A kind of Cp*Co (CO) I2Load the preparation method of Co-doped ZnO light anode nano-array
阅读说明：本技术 一种Cp*Co(CO)I2负载钴掺杂氧化锌光阳极纳米阵列的制备方法 (A kind of Cp*Co (CO) I2Load the preparation method of Co-doped ZnO light anode nano-array ) 是由 崔佳宝 陈俊霞 潘楠楠 姜聚慧 娄向东 于 2019-09-05 设计创作，主要内容包括：本发明公开了一种Cp*Co(CO)I_2负载钴掺杂氧化锌光阳极纳米阵列的制备方法,将含有氧化锌种子层的FTO基底放入聚四氟乙烯高压反应釜中,再加入Zn(NO_3)_2·6H_2O与六亚甲基四胺的混合液,于90℃水热反应5~10h得到ZnO光阳极纳米阵列；在水热反应液中加入硝酸钴,于90℃水热反应5~10h得到Co-ZnO光电阳极纳米阵列；将Co-ZnO光电阳极纳米阵列于室温下在黑暗条件下浸入Cp*Co(CO)I_2的N,N-二甲基甲酰胺溶液中6~10h,最后用乙醇和水冲洗得到目标产物。本发明制得的Cp*Co(CO)I_2负载钴掺杂氧化锌光阳极纳米阵列不仅能够保持较好的氧化锌阵列形貌,而且加快了光生电子的迁移率,具有较好的稳定性,最终展现出优异的光电化学性能。(The invention discloses a kind of Cp*Co (CO) I 2 The preparation method for loading Co-doped ZnO light anode nano-array, the FTO substrate containing zinc oxide seed layer is put into polytetrafluoroethylene (PTFE) autoclave, Zn (NO is added 3 ) 2 ·6H 2 The mixed liquor of O and hexa obtain ZnO photo-anode nano-array in 90 DEG C of 5 ~ 10h of hydro-thermal reaction；Cobalt nitrate is added in hydro-thermal reaction liquid, obtains Co-ZnO photo cathode nano-array in 90 DEG C of 5 ~ 10h of hydro-thermal reaction；Co-ZnO photo cathode nano-array is immersed under dark condition to Cp*Co (CO) I at room temperature 2 N,N-Dimethylformamide solution in 6 ~ 10h, finally rinse to obtain target product with second alcohol and water.Cp*Co (CO) I produced by the present invention 2 Load Co-doped ZnO light anode nano-array can not only keep preferable zinc oxide array pattern, and accelerate the mobility of light induced electron, have preferable stability, finally show excellent photoelectrochemical behaviour.)
1. a kind of Cp*Co (CO) I2Load the preparation method of Co-doped ZnO light anode nano-array, it is characterised in that specific step Suddenly are as follows:
Step S1: taking the zinc acetate ethanol solution drop coating of the 10mM of 10 ~ 200 μ L in the FTO substrate cleaned up, 2500 ~ 3500 revolutions per seconds continue 30 seconds, transfer in Muffle furnace, and it is obtained in FTO substrate to be warming up to 300 DEG C of calcining 2.5h through 40min Zinc oxide seed layer；
Step S2: the FTO substrate containing zinc oxide seed layer that step S1 is obtained is put into polytetrafluoroethylene (PTFE) autoclave, Add the Zn (NO of 0.01 ~ 0.25M3)2·6H2The 80mL of the hexa of O and 0.01 ~ 0.25M, molar ratio 1:1 is mixed Liquid is closed, obtains ZnO photo-anode nano-array in 90 DEG C of 5 ~ 10h of hydro-thermal reaction；
Step S3: the cobalt nitrate of molar ratio Co/Zn=1% ~ 5% is added in the hydro-thermal reaction liquid of step S2, in 90 DEG C of hydro-thermal reactions 5 ~ 10h obtains Co-ZnO light anode nano-array；
Step S4: the Co-ZnO light anode nano-array that step S3 is obtained is immersed into Cp*Co under dark condition at room temperature (CO)I2N,N-Dimethylformamide solution in 6 ~ 10h, finally rinsed to obtain target product Cp*Co (CO) I with second alcohol and water2 Load Co-doped ZnO light anode nano-array.
