CN110368960A - A kind of modified MoS2The preparation method and applications of/CdS base complex light electrode material - Google Patents

A kind of modified MoS2The preparation method and applications of/CdS base complex light electrode material Download PDF

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CN110368960A
CN110368960A CN201910651437.4A CN201910651437A CN110368960A CN 110368960 A CN110368960 A CN 110368960A CN 201910651437 A CN201910651437 A CN 201910651437A CN 110368960 A CN110368960 A CN 110368960A
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solution
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metal
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马旭莉
杨慧敏
田浩洋
梁振海
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Taiyuan University of Technology
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Abstract

The invention discloses a kind of modified MoS2The preparation method and applications of/CdS base complex light electrode material, belong to photo-electrocatalytic technology field.The MoS of source metal (Cu, Fe, Co, Ni) doping is prepared using simple two steps solvent-thermal method2/ CdS based composite catalyst, and be prepared into optoelectronic pole and be applied in photoelectrocatalysis hydrogen production by water decomposition solid/liquid/gas reactions, the MoS of prepared metal source doping2/ CdS base complex light electrode decomposes in water evolving hydrogen reaction in photoelectrocatalysis and shows good catalytic activity and Hydrogen Evolution Performance, stable circulation performance.

Description

A kind of modified MoS2The preparation method and applications of/CdS base complex light electrode material
Technical field
The present invention relates to a kind of modified MoS2The preparation method and applications of/CdS base complex light electrode material, belong to photoelectricity Catalysis technical field.
Background technique
It is shown according to version " BP world energy sources statistical yearbook " related data for delivering in 2018, global primary energy consumption amount 2.2% was increased than 2017.Wherein, China's energy consumption increases by 3.1%, and energy-output ratio accounts for the 23.2% of the whole world, continuously Become global energy within 17 years and consumes the maximum country of increment.The behind that world economy continued smooth increases is depended on to conventional fossil The demand of fuel, but in the long run/term, while bringing prosperity to human society, our conventional fossil fuel must not The trend of ametropia lack of energy and environmental degradation.Therefore, developing cleanliness without any pollution, alternative conventional fossil fuel novel This trend of the energy is extremely urgent.
The advantages that Hydrogen Energy is by feat of energy density height, rich reserves, cleanliness without any pollution and be acknowledged as the ideal energy.Hydrogen It can be a kind of secondary energy sources, calorific value is up to 118.4 KJg-1(being 3 times of petroleum), and combustion product is water, to environment Without any pollution.Traditional process for making hydrogen has water electrolysis hydrogen production, the hydrogen manufacturing of oil pyrolysis gas, Coal Gasification hydrogen manufacturing etc., and By large-scale application in fields such as industrial production, food processing and space flight.But traditional process for making hydrogen is usually associated with high consumption The problems such as energy, Gao Chengben and pollution environment.Thus, seek it is a kind of efficiently, cheap and low energy consumption process for making hydrogen be current The key problem that hydrogen preparation field is faced.
CdS is as a kind of important semiconductor photoelectrocatalysielectrode material because having photovoltaic effect, Nernst effect, photoconduction effect The advantages that answering and be widely used in the fields such as photoelectrocatalysis, photodetector, solar battery and luminescent device.CdS is A kind of common n-type semiconductor, forbidden bandwidth are 2.42 eV, can sunlight of the absorbing wavelength less than 512 nm, have good Optical response range and absorbing properties.Although CdS by its suitable forbidden bandwidth, good conduction band, valence band location and The advantages that synthesis technology is simple and be considered as a kind of efficient semiconductor material.But CdS inherently the shortcomings that also one Determine to limit its performance in light (electricity) catalytic field in degree to further increase.Wherein most important problem is too fast Photo-generated carrier is compound and most of sulfide semiconductor material common to photoetch phenomenon.
By p-type semiconductor such as CoO, AgGaS2、Cu2S、PbS、MoS2Deng, building p-n compound with n-type semiconductor CdS progress Heterojunction structure is a kind of effective means.Zong etc. is by a certain proportion of MoS2Compound, composition MoS is carried out with CdS2/ CdS is multiple Catalyst is closed, and has carried out the test of photoelectrocatalysis liberation of hydrogen in electrolyte environment of the lactic acid as hole trapping agents, the results showed that The liberation of hydrogen rate of composite catalyst has reached 500 μm of olh-1, when being higher than precious metals pt, Rh, Pd, Au etc. as co-catalyst Liberation of hydrogen rate (Zong X, Yan H, Wu G, et al. Enhancement of photocatalytic H2 evolution on CdS by loading MoS2 as cocatalyst under visible light irradiation[J]. Journal of the American Chemical Society, 2008, 130(23): 7176-7177.).Chang etc. is by by MoS2It is supported on CdS and synthesizes MoS2/ CdS composite catalyzing material, and by MoS2's The number of plies controls between 1-112 layers.Itself the result shows that, MoS2The number of plies it is fewer, MoS2The photoelectrocatalysis liberation of hydrogen of/CdS composite material Performance is higher.With Na2S-Na2SO3With lactic acid as in the electrolyte of hole trapping agents, single layer MoS2/ CdS composite material Liberation of hydrogen rate is respectively 2.01 × 10-3M·h-1With 2.59 × 10-3 M·h-1(Chang K, Li M, Wang T, et al. Drastic Layer-Number-Dependent Activity Enhancement in Photocatalytic H2 Evolution over nMoS2/CdS (n≥1) Under Visible Light[J]. Advanced Energy Materials, 2015, 5(10): 1402279-1402287.).How by a series of simple means to catalyst into Research hotspot when row is modified to obtain with efficient, stable catalytic hydrogen evolution material instantly.
