environmental problem.Have currently used for the photosensitizer for building decomposition water photocathode：Compound containing noble ruthenium, porphyrin and its
Derivant and pure organic dye etc.；Releasing hydrogen catalyst has：The compound of the elements such as iron content, cobalt, nickel.And want to realize photocathode point
Solution water efficiency reaches maximization, needs just photosensitizer to combine with catalyst, synergism.Therefore it is rational
Photocathode assembling mode is particularly important for photocathode is built.
The content of the invention
The invention aims to solve that the existing method for preparing photocathode is complicated and photocathode decomposition water efficiency is low, hydrogen is produced
Slow-footed problem, and a kind of preparation method based on zinc porphyrin and the NiO photocathodes of diacetyldioxime cobalt self assembly is provided.
A kind of preparation method based on zinc porphyrin and the NiO photocathodes of diacetyldioxime cobalt self assembly, specifically by following step
Suddenly complete：
First, NiO compacted zone precursor liquids are prepared：By NiCl2·6H2The mixing of O, P123, deionized water and dehydrated alcohol, stirring
Put into after uniform in centrifuge and be centrifuged, remove precipitation, the supernatant for obtaining is NiO compacted zone precursor liquids；
NiCl described in step one2·6H2The mass ratio of O and P123 is 1:(0.5~0.8)；
NiCl described in step one2·6H2O is 1 with the mass ratio of deionized water:(1.3~1.66)；
NiCl described in step one2·6H2O is 1 with the mass ratio of dehydrated alcohol:(3~3.3)；
The centrifugal speed of the centrifuge described in step one be 7000r/min~9000r/min, centrifugation time be 3min~
7min；
2nd, NiO compacted zones are prepared：
1., the NiO compacted zone precursor liquids obtained in step one are spun to into leading for FTO electro-conductive glass by way of spin coating
On electric face, then it is placed in again in the baking oven that temperature is 65 DEG C~80 DEG C and is dried 3min~7min；
2., repeat step two 1. 1 time~4 times, then 30min~60min is sintered in the case where temperature is for 300 DEG C~350 DEG C, 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 powder body, terpineol and ethyl cellulose are distributed in dehydrated alcohol, 2 are aged after stirring at room temperature
~3 days, obtain slurry；
NiO powder body described in step 3 is 1 with the mass ratio of terpineol:(3.5~4)；
NiO powder body described in step 3 is 1 with the mass ratio of ethyl cellulose:(0.1~0.2)；
NiO powder body described in step 3 is 1 with the mass ratio of dehydrated alcohol:(3~5)；
NiO powder body described in step 3 is the spherical alumina nickel that particle diameter is 30nm；
The 4th, the slurry obtained in step 3 is printed onto the surface obtained in step 2 using the method for silk screen printing to contain
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, is subsequently placed in temperature for 65
DEG C~80 DEG C of baking oven in be dried 3min~7min, then be to sinter 30min~60min at 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 into heating 5min~10min in the baking oven that temperature is 80 DEG C, then is soaked
Steep 8h~10h in methanol solution of the concentration for four (p-hydroxybenzene) zinc porphyrins of 10mmol/L~15mmol/L；
2., NiO blank is taken out, first by absolute ethanol washing 1 time, deionized water wash 1 time is reused；
3., repeat step five 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
Prepare according to following steps：
(1), 6.5g hydroxy benzaldehydes are dissolved in 240mL propanoic acid, then are heated to reflux in the case where temperature is for 140 DEG C, then
4.3mL pyrroles is added drop-wise in propanoic acid in 5min, then 1.5h is heated to reflux in the case where temperature is for 140 DEG C, be cooled to room temperature, then added
Enter 100mL methanol, then the cooling and standings 0.5h under ice bath, have violet solid to separate out, then carry out sucking filtration, using methanol filter cake is cleaned
It is colourless to cleanout fluid, obtain solid matter；Solid matter is dissolved in mixed liquor of the dichloromethane with methanol, 12h is stood, then
Sucking filtration is carried out, purple crystals, as tetrahydroxy phenyl porphyrin are obtained；Described dichloromethane and dichloromethane in the mixed liquor of methanol
Alkane is 1 with the volume ratio of methanol:1；
(2), 0.1064g tetrahydroxy phenyl porphyrins and 0.5054g zinc acetates are mixed, agate mortar is reused and is ground
30min, obtains mixed-powder A；Mixed-powder A is distributed in 50mL dimethylformamides, then is heated in the case where temperature is for 150 DEG C
Backflow 45min, then pour in 100mL frozen water, then 12h is stood in the case where temperature is for -4 DEG C, then sucking filtration is carried out, four are obtained (to hydroxyl
Phenyl) zinc porphyrin；
6th, the NiO photocathodes of ZnTHPP-bpy sensitizations are prepared：
1., the NiO photocathodes that ZnTHPP is sensitized are placed in into heating 3min~7min in the baking oven that temperature is 65 DEG C~80 DEG C,
8h~10h in the methanol solution of the 4,4- bipyridyls that concentration is 10mmol/L~15mmol/L is immersed in again；
2., the NiO photocathodes for being sensitized ZnTHPP take out, and first by absolute ethanol washing 1 time, reuse deionized water
Washing 1 time；
3., repeat step six 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., by ZnTHPP-bpy be sensitized NiO photocathodes be placed in the baking oven that temperature is 65 DEG C~80 DEG C heat 3min~
7min, then it is immersed in the Co that concentration is 10mmol/L~15mmol/LII(dmgH)2Cl2In methanol solution, triethylamine is added,
Immersion 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 cobalt chloride hexahydrate is dissolved in 60mL acetone, 16.81mmol diacetyldioximes are added, then in stirring
Speed is stirring reaction 10min under 300r/min~500r/min, then is filtered, and filters out unreacted precipitate, is obtained
Filtrate；Filtrate is stood into 12h, green crystal is obtained；Using acetone cleaning green crystal 3 times~5 times, Co is obtainedII(dmgH)2Cl2；
Step 7 1. described in concentration for 10mmol/L~15mmol/L CoII(dmgH)2Cl2Methanol solution and three second
The volume ratio of amine is 100:1；
2., the NiO photocathodes for being sensitized ZnTHPP-bpy take out, and using absolute ethanol washing 1 time, reuse deionized water
Washing 1 time；
3., repeat step seven it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain ZnTHPP-bpy-Codmg from
The NiO photocathodes of assembling 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 are heated
5min~10min, then be immersed in the methanol solution of four (carboxyl phenyl) zinc porphyrins that concentration is 10mmol/L~15mmol/L
Immersion 8h~10h；
Step 8 1. described in four (carboxyl phenyl) zinc porphyrins methanol solution in four (carboxyl phenyl) zinc porphyrins it is concrete