2. Cp*Co (CO) I according to claim 12The preparation method of Co-doped ZnO light anode nano-array is loaded, It is characterized by: Zn (NO described in step S23)2·6H2The molar concentration of O is 0.05M, the molar concentration of hexa For 0.05M, the cobalt nitrate of molar ratio Co/Zn=3%, Cp*Co made from the condition is added in step S3 in hydro-thermal reaction liquid (CO)I2Load Co-doped ZnO light anode nano-array impedance value substantially reduce, the separation of photo-generate electron-hole pair with Transmission is substantially improved, and density of photocurrent reaches 1.16mA/cm in 1.23V2。
3. Cp*Co (CO) I according to claim 12The preparation method of Co-doped ZnO light anode nano-array is loaded, It is characterized by: Cp*Co (CO) I2Load Cp*Co (CO) I in Co-doped ZnO light anode nano-array2Load and cobalt Doping is all without the pattern for changing ZnO photo-anode nano-array, Cp*Co (CO) I2Load Co-doped ZnO light anode nanometer The average vertical height of array is 2.2 μm.
Technical field
The invention belongs to the synthesis technical fields of nanometer photoelectronic material, and in particular to a kind of transition metals cobalt organic molecule is urged Agent-pentamethylcyclopentadiene base cobalt diiodide (Cp*Co (CO) I2) load Co-doped ZnO light anode nano-array system Preparation Method.
Background technique
With the development of science and technology with the progress of human civilization, energy problem is increasingly prominent.Fossil fuel etc. can not be again The raw energy constantly consumes, and forces researcher to be continually developed and utilizes renewable energy.Solar energy electrocatalytic decomposition water technology Fine blueprint is constructed for the green cleaning sustainable development of the mankind, but PhotoelectrocatalytiPerformance Performance water oxidation kinetics is slow, photoproduction Electron-hole is compound rapidly, and the more low factor of electron transfer rate hinders its large-scale development.
Zinc oxide (ZnO) is as a kind of novel semiconductor material, and since the valence band band of ZnO can be higher, take-off potential is more Negative, electron transfer rate with higher and longer electron lifetime can promote the injection and transmission of charge, make it in conduct Have wide practical use in terms of light anode.Cobalt is a kind of typically more active transition metal element, catalysis with higher Activity, since it is easily oxidized to divalent cobalt in air, and the cobalt of divalent is easily oxidised the cobalt ions for higher price, Therefore cobalt has very strong oxygen adsorption capacity, this has cobalt in terms of photoelectrocatalysis to be widely applied very much.It is urged compared to inorganic Agent, organic molecule catalyst have preferably modification space and processed and applied prospect, from the point of long-term development, it will be one Very potential research direction.The present invention synthesizes Co-doped ZnO array using simple hydro-thermal method on FTO, then passes through Normal temperature dipping method success load C p*Co (CO) I on Co-doped ZnO array2, cobalt is evenly distributed in zinc-oxide nano battle array The inside and surface of column greatly improve the oxygen adsorption capacity of material, induce the quick separating of photo-generate electron-hole pair, with Pure zinc oxide nano-array is compared, and photoelectrochemical behaviour is largely promoted.
In addition, this project jumps out the design limitation of Traditional photovoltaic catalyst, using Cp*Co (CO) I2It is aoxidized as cobalt doped The co-catalyst of zinc light anode shows excellent properties in photoelectrochemical behaviour test.Currently, organic about transition metals cobalt The research of co-catalyst load Co-doped ZnO light anode yet there are no relevant report.
Summary of the invention
It is an object of the invention to propose a kind of new transition metals cobalt organic molecule co-catalyst Cp*Co (CO) I2It is negative Carry the preparation method of Co-doped ZnO light anode nano-array, Cp*Co (CO) I made from this method2Load cobalt doped oxidation Zinc light anode nano-array can not only keep preferable zinc oxide array pattern, and accelerate the mobility of light induced electron, With preferable stability, excellent photoelectrochemical behaviour is finally shown.