Summary of the invention
The present invention lives for low to visible light utilization efficiency present in existing photoelectrocatalysis hydrogen production by water decomposition solid/liquid/gas reactions, catalysis The problems such as property is low, liberation of hydrogen rate is low, Hydrogen Evolution Performance is unstable, provides a kind of modified MoS2The system of/CdS base complex light electrode material Application in Preparation Method and its photoelectrocatalysis hydrogen production by water decomposition gas.
The present invention provides a kind of metal-doped MoS2The preparation method of/CdS base complex light electrode material, including it is as follows Step:
The first step, by the Cd (NO of 2-5mmol3)2·4H2The thiocarbamide of O and 6-10mmol is dissolved in 30-60mL decentralized medium, is stirred Mix 20-120 min to solution be uniformly mixed, by the mixed solution under the conditions of 150-220 DEG C solvent-thermal process 14-48 h, it is molten After agent thermal synthesis, it is cooled to room temperature, after then impregnating 1 h with 20-50 mL ethyl alcohol, 30 min of ultrasound, then with 20-50 mL After water impregnates 1 h, 30 min of ultrasound are then centrifuged for, and are repeated 3-5 times, until pH=5-8, are obtained golden yellow precipitate object, will The golden yellow precipitate object is ground after drying under the conditions of 50-120 DEG C, and obtaining golden yellow powder is CdS；
Second step, by 2-5mmol Na2MoO4·2H2O and 6-10mmol thiocarbamide are placed in 30-60 ml decentralized medium, are then pressed According to source metal: the molar ratio of Mo is the ratio of 0.1:10-1:10, weighs source metal and is added in solution, after stirring 3-5 h, is surpassed Sound 0.5-1 h, obtains mixed solution.By the mixed solution under the conditions of 150-220 DEG C solvent-thermal process 14-48 h, solvent heat After synthesis, it is cooled to room temperature, after then impregnating 1 h with 20-50 mL ethyl alcohol, 30 min of ultrasound, then with 20-50 mL water logging After steeping 1 h, 30 min of ultrasound are then centrifuged for, and are repeated 3-5 times, until pH=5-8, black precipitate are obtained, by the black Sediment is ground after drying under the conditions of 50-120 DEG C, obtains black powder, the as MoS of metal source doping2；
Third step weighs the MoS of 0.05-0.1 g second step metal source doping2Catalyst, the dispersion for being scattered in 10-60 mL are situated between In matter, it is ultrasonically treated 3-8 h in ultrasonic washing instrument, obtains the metal-doped MoS by abundant lift-off processing2Catalysis Then agent weighs the CdS catalyst that the 0.5-1 g first step prepares and is added in above-mentioned decentralized medium mixed solution, continues ultrasound 1-3 h is handled, is then centrifuged for separating, and after isolate is transferred to impregnating 1 h in 20-50 mL ethanol solution, ultrasound 30 Min, then with after 1 h of 20-50 mL water immersion, 30 min of ultrasound, centrifugal treating is repeated 3-5 times, until pH=5-8, is obtained Khaki sediment.It is ground after the khaki sediment is dried under the conditions of 50-120 DEG C, obtains khaki powder, as Modified metal-doped MoS2And the compound catalyst with CdS；
It is big to be cut to the cm size of 1 cm × 4 by the 4th step for the sheet metal that ITO or FTO electro-conductive glass or purity are 99% or more It is small, as electrode matrix, 1 h is impregnated in the inorganic acid solution that 100 DEG C of mass fractions are 30%, then takes out, uses deionization Water repeated flushing；It is ultrasonically treated 1 h in the acetone soln of 25 mL, take out and is rinsed with deionized water；In the anhydrous second of 25 mL It is ultrasonically treated 1 h in alcohol, then uses deionized water repeated flushing；Impregnated in the inorganic acid of 25 mL take out after 20 min and according to It is ultrasonically treated in the secondary dehydrated alcohol for being transferred to 25 mL and deionized water 2-3 times, 10 min, is made electrode matrix every time, dry It saves.