Prepare according to the following steps：
(1), 3.11g p formylbenzoic acid methyl ester is dissolved in 50mL propanoic acid, 3mL dimethyl sulfoxide is added, is obtained
To mixed liquor；Mixed liquor is heated to into 130 DEG C, then 1.3mL pyrroles is added drop-wise in mixed liquor in 5min, then be in temperature
40min is heated to reflux at 130 DEG C, then carries out filtration under diminished pressure, obtain filter cake；Filter cake is cleaned 3 times~5 times using propanoic acid, then is made
With washes of absolute alcohol 3 times~5 times, then filter cake is dried, obtains purple crystals, as four ester group phenyl porphyrins；
(2), the ester group phenyl porphyrins of 250mg tetra- and the acetate hydrate zinc of 400mg bis- are mixed, 30mL chloroforms and 10mL is added
Methanol, obtains reactant liquor；Reactant liquor is heated to reflux into 4h in the case where temperature is for 65 DEG C, reaction carries out vacuum distillation after terminating, and removes
Solvent, adds 25mL tetrahydrofurans and potassium hydroxide aqueous solution that 5mL mass fractions are 4%, then temperature be at 60 DEG C plus
Hot reflux 24h, then vacuum distillation is carried out, remove solvent；Obtain solid matter；25mL deionizations are added in 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 be centrifuged, centrifugal liquid is removed, obtain purple precipitation；Using distilled water to purple precipitation cleaning 3 times~5 times, then carry out
It is dried, obtains four (carboxyl phenyl) zinc porphyrins；
2., the NiO photocathodes for being sensitized ZnTHPP-bpy-Codmg self assemblies take out, using absolute ethanol washing 1 time, then
Using deionized water wash 1 time；
3., repeat step eight it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain the NiO light of ZnTPPC sensitizations
Negative electrode；
9th, the NiO photocathodes of ZnTPPC-bpy sensitizations are prepared：
1., the NiO photocathodes that ZnTPPC is sensitized are placed in into heating 3min~7min in the baking oven that temperature is 65 DEG C~80 DEG C,
8h~10h in the methanol solution of the 4,4- bipyridyls that concentration is 10mmol/L~15mmol/L is immersed in again；
2., the NiO photocathodes for being sensitized ZnTPPC take out, and with absolute ethanol washing 1 time, reuse deionized water wash 1
It is secondary；
3., repeat step nine it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain ZnTPPC-bpy sensitizations
NiO photocathodes；
Tenth, immersion, cleaning：
1., by ZnTPPC-bpy be sensitized NiO photocathodes be placed in the baking oven that temperature is 65 DEG C~80 DEG C heat 3min~
7min, then it is immersed in the Co that concentration is 10mmol/L~15mmol/LII(dmgH)2Cl2In methanol solution, triethylamine is added,
Immersion 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 cobalt chloride hexahydrate is dissolved in 60mL acetone, 16.81mmol diacetyldioximes, then low whipping speed is added
For stirring reaction 10min under 300r/min~500r/min, then filtered, filtered out unreacted precipitate, obtained filtrate；
Filtrate is stood into 12h, green crystal is obtained；Using acetone cleaning green crystal 3 times~5 times, Co is obtainedII(dmgH)2Cl2；
Step 10 1. described in concentration for 10mmol/L~15mmol/L CoII(dmgH)2Cl2Methanol solution and three second
The volume ratio of amine is 100:1；
2., the NiO photocathodes for being sensitized ZnTPPC-bpy take out, and using absolute ethanol washing 1 time, reuse deionized water
Washing 1 time；
3., the operation of repeat step ten 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 is with advantages below：
First, have been reported release hydrogen photocathode commonly use more complicated assembling mode build photocathode and stability compared with
Difference, the present invention adopts a kind of simple method by two kinds of photosensitizer four (p-hydroxybenzene) zinc porphyrin (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 can be stable raising hydrogen generation efficiency because light excites porphyrin directly by electron transfer
Hydrion in feedwater, such catalytic effect is low, adds CoII(dmgH)2Cl2(Codmg) after catalyst, photoelectric current is improved,
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 is changed into hydrogen, and catalytic effect is improved；
2nd, the NiO photocathodes of ZnTHPP-bpy-Codmg self assemblies sensitization adsorb ZnTHPP relative to simple in the present invention
NiO photocathode photocurrent responses be significantly improved, efficiency improves 50%~55%, and current stabilization；
What the 3rd, prepared by the present invention is adsorbed based on zinc porphyrin and the NiO photocathodes of diacetyldioxime cobalt self assembly relative to simple
The NiO photocathode photocurrent responses of ZnTPPC are significantly improved, and efficiency improves 75%~80%, and current stabilization.
The present invention can obtain a kind of preparation method based on zinc porphyrin and the NiO photocathodes of diacetyldioxime cobalt self assembly.
Description of the drawings
Fig. 1 is photoelectric current comparison diagram, and 1 is the NiO photocathodes of the ZnTHPP sensitizations obtained in the step 5 of embodiment one in Fig. 1
Photocurrent curve, 2 is the NiO photocathodes of the ZnTHPP-bpy-Codmg self assemblies sensitization obtained in embodiment one step 7
Photocurrent curve；
Fig. 2 is solid ultraviolet-ray visible absorbing figure comparison diagram, and 1 is that the ZnTHPP obtained in the step 5 of embodiment one is quick in Fig. 2
The solid ultraviolet-ray visible absorbing curve of the NiO photocathodes of change, 2 is the ZnTHPP-bpy- obtained in the step 7 of embodiment one
The solid ultraviolet-ray visible absorbing curve of the NiO photocathodes of Codmg self assemblies sensitization；
Fig. 3 is photoelectric current comparison diagram, and 1 is the NiO photocathodes of the ZnTPPC sensitizations obtained in the step 8 of embodiment one in Fig. 3
Photocurrent curve, 2 is the NiO photocathodes based on zinc porphyrin and diacetyldioxime cobalt self assembly that the step 10 of embodiment one is obtained
Photocurrent curve；
Fig. 4 is solid ultraviolet-ray visible absorbing figure comparison diagram, and 1 is that the ZnTPPC obtained in the step 8 of embodiment one is quick in Fig. 4
The solid ultraviolet-ray visible absorbing curve of the NiO photocathodes of change, 2 be the step 10 of embodiment one 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 the schematic flow sheet of the step 5 of embodiment one to step 7；
Fig. 6 is the schematic flow sheet of the step 8 of embodiment one to step 10.
Specific embodiment
Technical scheme is further described with reference to the accompanying drawings and examples, but not limitation thus,
It is every technical solution of the present invention to be modified or equivalent, without deviating from the spirit and scope of technical solution of the present invention,
All should cover in protection scope of the present invention.