The present invention adopts the following technical scheme that achieve the above object, a kind of Cp*Co (CO) I2Load Co-doped ZnO The preparation method of light anode nano-array, it is characterised in that specific steps are as follows:
Step S1: taking the zinc acetate ethanol solution drop coating of the 10mM of 10 ~ 200 μ L in the FTO substrate cleaned up, 2500 ~ 3500 revolutions per seconds continue 30 seconds, transfer in Muffle furnace, and it is obtained in FTO substrate to be warming up to 300 DEG C of calcining 2.5h through 40min Zinc oxide seed layer；
Step S2: the FTO substrate containing zinc oxide seed layer that step S1 is obtained is put into polytetrafluoroethylene (PTFE) autoclave, Add the Zn (NO of 0.01 ~ 0.25M3)2·6H2The 80mL of the hexa of O and 0.01 ~ 0.25M, molar ratio 1:1 is mixed Liquid is closed, obtains ZnO photo-anode nano-array in 90 DEG C of 5 ~ 10h of hydro-thermal reaction；
Step S3: the cobalt nitrate of molar ratio Co/Zn=1% ~ 5% is added in the hydro-thermal reaction liquid of step S2, in 90 DEG C of hydro-thermal reactions 5 ~ 10h obtains Co-ZnO light anode nano-array；
Step S4: the Co-ZnO light anode nano-array that step S3 is obtained is immersed into Cp*Co under dark condition at room temperature (CO)I2N,N-Dimethylformamide solution in 6 ~ 10h, finally rinsed to obtain target product Cp*Co (CO) I with second alcohol and water2 Load Co-doped ZnO light anode nano-array.
Further preferably, Zn (NO described in step S23)2·6H2The molar concentration of O is 0.05M, hexa Molar concentration is 0.05M, is added the cobalt nitrate of molar ratio Co/Zn=3% in step S3 in hydro-thermal reaction liquid, made from the condition Cp*Co(CO)I2The impedance value of load Co-doped ZnO light anode nano-array substantially reduces, and photo-generate electron-hole is to dividing It is substantially improved from transmission, density of photocurrent reaches 1.16mA/cm in 1.23V2。
Further preferably, Cp*Co (CO) I2Load Cp*Co (CO) I in Co-doped ZnO light anode nano-array2 Load and cobalt doped are all without the pattern for changing ZnO nano array, Cp*Co (CO) I2Load Co-doped ZnO light anode is received The average vertical height of rice array is 2.2 μm.
Compared with the prior art, the present invention has the following advantages: 1, the present invention by two steps different method ZnO inside With surface doping or Supported Co, the active site on ZnO is increased；2, Cp*Co (CO) I that the present invention uses2It is a kind of novelty Efficient water oxidation promoters are conducive to the oxygen adsorption capacity for improving target product, induce the quick of photo-generate electron-hole pair Separation；3, Cp*Co (CO) I produced by the present invention2Load Co-doped ZnO light anode nano-array has both good electronics and moves Shifting rate and excellent photocatalysis performance can quickly realize the separation and transmission of photo-generate electron-hole pair, have good light Chemical property.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph that ZnO, CZ3 and Co/CZ3 light anode nano-array is made in embodiment 2, (a) ZnO, (b) CZ3, (c) Co/CZ3, (d) Co/CZ3 sectional view, the shape characteristic of ZnO nano array is not with the addition of cobalt source as seen from the figure And change, the height of Co/CZ3 light anode nano-array is about 2.2 μm；
Fig. 2 is the EDS energy spectrum analysis figure of Co/CZ3 light anode nano-array made from embodiment 2, is contained in sample as seen from the figure Zn, O, Co, in addition I is from Cp*Co (CO) I2, the organic matter of C, N in reaction；
Fig. 3 is the density of photocurrent voltage curve (J- of embodiment 1,2 and 3 obtained ZnO, CZ3 and Co/CZ3 light anode nano-arrays V curve), as seen from the figure, the photoelectric current of Co/CZ3 light anode nano-array is most strong, is 1.16 mA/cm in 1.23V2 vs. RHE；
Fig. 4 is the optical electro-chemistry impedance diagram of embodiment 1,2 and 3 obtained ZnO, CZ3 and Co/CZ3 light anode nano-arrays, can be seen The resistance value of Co/CZ3 light anode nano-array is minimum out.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair Bright range.