The present invention provides a kind of metal-doped CdS/MoS2The preparation method of base complex light electrode material, including it is as follows Step:
The first step, by 2-5 mmol Na2MoO4·2H2O and 6-10mmol thiocarbamide are placed in 40-60 ml decentralized medium, are stirred After 3-5 h, ultrasonic 0.5-1 h obtains mixed solution.By the mixed solution under the conditions of 150-220 DEG C solvent-thermal process 14- 48 h after solvent-thermal process, are cooled to room temperature, after then impregnating 1 h with 20-50 mL ethyl alcohol, 30 min of ultrasound, then use After 20-50 mL water impregnates 1 h, 30 min of ultrasound are then centrifuged for, and are repeated 3-5 times, until pH=5-8, are obtained black precipitate Object grinds after drying the black precipitate under the conditions of 50-120 DEG C, obtains black powder, as MoS2；
Second step, by the Cd (NO of 2-5mmol mmol3)2·4H2The thiocarbamide of O and 6-10mmol mmol is dissolved in 30-60 dispersion In medium, stirring 20-120 min is uniform to solution, according to source metal: the molar ratio of CdS is 0.1:10-1:10 ratio, is weighed Source metal is simultaneously added in solution, and after stirring 3-5 h, ultrasonic 0.5-1 h obtains mixed solution.By the mixed solution in 150-220 Solvent-thermal process 14-48 h under the conditions of DEG C after solvent-thermal process, is cooled to room temperature, and then impregnates 1 with 20-50 mL ethyl alcohol After h, 30 min of ultrasound, then with after 1 h of 20-50 mL water immersion, 30 min of ultrasound are then centrifuged for, and are repeated 3-5 times, until pH= Until 5-8, golden yellow precipitate object is obtained.It grinds, obtains golden yellow after the golden yellow precipitate object is dried under the conditions of 50-120 DEG C Color powder, the as CdS of metal source doping；
Third step, the CdS for weighing the metal source doping that 0.5-1 g second step is produced are scattered in 10-60 mL decentralized medium, add Enter in 10-60 mL decentralized medium, 10 min are ultrasonically treated in ultrasonic washing instrument, obtains uniform mixed solution.Then it presses According to Na2MoO4·2H2Na is added in the ratio that O:M-CdS is 0.1:10-1:102MoO4·2H2Sulphur is added after 6 h in O and magnetic agitation Urea (Na2MoO4·2H2O: the molar ratio of thiocarbamide is 1:5), it is stirred for 1 h, then ultrasound 0.5-1 h, obtains mixed solution, will Mixed solution solvent-thermal process 14-48 h under the conditions of 150-220 DEG C, after, it is cooled to room temperature.Then 20-50 is used After mL ethyl alcohol impregnates 1 h, 30 min of ultrasound, then with after 1 h of 20-50 mL water immersion, 30 min of ultrasound, centrifugation is repeated 3-5 times, Until pH=7, green precipitate object is obtained.It grinds, obtains green after the green precipitate object is dried under the conditions of 50-120 DEG C Color powder, as modified metal-doped CdS and MoS2Composite catalyst；
It is big to be cut to the cm size of 1 cm × 4 by the 4th step for the sheet metal that ITO or FTO electro-conductive glass or purity are 99% or more It is small, as electrode matrix, 1 h is impregnated in the inorganic acid solution that 100 DEG C of mass fractions are 30%, then takes out, uses deionization Water repeated flushing；It is ultrasonically treated 1 h in the acetone soln of 25 mL, take out and is rinsed with deionized water；In the anhydrous second of 25 mL It is ultrasonically treated 1 h in alcohol, then uses deionized water repeated flushing；Impregnated in the inorganic acid of 25 mL take out after 20 min and according to It is ultrasonically treated in the secondary dehydrated alcohol for being transferred to 25 mL and deionized water 2-3 times, 10 min, is made electrode matrix every time, dry It saves.
Above-mentioned preparation method, the metal of the source metal are any one in Cu, Fe, Co or Ni, the source metal For CuCl2、CuSO4、FeCl2、FeSO4、CoCl2、Co(NO3)2Or Ni (NO3)2In any one.
Above-mentioned preparation method, the inorganic acid are the H that mass fraction is 30%2O2With dense H2SO4、 3 mol·L-1Oxalic acid With 6 molL-1Hydrochloric acid, 3mol/L hydrochloric acid and 3mol/L nitric acid or 6 molL-1Sulfuric acid and 6 molL-1The mixed liquor of hydrochloric acid In any one, the volume ratio of two kinds of solution in mixed liquor is any one in 1:1,2:1,1:2,3:1 or 3:2.
Above-mentioned preparation method, the decentralized medium are methanol, ethyl alcohol, isopropanol, n-butanol, acetone, N, N- dimethyl Formamide or N, the mixed liquor of one or both of N- diethylformamide.
The present invention provides MoS metal-doped made from the above method2/ CdS based composites are metal-doped CdS/MoS2Based composites.
The present invention provides above-mentioned modified MoS2/ CdS base complex light electrode material is in photoelectrocatalysis hydrogen production by water decomposition gas Application.
In the application, by the MoS of metal source doping obtained2/ CdS base complex light electrode selects the H-type electricity with diaphragm Slot is solved, 25 mL electrolyte are respectively added in two Room of yin, yang, and impose in D.C. regulated power supply, pulse power supply or dual-pulse power supply Any one, potential window is -1.23-1.23 V；In the cathodic compartment with 2-5 mLs-1Speed be passed through 30 min N2, Again to modified MoS2/ CdS base complex light electrode carries out PhotoelectrocatalytiPerformance Performance test.