Specific embodiment one：Present embodiment is a kind of NiO time based on zinc porphyrin and diacetyldioxime cobalt self assembly
The preparation method of pole, it is characterised in that what the method was specifically realized by the following steps：
First, NiO compacted zone precursor liquids are prepared：By NiCl2·6H2The mixing of O, P123, deionized water and dehydrated alcohol, stirring
Put into after uniform in centrifuge and be centrifuged, remove precipitation, the supernatant for obtaining is NiO compacted zone precursor liquids；
NiCl described in step one2·6H2The mass ratio of O and P123 is 1:(0.5~0.8)；
NiCl described in step one2·6H2O is 1 with the mass ratio of deionized water:(1.3~1.66)；
NiCl described in step one2·6H2O is 1 with the mass ratio of dehydrated alcohol:(3~3.3)；
The centrifugal speed of the centrifuge described in step one be 7000r/min~9000r/min, centrifugation time be 3min~
7min；
2nd, NiO compacted zones are prepared：
1., the NiO compacted zone precursor liquids obtained in step one are spun to into leading for FTO electro-conductive glass by way of spin coating
On electric face, then it is placed in again in the baking oven that temperature is 65 DEG C~80 DEG C and is dried 3min~7min；
2., repeat step two 1. 1 time~4 times, then 30min~60min is sintered in the case where temperature is for 300 DEG C~350 DEG C, 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 powder body, terpineol and ethyl cellulose are distributed in dehydrated alcohol, 2 are aged after stirring at room temperature
~3 days, obtain slurry；
NiO powder body described in step 3 is 1 with the mass ratio of terpineol:(3.5~4)；
NiO powder body described in step 3 is 1 with the mass ratio of ethyl cellulose:(0.1~0.2)；
NiO powder body described in step 3 is 1 with the mass ratio of dehydrated alcohol:(3~5)；
NiO powder body described in step 3 is the spherical alumina nickel that particle diameter is 30nm；
The 4th, the slurry obtained in step 3 is printed onto the surface obtained in step 2 using the method for silk screen printing to contain
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, is subsequently placed in temperature for 65
DEG C~80 DEG C of baking oven in be dried 3min~7min, then be to sinter 30min~60min at 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 into heating 5min~10min in the baking oven that temperature is 80 DEG C, then is soaked
Steep 8h~10h in methanol solution of the concentration for four (p-hydroxybenzene) zinc porphyrins of 10mmol/L~15mmol/L；
2., NiO blank is taken out, first by absolute ethanol washing 1 time, deionized water wash 1 time is reused；
3., repeat step five 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
Prepare according to following steps：
(1), 6.5g hydroxy benzaldehydes are dissolved in 240mL propanoic acid, then are heated to reflux in the case where temperature is for 140 DEG C, then
4.3mL pyrroles is added drop-wise in propanoic acid in 5min, then 1.5h is heated to reflux in the case where temperature is for 140 DEG C, be cooled to room temperature, then added
Enter 100mL methanol, then the cooling and standings 0.5h under ice bath, have violet solid to separate out, then carry out sucking filtration, using methanol filter cake is cleaned
It is colourless to cleanout fluid, obtain solid matter；Solid matter is dissolved in mixed liquor of the dichloromethane with methanol, 12h is stood, then
Sucking filtration is carried out, purple crystals, as tetrahydroxy phenyl porphyrin are obtained；Described dichloromethane and dichloromethane in the mixed liquor of methanol
Alkane is 1 with the volume ratio of methanol:1；
(2), 0.1064g tetrahydroxy phenyl porphyrins and 0.5054g zinc acetates are mixed, agate mortar is reused and is ground
30min, obtains mixed-powder A；Mixed-powder A is distributed in 50mL dimethylformamides, then is heated in the case where temperature is for 150 DEG C
Backflow 45min, then pour in 100mL frozen water, then 12h is stood in the case where temperature is for -4 DEG C, then sucking filtration is carried out, four are obtained (to hydroxyl
Phenyl) zinc porphyrin；
6th, the NiO photocathodes of ZnTHPP-bpy sensitizations are prepared：
1., the NiO photocathodes that ZnTHPP is sensitized are placed in into heating 3min~7min in the baking oven that temperature is 65 DEG C~80 DEG C,
8h~10h in the methanol solution of the 4,4- bipyridyls that concentration is 10mmol/L~15mmol/L is immersed in again；
2., the NiO photocathodes for being sensitized ZnTHPP take out, and first by absolute ethanol washing 1 time, reuse deionized water
Washing 1 time；
3., repeat step six 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., by ZnTHPP-bpy be sensitized NiO photocathodes be placed in the baking oven that temperature is 65 DEG C~80 DEG C heat 3min~
7min, then it is immersed in the Co that concentration is 10mmol/L~15mmol/LII(dmgH)2Cl2In methanol solution, triethylamine is added,
Immersion 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 cobalt chloride hexahydrate is dissolved in 60mL acetone, 16.81mmol diacetyldioximes are added, then in stirring
Speed is stirring reaction 10min under 300r/min~500r/min, then is filtered, and filters out unreacted precipitate, is obtained
Filtrate；Filtrate is stood into 12h, green crystal is obtained；Using acetone cleaning green crystal 3 times~5 times, Co is obtainedII(dmgH)2Cl2；
Step 7 1. described in concentration for 10mmol/L~15mmol/L CoII(dmgH)2Cl2Methanol solution and three second
The volume ratio of amine is 100:1；
2., the NiO photocathodes for being sensitized ZnTHPP-bpy take out, and using absolute ethanol washing 1 time, reuse deionized water
Washing 1 time；
3., repeat step seven it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain ZnTHPP-bpy-Codmg from
The NiO photocathodes of assembling 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 are heated
5min~10min, then be immersed in the methanol solution of four (carboxyl phenyl) zinc porphyrins that concentration is 10mmol/L~15mmol/L
Immersion 8h~10h；
Step 8 1. described in four (carboxyl phenyl) zinc porphyrins methanol solution in four (carboxyl phenyl) zinc porphyrins it is concrete
Prepare according to the following steps：
(1), 3.11g p formylbenzoic acid methyl ester is dissolved in 50mL propanoic acid, 3mL dimethyl sulfoxide is added, is obtained
To mixed liquor；Mixed liquor is heated to into 130 DEG C, then 1.3mL pyrroles is added drop-wise in mixed liquor in 5min, then be in temperature
40min is heated to reflux at 130 DEG C, then carries out filtration under diminished pressure, obtain filter cake；Filter cake is cleaned 3 times~5 times using propanoic acid, then is made
With washes of absolute alcohol 3 times~5 times, then filter cake is dried, obtains purple crystals, as four ester group phenyl porphyrins；
(2), the ester group phenyl porphyrins of 250mg tetra- and the acetate hydrate zinc of 400mg bis- are mixed, 30mL chloroforms and 10mL is added
Methanol, obtains reactant liquor；Reactant liquor is heated to reflux into 4h in the case where temperature is for 65 DEG C, reaction carries out vacuum distillation after terminating, and removes
Solvent, adds 25mL tetrahydrofurans and potassium hydroxide aqueous solution that 5mL mass fractions are 4%, then temperature be at 60 DEG C plus
Hot reflux 24h, then vacuum distillation is carried out, remove solvent；Obtain solid matter；25mL deionizations are added in 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 be centrifuged, centrifugal liquid is removed, obtain purple precipitation；Using distilled water to purple precipitation cleaning 3 times~5 times, then carry out
It is dried, obtains four (carboxyl phenyl) zinc porphyrins；
2., the NiO photocathodes for being sensitized ZnTHPP-bpy-Codmg self assemblies take out, using absolute ethanol washing 1 time, then
Using deionized water wash 1 time；
3., repeat step eight it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain the NiO light of ZnTPPC sensitizations
Negative electrode；
9th, the NiO photocathodes of ZnTPPC-bpy sensitizations are prepared：
1., the NiO photocathodes that ZnTPPC is sensitized are placed in into heating 3min~7min in the baking oven that temperature is 65 DEG C~80 DEG C,
8h~10h in the methanol solution of the 4,4- bipyridyls that concentration is 10mmol/L~15mmol/L is immersed in again；
2., the NiO photocathodes for being sensitized ZnTPPC take out, and with absolute ethanol washing 1 time, reuse deionized water wash 1
It is secondary；
3., repeat step nine it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain ZnTPPC-bpy sensitizations
NiO photocathodes；
Tenth, immersion, cleaning：
1., by ZnTPPC-bpy be sensitized NiO photocathodes be placed in the baking oven that temperature is 65 DEG C~80 DEG C heat 3min~
7min, then it is immersed in the Co that concentration is 10mmol/L~15mmol/LII(dmgH)2Cl2In methanol solution, triethylamine is added,
Immersion 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 cobalt chloride hexahydrate is dissolved in 60mL acetone, 16.81mmol diacetyldioximes, then low whipping speed is added
For stirring reaction 10min under 300r/min~500r/min, then filtered, filtered out unreacted precipitate, obtained filtrate；
Filtrate is stood into 12h, green crystal is obtained；Using acetone cleaning green crystal 3 times~5 times, Co is obtainedII(dmgH)2Cl2；
Step 10 1. described in concentration for 10mmol/L~15mmol/L CoII(dmgH)2Cl2Methanol solution and three second
The volume ratio of amine is 100:1；
2., the NiO photocathodes for being sensitized ZnTPPC-bpy take out, and using absolute ethanol washing 1 time, reuse deionized water
Washing 1 time；
3., the operation of repeat step ten 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 applied to ZnTHPP and ZnTPPC as sensitizer, diacetyldioxime cobalt complex CoII(dmgH)2Cl2As catalyst, and hydrogen photocathode is released by what self assembly mode built as linking group with 4,4- bipyridyls.
With existing Technical comparing, this embodiment presents the advantage that：
First, have been reported release hydrogen photocathode commonly use more complicated assembling mode build photocathode and stability compared with
Difference, present embodiment using a kind of simple method by two kinds of photosensitizer four (p-hydroxybenzene) zinc porphyrin (ZnTHPP) and
Four (carboxyl phenyl) zinc porphyrins (ZnTPPC) and catalyst CoII(dmgH)2Cl2(Codmg) by matching somebody with somebody with 4,4- bipyridyls (bpy)
Position self assembly release hydrogen photocathode to build, and can be stable raising hydrogen generation efficiency because light excite porphyrin directly by electronics turn
The hydrion moved in feedwater, such catalytic effect is low, adds CoII(dmgH)2Cl2(Codmg) after catalyst, photoelectric current is carried
Height, illustrates that electronics is transferred to Co from porphyrin under illumination conditionII(dmgH)2Cl2(Codmg) on catalyst, and then in catalytic water
Hydrion be changed into hydrogen, catalytic effect is improved；
2nd, the NiO photocathodes of ZnTHPP-bpy-Codmg self assemblies sensitization adsorb relative to simple in present embodiment
The NiO photocathode photocurrent responses of ZnTHPP are significantly improved, and efficiency improves 50%~55%, and current stabilization；
3rd, present embodiment prepare based on zinc porphyrin and the NiO photocathodes of diacetyldioxime 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 and the NiO photocathodes of diacetyldioxime cobalt self assembly
Method.
Specific embodiment two：Present embodiment is with the difference of specific embodiment one：Described in step
NiCl2·6H2The mass ratio of O and P123 is 1:(0.5~0.65)；NiCl described in step one2·6H2O and deionized water
Mass ratio is 1:(1.3~1.45)；NiCl described in step one2·6H2O is 1 with the mass ratio of dehydrated alcohol:(3~
3.15).Other steps are identical with specific embodiment one.
Specific embodiment three：Present embodiment is with the difference of specific embodiment one or one of two：Step 2 1. in
On the conducting surface of FTO electro-conductive glass, then the NiO compacted zone precursor liquids obtained in step one are spun to by way of spin coating
It is placed in again in the baking oven that temperature is 65 DEG C~75 DEG C and is dried 3min~5min；Step 2 2. middle repeat step two 1. 1 time~2 times,
Again 30min~40min is sintered in the case where temperature is for 300 DEG C~350 DEG C, obtain the FTO electro-conductive glass that NiO compacted zones are contained on surface.
Other steps are identical with specific embodiment one or two.
Specific embodiment four：One of present embodiment and specific embodiment one to three difference is：Institute in step 3
The NiO powder body stated is 1 with the mass ratio of terpineol:(3.5~3.8)；NiO powder body described in step 3 and ethyl cellulose
Mass ratio is 1:(0.1~0.15)；NiO powder body described in step 3 is 1 with the mass ratio of dehydrated alcohol:(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 is：Adopt in step 4
The slurry obtained in step 3 is printed onto the surface obtained in step 2 with the method for silk screen printing 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
3min~5min is dried in baking oven, then 30min~40min is sintered in the case where temperature is for 400 DEG C~450 DEG C, 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 is：Step 5 1. in
The NiO blank obtained in step 4 is placed in into heating 5min~8min in the baking oven that temperature is 80 DEG C, then is immersed in concentration and be
8h~9h in the methanol solution of four (p-hydroxybenzene) zinc porphyrins of 10mmol/L~13mmol/L.Other steps be embodied as
Mode one to five is identical.
Specific embodiment seven：One of present embodiment and specific embodiment one to six difference is：Step 6 1. in
The NiO photocathodes that ZnTHPP is sensitized are placed in into heating 3min~5min in the baking oven that temperature is 65 DEG C~70 DEG C, then are 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 is：Step 7 1. in
The NiO photocathodes that ZnTHPP-bpy is sensitized are placed in into heating 3min~5min in the baking oven that temperature is 65 DEG C~70 DEG C, then are soaked
In the Co that concentration is 10mmol/L~15mmol/LII(dmgH)2Cl2In methanol solution, triethylamine is added, soak 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 is：Step 8 1. in
The NiO photocathodes that ZnTHPP-bpy-Codmg self assemblies are sensitized are placed in into heating 5min~8min in the baking oven that temperature is 80 DEG C,
It is immersed in again in the methanol solution of four (carboxyl phenyl) zinc porphyrins that concentration is 10mmol/L~13mmol/L and soaks 8h~9h.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 is：Step 9 1. in
The NiO photocathodes that ZnTPPC is sensitized are placed in into heating 3min~5min in the baking oven that temperature is 65 DEG C~70 DEG C, then are 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 examples：
Embodiment one：A kind of preparation method based on zinc porphyrin and the NiO photocathodes of diacetyldioxime cobalt self assembly, specifically
Complete according to the following steps：
First, NiO compacted zone precursor liquids are prepared：By NiCl2·6H2The mixing of O, P123, deionized water and dehydrated alcohol, stirring
Put into after uniform in centrifuge and be centrifuged, remove precipitation, the supernatant for obtaining is NiO compacted zone precursor liquids；
NiCl described in step one2·6H2The mass ratio of O and P123 is 1:0.8；
NiCl described in step one2·6H2O is 1 with the mass ratio of deionized water:1.66；
NiCl described in step one2·6H2O is 1 with the mass ratio of dehydrated alcohol:3.3；
The centrifugal speed of the centrifuge described in step one is 8000r/min, and centrifugation time is 5min；
2nd, NiO compacted zones are prepared：
1., the NiO compacted zone precursor liquids obtained in step one are spun to into leading for FTO electro-conductive glass by way of spin coating
On electric face, then it is placed in again in the baking oven that temperature is 80 DEG C and is dried 5min；
2., repeat step two 1. 1 time, then 30min is sintered in the case where temperature is for 350 DEG C, 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 powder body, terpineol and ethyl cellulose are distributed in dehydrated alcohol, 2 are aged after stirring at room temperature
~3 days, obtain slurry；
NiO powder body described in step 3 is 1 with the mass ratio of terpineol:3.5；
NiO powder body described in step 3 is 1 with the mass ratio of ethyl cellulose:0.15；
NiO powder body described in step 3 is 1 with the mass ratio of dehydrated alcohol:3；
NiO powder body described in step 3 is the spherical alumina nickel that particle diameter is 30nm；
The 4th, the slurry obtained in step 3 is printed onto the surface obtained in step 2 using the method for silk screen printing to contain
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, is subsequently placed in temperature for 80
DEG C baking oven in be dried 5min, then be to sinter 30min at 450 DEG C in temperature, NiO blank is 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 is taken out, first by absolute ethanol washing 1 time, deionized water wash 1 time is reused；