In above-mentioned application, the diaphragm of the electrolytic cell is any one in Nafion membrane, cationic membrane or Bipolar Membrane.
In above-mentioned application, the two Room electrolyte of yin, yang can be 0.5-6 molL-1Na2CO3Solution, Na2SO4It is molten Liquid, Na2S and Na2SO3Mixed liquor, KOH solution, any one or a few solution in lactic acid solution mixed solution.
In above-mentioned application, the power supply is any one in D.C. regulated power supply, pulse power supply or dual-pulse power supply.
Beneficial effects of the present invention:
Source metal (Cu, Fe, Co, Ni) doping is prepared using simple two steps solvent-thermal method the invention proposes a kind of MoS2/ CdS based composite catalyst is simultaneously prepared into optoelectronic pole applied in photoelectrocatalysis hydrogen production by water decomposition solid/liquid/gas reactions, prepared Metal source doping MoS2/ CdS base complex light electrode decomposes in water evolving hydrogen reaction in photoelectrocatalysis and shows good catalysis Activity and Hydrogen Evolution Performance use modified MoS made from this method2/ CdS based composite catalyst presents in photoelectrochemical behaviour 43 μA·cm-2With 77 μ Acm-2Photo-current intensity, while having in the reaction of photoelectrocatalysis hydrogen production by water decomposition gas 10.18 mmol· h-1g-1With 12.78 mmol h-1g-1Evolving hydrogen reaction rate.
Detailed description of the invention
Fig. 1 is that 1- of embodiment of the present invention embodiment 4 prepares CdS, MoS2/ CdS and MoS2The scanning electron microscope of/M-CdS Figure；
Fig. 2 is MoS prepared by 1- of embodiment of the present invention embodiment 42/ M-CdS transmission electron microscope figure；
Fig. 3 is M-MoS prepared by 5- of embodiment of the present invention embodiment 82/ CdS transmission electron microscope figure；
Fig. 4 is CdS and MoS prepared by 1- of embodiment of the present invention embodiment 42/ M-CdS photoelectrocatalysis liberation of hydrogen rate diagram；
Fig. 5 is CdS and M-MoS prepared by 5- of embodiment of the present invention embodiment 82/ CdS photoelectrocatalysis liberation of hydrogen rate diagram.
Specific embodiment
The present invention is further illustrated below by embodiment, but is not limited to following embodiment.
The CdS/MoS of embodiment 1:(Cu doping2The preparation method and application of based composites)
By 0.9995 g Cd (NO3)2·4H2O is dissolved in 60 mL distilled water, and 30 min are to uniform for stirring, according to Cd (NO3)2·4H2O molar ratio is that 10:0.7:30 weighs 0.0311 g CuCl respectively2, 0.6942 g thiocarbamide is added to above-mentioned molten In liquid, 3 h of magnetic agitation, 0.5 h of ultrasound.Then mixed solution is transferred to the stainless steel reaction under high pressure of polytetrafluoroethyllining lining In kettle, 160 DEG C of 16 h of hydro-thermal are cooled to room temperature after hydro-thermal, successively impregnate 1 h, ultrasound 30 with 20 mL ethyl alcohol, water Min is then centrifuged for, and is repeated 5 times, up to no Cl-1Detection, obtains golden yellow precipitate object, grinds after drying in 80 DEG C of drying boxes It grinds to get the CdS adulterated to Cu.
It weighs the above-mentioned Cu-CdS of 1 g to be placed in 100 mL beakers, and 60 mL distilled water is added, in ultrasonic washing instrument 10 min are ultrasonically treated, keep its fully dispersed.It is that 10:0.5 weighs 0.0403g Na respectively according to CdS molar ratio2MoO4· 2H2O, 0.0617g thiocarbamide (Na2MoO4·2H2The molar ratio of O/ thiocarbamide is 1:5) 6 h of magnetic agitation in above-mentioned solution is added, surpass 0.5 h of sound.Then mixed solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining, 210 DEG C of hydro-thermals 24 H is cooled to room temperature after hydro-thermal, is successively impregnated 1 h, 30 min of ultrasound with 20 mL ethyl alcohol, water, is then centrifuged for, is repeated 5 times, It is ground until pH=7, after obtained blackish green sediment is dried in 80 DEG C of drying box to get MoS is arrived2/Cu- CdS。
Electro-conductive glass (ITO) is cut to the size cm of 1 cm × 2, is pre-processed, at normal temperature first respectively ethyl alcohol, Acetone and distilled water are ultrasonically treated 20 min；FTO is then placed the solution that 50 mL volume ratios are 1:1, and (percentage is 30% H2O2With dense H2SO4Mixed liquor) in impregnate 30 min, 20 min of ultrasound；Then successively clear with dehydrated alcohol and distilled water ultrasound again 5 min are washed, are repeated twice, it is ensured that the pollutant and pickling solution of FTO conductive glass surface are fully erased clean, kept dry.