3., repeat step five 2. three times, then 4h is dried at room temperature for, 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
Prepare according to following steps：
(1), 6.5g hydroxy benzaldehydes are dissolved in 240mL propanoic acid, then are heated to reflux in the case where temperature is for 140 DEG C, then
4.3mL pyrroles is added drop-wise in propanoic acid in 5min, then 1.5h is heated to reflux in the case where temperature is for 140 DEG C, be cooled to room temperature, then added
Enter 100mL methanol, then the cooling and standings 0.5h under ice bath, have violet solid to separate out, then carry out sucking filtration, using methanol filter cake is cleaned
It is colourless to cleanout fluid, obtain solid matter；Solid matter is dissolved in mixed liquor of the dichloromethane with methanol, 12h is stood, then
Sucking filtration is carried out, purple crystals, as tetrahydroxy phenyl porphyrin are obtained；Described dichloromethane and dichloromethane in the mixed liquor of methanol
Alkane is 1 with the volume ratio of methanol:1；
(2), 0.1064g tetrahydroxy phenyl porphyrins and 0.5054g zinc acetates are mixed, agate mortar is reused and is ground
30min, obtains mixed-powder A；Mixed-powder A is distributed in 50mL dimethylformamides, then is heated in the case where temperature is for 150 DEG C
Backflow 45min, then pour in 100mL frozen water, then 12h is stood in the case where temperature is for -4 DEG C, then sucking filtration is carried out, four are obtained (to hydroxyl
Phenyl) zinc porphyrin；
6th, the NiO photocathodes of ZnTHPP-bpy sensitizations are prepared：
1., the NiO photocathodes that ZnTHPP is sensitized are placed in the baking oven that temperature is 80 DEG C and heat 5min, then be immersed in concentration
For 8h in the methanol solution of the 4,4- bipyridyls of 10mmol/L；
2., the NiO photocathodes for being sensitized ZnTHPP take out, and first by absolute ethanol washing 1 time, reuse deionized water
Washing 1 time；
3., repeat step six 2. three times, then 4h is dried at room temperature for, obtain the NiO photocathodes of ZnTHPP-bpy sensitizations；
7th, the NiO photocathodes of ZnTHPP-bpy-Codmg self assemblies sensitization are prepared：
1., the NiO photocathodes that ZnTHPP-bpy is sensitized are placed in the baking oven that temperature is 80 DEG C and heat 5min, then be immersed in
Concentration is the Co of 10mmol/LII(dmgH)2Cl2In methanol solution, triethylamine is added, soak 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 cobalt chloride hexahydrate is dissolved in 60mL acetone, 16.81mmol diacetyldioximes are added, then in stirring
Speed is stirring reaction 10min under 400r/min, then is filtered, and filters out unreacted precipitate, obtains filtrate；By filtrate
12h is stood, green crystal is obtained；Using acetone cleaning green crystal 5 times, Co is obtainedII(dmgH)2Cl2；
Step 7 1. described in concentration for 10mmol/L CoII(dmgH)2Cl2The volume ratio of methanol solution and triethylamine
For 100:1；
2., the NiO photocathodes for being sensitized ZnTHPP-bpy take out, and using absolute ethanol washing 1 time, reuse deionized water
Washing 1 time；
3., repeat step seven 2. three times, then 4h is dried at room temperature for, 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 are heated
5min, then be immersed in concentration be 10mmol/L four (carboxyl phenyl) zinc porphyrins methanol solution in soak 8h；
Step 8 1. described in four (carboxyl phenyl) zinc porphyrins methanol solution in four (carboxyl phenyl) zinc porphyrins it is concrete
Prepare according to the following steps：
(1), 3.11g p formylbenzoic acid methyl ester is dissolved in 50mL propanoic acid, 3mL dimethyl sulfoxide is added, is obtained
To mixed liquor；Mixed liquor is heated to into 130 DEG C, then 1.3mL pyrroles is added drop-wise in mixed liquor in 5min, then be in temperature
40min is heated to reflux at 130 DEG C, then carries out filtration under diminished pressure, obtain filter cake；Filter cake is cleaned 5 times using propanoic acid, is reused anhydrous
Ethanol purge 5 times, then filter cake is dried, obtain purple crystals, as four ester group phenyl porphyrins；
(2), the ester group phenyl porphyrins of 250mg tetra- and the acetate hydrate zinc of 400mg bis- are mixed, 30mL chloroforms and 10mL is added
Methanol, obtains reactant liquor；Reactant liquor is heated to reflux into 4h in the case where temperature is for 65 DEG C, reaction carries out vacuum distillation after terminating, and removes
Solvent, adds 25mL tetrahydrofurans and potassium hydroxide aqueous solution that 5mL mass fractions are 4%, then temperature be at 60 DEG C plus
Hot reflux 24h, then vacuum distillation is carried out, remove solvent；Obtain solid matter；25mL deionizations are added in 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 be centrifuged, centrifugal liquid is removed, obtain purple precipitation；Using distilled water to purple precipitation cleaning 3 times~5 times, then carry out
It is dried, obtains four (carboxyl phenyl) zinc porphyrins；
2., the NiO photocathodes for being sensitized ZnTHPP-bpy-Codmg self assemblies take out, using absolute ethanol washing 1 time, then
Using deionized water wash 1 time；
3., repeat step eight 2. three times, then 4h is dried at room temperature for, obtain the NiO photocathodes of ZnTPPC sensitizations；
9th, the NiO photocathodes of ZnTPPC-bpy sensitizations are prepared：
1., the NiO photocathodes that ZnTPPC is sensitized are placed in the baking oven that temperature is 80 DEG C and heat 5min, then be immersed in concentration
For 8h in the methanol solution of the 4,4- bipyridyls of 10mmol/L；
2., the NiO photocathodes for being sensitized ZnTPPC take out, and with absolute ethanol washing 1 time, reuse deionized water wash 1
It is secondary；
3., repeat step nine 2. three times, then 4h is dried at room temperature for, obtain the NiO photocathodes of ZnTPPC-bpy sensitizations；
Tenth, immersion, cleaning：
1., the NiO photocathodes that ZnTPPC-bpy is sensitized are placed in the baking oven that temperature is 80 DEG C and heat 5min, then be immersed in
Concentration is the Co of 10mmol/LII(dmgH)2Cl2In methanol solution, triethylamine is added, soak 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 cobalt chloride hexahydrate is dissolved in 60mL acetone, 16.81mmol diacetyldioximes, then low whipping speed is added
For stirring reaction 10min under 400r/min, then filtered, filtered out unreacted precipitate, obtained filtrate；Filtrate is stood
12h, obtains green crystal；Using acetone cleaning green crystal 5 times, Co is obtainedII(dmgH)2Cl2；
Step 10 1. described in concentration for 10mmol/L CoII(dmgH)2Cl2The volume ratio of methanol solution and triethylamine
For 100:1；
2., the NiO photocathodes for being sensitized ZnTPPC-bpy take out, and using absolute ethanol washing 1 time, reuse deionized water
Washing 1 time；
3., the operation of repeat step 10 three times, then 3h is dried at room temperature for, obtain based on zinc porphyrin with diacetyldioxime cobalt certainly
The NiO photocathodes of assembling.
With CHI 660E electrochemical workstations as platform, tested using three electrode standards systems, with Ag/AgCl electrodes
For reference electrode, Pt silks are the prepared time extremely working electrode to electrode, and the aqueous sodium persulfate solution of 0.1mol/L is used as electricity
Solution liquid, applies the bias voltage of -0.2V；Light source is simulated visible light (300W xenon lamps, illumination density 300mW/cm2, in addition
The long pass filters of 400nm are to filter off ultraviolet light)；Assembling photoelectrochemistrpool pool carries out I-T curve tests to photocurrent response.In order to
Remove needs to carry out bubbling argon 15min to electrolyte before the oxygen electro-chemical test in electrolyte.All of test is at 25 DEG C
Under carry out, such as Fig. 1 and as indicated at 3.
In the ZnTHPP obtained in the step 5 of embodiment one is sensitized NiO photocathodes respectively and the step 7 of embodiment one
, used as working electrode, assembling photoelectrochemistrpool pool is to photoelectric current for the NiO photocathodes of the ZnTHPP-bpy-Codmg self assemblies sensitization arrived
Response carries out I-T curve tests, as shown in Figure 1；
Fig. 1 is photoelectric current comparison diagram, and 1 is the NiO photocathodes of the ZnTHPP sensitizations obtained in the step 5 of embodiment one in Fig. 1
Photocurrent curve, 2 is the NiO photocathodes of the ZnTHPP-bpy-Codmg self assemblies sensitization obtained in embodiment one step 7
Photocurrent curve；
From fig. 1, it can be seen that the NiO photocathodes of the ZnTHPP-bpy-Codmg self assemblies sensitization obtained in the step 7 of embodiment one
It is significantly improved relative to the NiO photocathode photocurrent responses of simple absorption ZnTHPP, efficiency improves 50% or so,
And current stabilization.
The ZnTPPC obtained in the step 8 of embodiment one is sensitized NiO photocathodes and the step 10 of embodiment one respectively is obtained
The NiO photocathodes based on zinc porphyrin and diacetyldioxime cobalt self assembly as working electrode, assembling photoelectrochemistrpool pool is to photoelectric current
Response carries out I-T curve tests, as shown in Figure 3；
Fig. 3 is photoelectric current comparison diagram, and 1 is the NiO photocathodes of the ZnTPPC sensitizations obtained in the step 8 of embodiment one in Fig. 3
Photocurrent curve, 2 is the NiO photocathodes based on zinc porphyrin and diacetyldioxime cobalt self assembly that the step 10 of embodiment one is obtained
Photocurrent curve；
As can be seen from Figure 3, the NiO photocathodes based on zinc porphyrin and diacetyldioxime cobalt self assembly that the step 10 of embodiment one is obtained
It is significantly improved relative to the NiO photocathode photocurrent responses of simple absorption ZnTPPC, efficiency improves 75% or so,
And current stabilization.
Fig. 2 is solid ultraviolet-ray visible absorbing figure comparison diagram, and 1 is that the ZnTHPP obtained in the step 5 of embodiment one is quick in Fig. 2
The solid ultraviolet-ray visible absorbing curve of the NiO photocathodes of change, 2 is the ZnTHPP-bpy- obtained in the step 7 of embodiment one
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 the ZnTHPP sensitizations for obtaining in the step 5 of embodiment one are that 440nm is left in wavelength
The absworption peak of right appearance is the characteristic absorption of ZnTHPP, and the ZnTHPP- obtained in the step 7 of embodiment one after self assembly
The absorption in this place of the NiO photocathodes of bpy-Codmg self assemblies sensitization decreases, and this is due to the NiO light of ZnTHPP sensitizations
Repeatedly the immersion in methanol solution causes dye moiety desorption to cause to negative electrode.And the absorption after 450nm increased be by
Cause in catalyst Codmg absorption.
Fig. 4 is solid ultraviolet-ray visible absorbing figure comparison diagram, and 1 is that the ZnTPPC obtained in the step 8 of embodiment one is quick in Fig. 4
The solid ultraviolet-ray visible absorbing curve of the NiO photocathodes of change, 2 be the step 10 of embodiment one 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 the ZnTPPC sensitizations for obtaining in the step 8 of embodiment one are that 435nm is left in wavelength
The absworption peak of right appearance for ZnTPPC characteristic absorption, and the step 10 of embodiment one after autonomous dress is obtained based on porphyrin
The absorption in this place of the NiO photocathodes of zinc and diacetyldioxime cobalt self assembly decreases, and this is due to the NiO light of ZnTPPC sensitizations
Repeatedly the immersion in methanol solution causes dye moiety desorption to cause to negative electrode.And the absorption after 450nm increased be by
Cause in catalyst Codmg absorption.
Fig. 5 is the schematic flow sheet of the step 5 of embodiment one to step 7；
As can be seen from Figure 5, photosensitizer ZnTHPP forms adsorption by hydrogen bond by the hydroxy groups of its band with the hydroxyl on NiO surfaces
In NiO surfaces, afterwards the N formation coordinations on the Zn ions of ZnTHPP and one of pyridine of 4,4- bipyridyl, last Codmg
Self assembly is completed with the N formation coordinations on another pyridine of 4,4- bipyridyls obtain ZnTHPP-bpy-Codmg self assembly light
Negative electrode.
Fig. 6 is the schematic flow sheet of the step 8 of embodiment one to step 10；
It will be appreciated from fig. 6 that photosensitizer ZnTPPC forms ester bond absorption by the carboxyl group of its band with the hydroxyl on NiO surfaces
In NiO surfaces, afterwards the N formation coordinations on the Zn ions of ZnTPPC and one of pyridine of 4,4- bipyridyl, last Codmg
Self assembly is completed with the N formation coordinations on another pyridine of 4,4- bipyridyls obtain ZnTHPC-bpy-Codmg self assembly light
Negative electrode, i.e., based on zinc porphyrin and the NiO photocathodes of diacetyldioxime cobalt self assembly.