Weigh 10 mg MoS2/ Cu-CdS catalyst sample is scattered in 1 mL distilled water, and 5 μ L Nafion solutions are added (5 wt%) is ultrasonically treated 1 min afterwards with fully dispersed.The catalyst mixed solution of 100 μ L is taken uniformly to drip every time with liquid-transfering gun It is applied on ITO electro-conductive glass, and controlling drop coating area is the cm of 1 cm × 1, and test use is carried out after spontaneously drying, at this point, Light anode catalyst loadings are 1 mgcm-2.By the MoS of obtained modification2/ Cu-CdS electrode and dual-pulse power supply anode phase It connects, Pt electrodes connect with dual-pulse power supply cathode, select the H-type electrolytic cell of cationic membrane diaphragm, two Room of yin, yang respectively adds 50 mL 0.1 mol·L-1Na2SO40.1 molL of solution and 10 mL-1Lactic acid solution as electrolyte, in potential window is- 0.7 V is to modified MoS2/ Cu-CdS electrode carries out photoelectrocatalysis and decomposes the performance test of elutriation hydrogen, and test result is shown 10.18 mmol· h-1g-1Evolving hydrogen reaction rate.
Embodiment 2:(MoS2The preparation method and application of/Fe-CdS composite material)
By 0.9995 g Cd (NO3)2·4H2O is dissolved in 60mL distilled water, stirring 30 min wait for that solution is uniform, according to Cd (NO3)2·4H2O molar ratio is that 10:0.7:30 ratio weighs 0.0293 g FeCl respectively2, 0.6942g thiocarbamide, be added to above-mentioned In solution, 3 h of magnetic agitation, 0.5 h of ultrasound.Then the stainless steel high pressure for mixed solution being transferred to polytetrafluoroethyllining lining is anti- It answers in kettle, 160 DEG C of 16 h of hydro-thermal, is cooled to room temperature after hydro-thermal, successively impregnate 1 h, ultrasound 30 with 20 mL ethyl alcohol, water Min is then centrifuged, and is repeated 5 times, up to no Cl-Until detection, golden yellow precipitate object will be obtained and dried in 80 DEG C of drying box After grind to get to Fe-CdS.
It weighs the above-mentioned Fe-CdS of 1 g to be placed in the beaker of 100 mL, and 60 mL distilled water is added, in ultrasonic washing instrument 10 min of middle ultrasonic treatment, keep its fully dispersed.It then, is that 10:0.5 ratio weighs 0.0403g respectively according to CdS molar ratio Na2MoO4·2H2O, 0.0617g thiocarbamide (Na2MoO4·2H2The molar ratio of O/ thiocarbamide is added magnetic force in above-mentioned solution for 1:5) and stirs Mix 6 h, 0.5 h of ultrasound.Then mixed solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining, 210 DEG C 24 h of hydro-thermal is cooled to room temperature after hydro-thermal, is successively impregnated 1 h, 30 min of ultrasound with 20 mL ethyl alcohol, water, is then centrifuged for, It is repeated 5 times, until pH=7.Blackish green sediment will be obtained, grinding is after drying in 80 DEG C of drying box to get arriving MoS2/Fe-CdS。
Electro-conductive glass (ITO) is cut to the size cm of 1 cm × 2, is pre-processed, at normal temperature first respectively ethyl alcohol, Acetone and distilled water are ultrasonically treated 20 min；FTO is then placed the solution that 50 mL volume ratios are 1:1, and (percentage is 30% H2O2With dense H2SO4Mixed liquor) in impregnate 30 min, 20 min of ultrasound；Again successively with dehydrated alcohol and distilled water ultrasound after taking-up 5 min are cleaned, are repeated twice, it is ensured that the pollutant and pickling solution of FTO conductive glass surface are fully erased clean, kept dry.
Weigh 10 mg MoS2/ Fe-CdS catalyst sample is scattered in 1 mL distilled water, and it is molten that 5 μ L Nafion are added Liquid (5 wt%) is ultrasonically treated 1 min afterwards with fully dispersed.Take the catalyst mixed solution of 100 μ L uniform every time with liquid-transfering gun Drop coating to ITO electro-conductive glass on, and control drop coating area be the cm of 1 cm × 1, can be carried out after spontaneously drying test make With.At this point, the load capacity of catalyst is 1 mgcm in light anode-2.By the MoS of obtained modification2/ Fe-CdS electrode and dipulse Positive pole connects, and Pt electrodes connect with dual-pulse power supply cathode, selects the H-type electrolytic cell of cationic membrane diaphragm, yin, yang two Respectively add 50 mL, 0.1 molL in room-1 Na2SO40.1 molL of solution and 10mL-1Lactic acid solution is as electrolyte, in electricity Position window is -0.7 V to modified MoS2/ Fe-CdS electrode carries out photoelectrocatalysis and decomposes the performance test of elutriation hydrogen, test result Show 7.09 mmolh-1g-1Evolving hydrogen reaction rate.
Embodiment 3:(MoS2The preparation method and application of/Co-CdS composite material)
By 0.9995 g Cd (NO3)2·4H2O is dissolved in 60 mL distilled water, stirring 30 min wait for that solution is uniform, according to Cd (NO3)2·4H2O molar ratio is that 10:0.7:30 weighs 0.0228 g CoCl respectively2, 0.6942 g thiocarbamide, be added to above-mentioned molten In liquid, 3 h of magnetic agitation, 0.5 h of ultrasound.Then, the stainless steel high pressure for mixed solution being transferred to polytetrafluoroethyllining lining is anti- It answers in kettle, 160 DEG C of 16 h of hydro-thermal, is cooled to room temperature after hydro-thermal, successively impregnate 1 h, ultrasound 30 with 20 mL ethyl alcohol, water Min is then centrifuged for, and is repeated 5 times, up to no Cl-1Until detection.Golden yellow precipitate object will be obtained, will be dried in 80 DEG C of drying boxes After grind to get to Co-CdS.
It weighs the above-mentioned Co-CdS of 1 g to be placed in the beaker of 100 mL, and 60 mL distilled water is added, in ultrasonic washing instrument 10 min of middle ultrasonic treatment, keep its fully dispersed.It then, is that 10:0.5 weighs 0.0403g respectively according to CdS molar ratio Na2MoO4·2H2O, 0.0617g thiocarbamide (Na2MoO4·2H2The molar ratio of O/ thiocarbamide is added magnetic force in above-mentioned solution for 1:5) and stirs Mix 6 h, 0.5 h of ultrasound.Then mixed solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining, 210 DEG C 24 h of hydro-thermal is cooled to room temperature after hydro-thermal, is successively impregnated 1 h, 30 min of ultrasound with 20 mL ethyl alcohol, water, is then centrifuged, It is repeated 5 times, until pH=7.Blackish green sediment will be obtained, grinding is after drying in 80 DEG C of drying box to get arriving MoS2/Co-CdS。
Electro-conductive glass (ITO) is cut to the size cm of 1 cm × 2, is pre-processed, at normal temperature first respectively ethyl alcohol, Acetone and distilled water are ultrasonically treated 20 min；FTO is then placed the solution that 50mL volume ratio is 1:1, and (percentage is 30% H2O2With dense H2SO4Mixed liquor) in impregnate 30 min, 20 min of ultrasound；Again successively with dehydrated alcohol and distilled water ultrasound after taking-up 5 min are cleaned, are repeated twice, it is ensured that the pollutant and pickling solution of FTO conductive glass surface are fully erased clean, kept dry.
Weigh 10 mg MoS2/ Co-CdS catalyst sample is scattered in 1 mL distilled water, and it is molten that 5 μ L Nafion are added Liquid (5 wt%) is ultrasonically treated 1 min afterwards with fully dispersed.Take the catalyst mixed solution of 100 μ L uniform every time with liquid-transfering gun Drop coating to ITO electro-conductive glass on, and control drop coating area be the cm of 1 cm × 1, can be carried out after spontaneously drying test make With.At this point, the load capacity of catalyst is 1 mgcm in light anode-2.By the MoS of obtained modification2/ Co-CdS electrode and dipulse Positive pole connects, and Pt electrodes connect with dual-pulse power supply cathode, select the H-type electrolytic cell of cationic membrane diaphragm, yin, yang Respectively add 50 mL, 0.1 molL in two Room-1Na2SO4Solution and 10mL 0.1molL-1Lactic acid solution is as electrolyte, in electricity Position window is -0.7 V to modified MoS2/ Co-CdS electrode carries out photoelectrocatalysis and decomposes the performance test of elutriation hydrogen, test knot Fruit shows 8.48 mmoh-1g-1Evolving hydrogen reaction rate.
Embodiment 4:(MoS2The preparation method and application of/Ni-CdS composite material)
By 0.9995 g Cd (NO3)2·4H2O is dissolved in 60 mL distilled water, stirring 30min wait for that solution is uniform, according to Cd (NO3)2·4H2O molar ratio is that 10:0.7:30 weighs 0.0299 g NiCl respectively2, 0.6942 g thiocarbamide, be added to above-mentioned molten In liquid, 3 h of magnetic agitation, 0.5 h of ultrasound.Then mixed solution is transferred to the stainless steel reaction under high pressure of polytetrafluoroethyllining lining In kettle, 160 DEG C of 16 h of hydro-thermal are cooled to room temperature after hydro-thermal, successively impregnate 1 h, ultrasound 30 with 20 mL ethyl alcohol, water Min is then centrifuged, and is repeated 5 times, up to no Cl-1Until detection, golden yellow precipitate object will be obtained and dried in 80 DEG C of drying boxes After grind to get to Ni-CdS.