Claims (10)
1. a kind of preparation method based on zinc porphyrin and the NiO photocathodes of diacetyldioxime cobalt self assembly, it is characterised in that the method
It is specifically realized by the following steps：
First, NiO compacted zone precursor liquids are prepared：By NiCl2·6H2The mixing of O, P123, deionized water and dehydrated alcohol, stirs
After put in centrifuge be centrifuged, remove precipitation, the supernatant for obtaining be NiO compacted zone precursor liquids；
NiCl described in step one2·6H2The mass ratio of O and P123 is 1:(0.5~0.8)；
NiCl described in step one2·6H2O is 1 with the mass ratio of deionized water:(1.3~1.66)；
NiCl described in step one2·6H2O is 1 with the mass ratio of dehydrated alcohol:(3~3.3)；
The centrifugal speed of the centrifuge described in step one be 7000r/min~9000r/min, centrifugation time be 3min~
7min；
2nd, NiO compacted zones are prepared：
1., the NiO compacted zone precursor liquids obtained in step one are spun to the conducting surface of FTO electro-conductive glass by way of spin coating
On, then it is placed in again in the baking oven that temperature is 65 DEG C~80 DEG C and is dried 3min~7min；
2., repeat step two 1. 1 time~4 times, then 30min~60min is sintered in the case where temperature is for 300 DEG C~350 DEG C, obtain surface
FTO electro-conductive glass containing NiO compacted zones；
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 powder body, terpineol and ethyl cellulose are distributed in dehydrated alcohol, 2~3 are aged after stirring at room temperature
My god, obtain slurry；
NiO powder body described in step 3 is 1 with the mass ratio of terpineol:(3.5~4)；
NiO powder body described in step 3 is 1 with the mass ratio of ethyl cellulose:(0.1~0.2)；
NiO powder body described in step 3 is 1 with the mass ratio of dehydrated alcohol:(3~5)；
NiO powder body described in step 3 is the spherical alumina nickel that particle diameter is 30nm；
The 4th, the slurry obtained in step 3 is printed onto the surface obtained in step 2 using the method for silk screen printing and contains 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, is subsequently placed in temperature for 65 DEG C
3min~7min is dried in~80 DEG C of baking oven, then 30min~60min is sintered in the case where temperature is for 400 DEG C~500 DEG C, 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 into heating 5min~10min in the baking oven that temperature is 80 DEG C, then is immersed in
Concentration is 8h~10h in the methanol solution of four (p-hydroxybenzene) zinc porphyrins of 10mmol/L~15mmol/L；
2., NiO blank is taken out, first by absolute ethanol washing 1 time, deionized water wash 1 time is reused；
3., repeat step five 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 hydroxy benzaldehydes are dissolved in 240mL propanoic acid, then are heated to reflux in the case where temperature is for 140 DEG C, then will
4.3mL pyrroles is added drop-wise in propanoic acid in 5min, then is heated to reflux 1.5h in the case where temperature is for 140 DEG C, is cooled to room temperature, adds
100mL methanol, then the cooling and standings 0.5h under ice bath, have violet solid to separate out, then carry out sucking filtration, using methanol cleaning filter cake extremely
Cleanout fluid is colourless, obtains solid matter；Solid matter is dissolved in mixed liquor of the dichloromethane with methanol, 12h is stood, then is entered
Row sucking filtration, obtains purple crystals, as tetrahydroxy phenyl porphyrin；Described dichloromethane and dichloromethane in the mixed liquor of methanol
It is 1 with the volume ratio of methanol:1；
(2), 0.1064g tetrahydroxy phenyl porphyrins and 0.5054g zinc acetates are mixed, agate mortar is reused and is ground
30min, obtains mixed-powder A；Mixed-powder A is distributed in 50mL dimethylformamides, then is heated in the case where temperature is for 150 DEG C
Backflow 45min, then pour in 100mL frozen water, then 12h is stood in the case where temperature is for -4 DEG C, then sucking filtration is carried out, four are obtained (to hydroxyl
Phenyl) zinc porphyrin；
6th, the NiO photocathodes of ZnTHPP-bpy sensitizations are prepared：
1., the NiO photocathodes that ZnTHPP is sensitized are placed in into heating 3min~7min in the baking oven that temperature is 65 DEG C~80 DEG C, then are soaked
Steep 8h~10h in methanol solution of the concentration for the 4,4- bipyridyls of 10mmol/L~15mmol/L；
2., the NiO photocathodes for being sensitized ZnTHPP take out, and first by absolute ethanol washing 1 time, reuse deionized water wash
1 time；
3., repeat step six it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain the NiO light of ZnTHPP-bpy sensitizations
Negative electrode；
7th, the NiO photocathodes of ZnTHPP-bpy-Codmg self assemblies sensitization are prepared：
1., the NiO photocathodes that ZnTHPP-bpy is sensitized are placed in into heating 3min~7min in the baking oven that temperature is 65 DEG C~80 DEG C,
The Co that concentration is 10mmol/L~15mmol/L is immersed in againII(dmgH)2Cl2In methanol solution, triethylamine is added, soak 8h
~10h；
Step 7 1. described in CoII(dmgH)2Cl2Co in methanol solutionII(dmgH)2Cl2Prepare according to the following steps：
8.40mmol cobalt chloride hexahydrate is dissolved in 60mL acetone, 16.81mmol diacetyldioximes, then low whipping speed is added
For stirring reaction 10min under 300r/min~500r/min, then filtered, filtered out unreacted precipitate, obtained filtrate；
Filtrate is stood into 12h, green crystal is obtained；Using acetone cleaning green crystal 3 times~5 times, Co is obtainedII(dmgH)2Cl2；
Step 7 1. described in concentration for 10mmol/L~15mmol/L CoII(dmgH)2Cl2Methanol solution and triethylamine
Volume ratio is 100:1；
2., the NiO photocathodes for being sensitized ZnTHPP-bpy take out, and using absolute ethanol washing 1 time, reuse deionized water wash
1 time；
3., repeat step seven 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 it is immersed in immersion in the methanol solution of four (carboxyl phenyl) zinc porphyrins that concentration is 10mmol/L~15mmol/L
8h~10h；
Step 8 1. described in four (carboxyl phenyl) zinc porphyrins methanol solution in four (carboxyl phenyl) zinc porphyrins specifically press
Prepared by following steps：
(1), 3.11g p formylbenzoic acid methyl ester is dissolved in 50mL propanoic acid, 3mL dimethyl sulfoxide is added, is mixed
Close liquid；Mixed liquor is heated to into 130 DEG C, then 1.3mL pyrroles is added drop-wise in mixed liquor in 5min, then be 130 DEG C in temperature
Under be heated to reflux 40min, then carry out filtration under diminished pressure, obtain filter cake；Filter cake is cleaned 3 times~5 times using propanoic acid, is reused anhydrous
Ethanol purge 3 times~5 times, then filter cake is dried, obtain purple crystals, as four ester group phenyl porphyrins；
(2), the ester group phenyl porphyrins of 250mg tetra- and the acetate hydrate zinc of 400mg bis- are mixed, 30mL chloroforms and 10mL first is added
Alcohol, obtains reactant liquor；Reactant liquor is heated to reflux into 4h in the case where temperature is for 65 DEG C, reaction carries out vacuum distillation after terminating, remove molten
Agent, adds 25mL tetrahydrofurans and potassium hydroxide aqueous solution that 5mL mass fractions are 4%, then is to heat at 60 DEG C in temperature
Backflow 24h, then vacuum distillation is carried out, remove solvent；Obtain solid matter；25mL deionizations are added in 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 be centrifuged, centrifugal liquid is removed, obtain purple precipitation；Using distilled water to purple precipitation cleaning 3 times~5 times, then carry out