It weighs the above-mentioned Ni-CdS of 1 g to be placed in the beaker of 100 mL, and 60 mL distilled water is added, in ultrasonic washing instrument 10 min of middle ultrasonic treatment, keep its fully dispersed.It then, is that 10:0.5 weighs 0.0403g respectively according to CdS molar ratio Na2MoO4·2H2O, 0.0617g thiocarbamide (Na2MoO4·2H2The molar ratio of O/ thiocarbamide is added magnetic force in above-mentioned solution for 1:5) and stirs Mix 6 h, 0.5 h of ultrasound.Then mixed solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining, 210 DEG C 24 h of hydro-thermal is cooled to room temperature after hydro-thermal, is successively impregnated 1 h, 30 min of ultrasound with 20 mL ethyl alcohol, water, is then centrifuged, It is repeated 5 times, until pH=7, blackish green sediment will be obtained, ground after being dried in 80 DEG C of drying boxes to get MoS is arrived2/ Ni-CdS。
Electro-conductive glass (ITO) is cut to the size cm of 1 cm × 2, is pre-processed, at normal temperature first respectively in ethyl alcohol, acetone 20 min are ultrasonically treated with distilled water；FTO is then placed into the solution (H that percentage is 30% that 50 mL volume ratios are 1:12O2With Dense H2SO4Mixed liquor) in impregnate 30 min, 20 min of ultrasound；Again successively with dehydrated alcohol and distilled water ultrasonic cleaning 5 after taking-up Min is repeated twice, it is ensured that the pollutant and pickling solution of FTO conductive glass surface are fully erased clean, kept dry.Weigh 10 mg MoS2/ Ni-CdS catalyst sample is scattered in 1 mL distilled water, and after 5 μ L Nafion solutions (5 wt%) of addition It is fully dispersed to be ultrasonically treated 1 min.Take the uniform drop coating of catalyst mixed solution of 100 μ L to ITO conduction every time with liquid-transfering gun On glass, and controlling drop coating area is the cm of 1 cm × 1, and test use can be carried out after spontaneously drying.At this point, in light anode The load capacity of catalyst is 1 mgcm-2.By the MoS of obtained modification2/ Ni-CdS electrode connects with dual-pulse power supply anode, Pt Silk electrode connects with dual-pulse power supply cathode, selects the H-type electrolytic cell of cationic membrane diaphragm, 50 mL are respectively added in two Room of yin, yang 0.1 mol·L-1Na2SO4Solution and 10mL 0.1molL-1Lactic acid solution is -0.7 V pairs in potential window as electrolyte Modified MoS2/ Ni-CdS electrode carries out photoelectrocatalysis and decomposes the performance test of elutriation hydrogen, and test result shows 5.93 mmol h-1g-1Evolving hydrogen reaction rate.
(a), (b) are CdS microscopic appearances in Fig. 1, can clearly tell CdS with club shaped structure, and size is controlled in 20-30 nm range.(c) is MoS in Fig. 12/ CdS composite material, the MoS of laminated structure2It is evenly distributed on club shaped structure On CdS.Compared with figure (c), Fig. 1 (d) is MoS2It is carried on Cu2+Microscopic appearance on the CdS of doping, it can be found that nanometer sheet Nanorod surfaces structure is evenly distributed on not to be changed.Meanwhile the lamella packing phenomenon of material surface obtained it is a degree of It reduces, the hydrogen evolution activity site for being conducive to composite material sufficiently exposes, and shortens electronic transmission path, while improving reaction system Photoelectrochemical behaviour.
The MoS that (A), (C) show two-dimensional sheet, lack layer structure in Fig. 22It is successfully supported on the CdS of club shaped structure, and MoS2Active site is located at lamella edge.(D)-(G) is MoS in Fig. 22/ Cu-CdS composite material is micro- in high magnification electronic transmission Image under mirror can clearly tell the type of lattice fringe and the numerical value of lattice fringe spacing.In conjunction with Fig. 2 (B) MoS2、CdS XRD diagram, through calculating, 0.61 nm and 0.36 nm lattice fringe spacing respectively correspond MoS2(002) plane and CdS(100) it is flat Face, and the heterojunction structure of close contact is formd at the two contact interface.In Fig. 2 (F) CdS material occur having a size of The lattice fringe spacing of 0.58 nm is Cu according to relevant research2+Caused by doping.
If the upper figure of Fig. 4 is different mol ratio Cu2+CdS sample liberation of hydrogen rate diagram is adulterated, 7% Cu-CdS has highest liberation of hydrogen Performance reaches 1115 μm of olh-1g-1, it is 5.3 times of undoped CdS.Fig. 4 following figure, 5 % MoS2The analysis of/Cu-CdS Hydrogen rate is up to 10.18 mmolh-1g-1, and its liberation of hydrogen rate is without Cu2+48 times for adulterating CdS.MoS2/Cu-CdS Catalyst system shows the photoelectrochemical behaviour haveing excellent performance and efficient photoelectrocatalysis liberation of hydrogen efficiency.
Embodiment 5:(Cu-MoS2The preparation method and application of/CdS composite material)
By 0.9995 g Cd (NO3)2·4H2O is dissolved in 60mL distilled water, stirring 30min wait for that solution is uniform, according to Cd (NO3)2·4H2O molar ratio is that 10:3 weighs 0.6942g thiocarbamide, is added in above-mentioned solution, magnetic agitation 3h, ultrasonic 0.5h. Then mixed solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining, 160 DEG C of hydro-thermal 16h, hydro-thermal terminates After be cooled to room temperature, successively with 20 mL ethyl alcohol, water impregnate 1h, 30 min of ultrasound, be then centrifuged, be repeated 5 times, up to no Cl-Inspection Until out, golden yellow precipitate object will be obtained, is ground after being dried in 80 DEG C of drying box to get CdS is arrived.