It is dried, obtains four (carboxyl phenyl) zinc porphyrins；
2., the NiO photocathodes for being sensitized ZnTHPP-bpy-Codmg self assemblies take out, and using absolute ethanol washing 1 time, reuse
Deionized water wash 1 time；
3., repeat step eight 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 NiO photocathodes that ZnTPPC is sensitized are placed in into heating 3min~7min in the baking oven that temperature is 65 DEG C~80 DEG C, then are soaked
Steep 8h~10h in methanol solution of the concentration for the 4,4- bipyridyls of 10mmol/L~15mmol/L；
2., the NiO photocathodes for being sensitized ZnTPPC take out, and with absolute ethanol washing 1 time, reuse deionized water wash 1 time；
3., repeat step nine it is 2. secondary~tetra- times, then be dried at room temperature for 2h~4h, obtain the NiO light of ZnTPPC-bpy sensitizations
Negative electrode；
Tenth, immersion, cleaning：
1., the NiO photocathodes that ZnTPPC-bpy is sensitized are placed in into heating 3min~7min in the baking oven that temperature is 65 DEG C~80 DEG C,
The Co that concentration is 10mmol/L~15mmol/L is immersed in againII(dmgH)2Cl2In methanol solution, triethylamine is added, soak 8h
~10h；
Step 10 1. described in CoII(dmgH)2Cl2Co in methanol solutionII(dmgH)2Cl2Prepare according to the following steps：Will
8.40mmol cobalt chloride hexahydrate is dissolved in 60mL acetone, adds 16.81mmol diacetyldioximes, then low whipping speed is
Stirring reaction 10min under 300r/min~500r/min, then filtered, unreacted precipitate is filtered out, obtain filtrate；Will
Filtrate stands 12h, obtains green crystal；Using acetone cleaning green crystal 3 times~5 times, Co is obtainedII(dmgH)2Cl2；
Step 10 1. described in concentration for 10mmol/L~15mmol/L CoII(dmgH)2Cl2Methanol solution and triethylamine
Volume ratio is 100:1；
2., the NiO photocathodes for being sensitized ZnTPPC-bpy take out, and using absolute ethanol washing 1 time, reuse deionized water wash
1 time；
3., the operation of repeat step ten 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. a kind of preparation side based on zinc porphyrin and the NiO photocathodes of diacetyldioxime cobalt self assembly according to claim 1
Method, it is characterised in that the NiCl described in step one2·6H2The mass ratio of O and P123 is 1:(0.5~0.65)；Institute in step one
The NiCl for stating2·6H2O is 1 with the mass ratio of deionized water:(1.3~1.45)；NiCl described in step one2·6H2O and nothing
The mass ratio of water-ethanol is 1:(3~3.15).
3. a kind of preparation side based on zinc porphyrin and the NiO photocathodes of diacetyldioxime 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 one are spun to into FTO by way of spin coating
On the conducting surface of electro-conductive glass, then it is placed in again in the baking oven that temperature is 65 DEG C~75 DEG C and is dried 3min~5min；Step 2 is 2.
Middle repeat step two 1. 1 time~2 times, then 30min~40min is sintered in the case where temperature is for 300 DEG C~350 DEG C, obtain surface and contain
The FTO electro-conductive glass of NiO compacted zones.
4. a kind of preparation side based on zinc porphyrin and the NiO photocathodes of diacetyldioxime cobalt self assembly according to claim 1
Method, it is characterised in that the NiO powder body described in step 3 is 1 with the mass ratio of terpineol:(3.5~3.8)；Described in step 3
The mass ratio of NiO powder body and ethyl cellulose be 1:(0.1~0.15)；NiO powder body and dehydrated alcohol described in step 3
Mass ratio be 1:(3~4).
5. a kind of preparation side based on zinc porphyrin and the NiO photocathodes of diacetyldioxime cobalt self assembly according to claim 1
Method, it is characterised in that in step 4 the slurry obtained in step 3 is printed onto in step 2 using the method for silk screen printing and is obtained
The surface FTO electro-conductive glass that contains NiO compacted zones NiO compacted zones on, the thickness of slurry printing is 1 μm~2 μm, is then put
Be dried 3min~5min in the baking oven that temperature is 65 DEG C~75 DEG C, then temperature be sinter at 400 DEG C~450 DEG C 30min~
40min, obtains NiO blank after natural cooling.
6. a kind of preparation side based on zinc porphyrin and the NiO photocathodes of diacetyldioxime cobalt self assembly according to claim 1
Method, it is characterised in that step 5 1. in the NiO blank obtained in step 4 be placed in the baking oven that temperature is 80 DEG C heat 5min
~8min, then be immersed in concentration be 10mmol/L~13mmol/L four (p-hydroxybenzene) zinc porphyrins methanol solution in 8h~
9h。
7. a kind of preparation side based on zinc porphyrin and the NiO photocathodes of diacetyldioxime cobalt self assembly according to claim 1
Method, it is characterised in that step 6 1. in the NiO photocathodes that ZnTHPP is sensitized are placed in the baking oven that temperature is 65 DEG C~70 DEG C plus
Hot 3min~5min, then it is immersed in 8h~9h in the methanol solution of 4, the 4- bipyridyls that concentration is 10mmol/L~13mmol/L.
8. a kind of preparation side based on zinc porphyrin and the NiO photocathodes of diacetyldioxime cobalt self assembly according to claim 1
Method, it is characterised in that step 7 1. in by ZnTHPP-bpy be sensitized NiO photocathodes be placed in the baking oven that temperature is 65 DEG C~70 DEG C
Middle heating 3min~5min, then it is immersed in the Co that concentration is 10mmol/L~15mmol/LII(dmgH)2Cl2In methanol solution, then
Triethylamine is added, 8h~9h is soaked.
9. a kind of preparation side based on zinc porphyrin and the NiO photocathodes of diacetyldioxime 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 into temperature for 80 DEG C
Baking oven in heat 5min~8min, then be immersed in four (carboxyl phenyl) zinc porphyrins that concentration is 10mmol/L~13mmol/L
8h~9h is soaked in methanol solution.
10. a kind of preparation side based on zinc porphyrin and the NiO photocathodes of diacetyldioxime cobalt self assembly according to claim 1
Method, it is characterised in that step 9 1. in the NiO photocathodes that ZnTPPC is sensitized are placed in the baking oven that temperature is 65 DEG C~70 DEG C plus
Hot 3min~5min, then it is immersed in 8h~9h in the methanol solution of 4, the 4- bipyridyls that concentration is 10mmol/L~13mmol/L.
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| CN107301920A (en) * | 2017-06-20 | 2017-10-27 | 哈尔滨工业大学 | A kind of high oxidative porphyrin is sensitized SnO2Bionical light anode preparation method |
| CN111185238A (en) * | 2020-02-20 | 2020-05-22 | 辽宁大学 | Copper doped ultra-thin TiO2Nanosheet-loaded cobalt oxime complex composite photocatalyst and preparation method and application thereof |
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| CN105239091A (en) * | 2014-07-10 | 2016-01-13 | 中国科学院理化技术研究所 | Photocathode based on metal oxide, quantum dot and hydrogen production catalyst, and preparation and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107301920A (en) * | 2017-06-20 | 2017-10-27 | 哈尔滨工业大学 | A kind of high oxidative porphyrin is sensitized SnO2Bionical light anode preparation method |
| CN111185238A (en) * | 2020-02-20 | 2020-05-22 | 辽宁大学 | Copper doped ultra-thin TiO2Nanosheet-loaded cobalt oxime complex composite photocatalyst and preparation method and application thereof |
| CN111185238B (en) * | 2020-02-20 | 2022-07-19 | 辽宁大学 | Copper doped ultra-thin TiO2Nanosheet-loaded cobalt oxime complex composite photocatalyst and preparation method and application thereof |
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