Weigh 0.6048 g Na2MoO4·2H2O, according to Na2MoO4·2H2O molar ratio is that 10:0.5:50 claims respectively Take 0.0168 g CuCl2, 0.9244 g thiocarbamide, be added to 6 h of magnetic agitation in above-mentioned solution, 0.5 h of ultrasound.Then it will mix It closes solution to be transferred in the stainless steel autoclave of polytetrafluoroethyllining lining, 210 DEG C of 24 h of hydro-thermal, it is cooling after hydro-thermal To room temperature, 1 h, 30 min of ultrasound successively are impregnated with 20 mL ethyl alcohol, water, is then centrifuged, is repeated 5 times, it, will until pH=7 Black precipitate is obtained, is ground after being dried in 80 DEG C of drying box to get Cu-MoS is arrived2。
By 0.05 g Cu-MoS2Catalyst is placed in 20ml and goes in DMF to be ultrasonically treated 5 h, obtains sufficiently to catalyst sample Continue that 1g CdS catalyst is added thereto after removing, continues 3 h of ultrasound.Then mixed solution centrifugation washing is obtained into khaki Sediment, and 1 h, 30 min of ultrasound successively are impregnated with 20 mL ethyl alcohol, water, it is then centrifuged, is repeated 5 times, until pH=7, Obtained khaki sediment is placed in 80 DEG C of drying boxes after drying and is ground to get Cu-MoS is arrived2/CdS。
Electro-conductive glass (ITO) is cut to the size cm of 1 cm × 2, is pre-processed, at normal temperature first respectively ethyl alcohol, Acetone and distilled water are ultrasonically treated 20min；Solution (the H that percentage is 30% for being then 1:1 by FTO placement 50mL volume ratio2O2 With dense H2SO4Mixed liquor) in impregnate 30 min, 20 min of ultrasound；Successively it is cleaned by ultrasonic again with dehydrated alcohol and distilled water after taking-up 5 min, are repeated twice, it is ensured that the pollutant and pickling solution of FTO conductive glass surface are fully erased clean, kept dry.It weighs 10 mg Cu-MoS2/ CdS catalyst sample is scattered in 1 mL distilled water, and after 5 μ L Nafion solutions (5 wt%) of addition It is fully dispersed to be ultrasonically treated 1 min.Take the uniform drop coating of catalyst mixed solution of 100 μ L to ITO conduction every time with liquid-transfering gun On glass, and controlling drop coating area is the cm of 1 cm × 1, and test use can be carried out after spontaneously drying.At this point, in light anode The load capacity of catalyst is 1 mgcm-2.By the Cu-MoS of obtained modification2/ CdS electrode connects with dual-pulse power supply anode, Pt Silk electrode connects with dual-pulse power supply cathode, selects the H-type electrolytic cell of cationic membrane diaphragm, 50 mL are respectively added in two Room of yin, yang 0.1 mol·L-1Na2SO40.1 molL of solution and 10mL-1Lactic acid solution is -0.7 V in potential window as electrolyte To modified Cu-MoS2/ CdS electrode carries out photoelectrocatalysis and decomposes the performance test of elutriation hydrogen, and test result shows 12.78 mmol· h-1g-1Evolving hydrogen reaction rate.
Embodiment 6:(Fe-MoS2The preparation method and application of/CdS composite material)
By 0.9995 g Cd (NO3)2·4H2O is dissolved in 60mL distilled water, stirring 30min wait for that solution is uniform, according to Cd (NO3)2·4H2O molar ratio is that 10:3 weighs 0.6942g thiocarbamide, is added in above-mentioned solution, magnetic agitation 3h, 0.5 h of ultrasound. Then mixed solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining, 160 DEG C of 16 h of hydro-thermal, hydro-thermal knot It is cooled to room temperature after beam, successively impregnates 1h, 30 min of ultrasound with 20 mL ethyl alcohol, water, be then centrifuged, be repeated 5 times, up to no Cl- Until detection, golden yellow precipitate object will be obtained, is ground after being dried in 80 DEG C of drying box to get CdS is arrived.
Weigh 0.6048 g Na2MoO4·2H2O, according to Na2MoO4·2H2O molar ratio is that 10:0.5:50 claims respectively Take 0.0154 g FeCl2, 0.9244g thiocarbamide, be added to 6 h of magnetic agitation in above-mentioned solution, 0.5 h of ultrasound.It then will mixing Solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining, 210 DEG C of 24 h of hydro-thermal, is cooled to after hydro-thermal Room temperature successively impregnates 1 h, 30 min of ultrasound with 20 mL ethyl alcohol, water, is then centrifuged, is repeated 5 times, until pH=7, will It is ground after being dried in 80 DEG C of drying boxes to black precipitate to get Fe-MoS is arrived2。
By 0.05g Fe-MoS2Catalyst is placed in 20 mL and goes in DMF to be ultrasonically treated 5 h, obtains sufficiently to catalyst sample Continue that 1g CdS catalyst is added thereto after removing, continues 3 h of ultrasound.Then mixed solution centrifugation washing is obtained into khaki Sediment, and 1 h, 30 min of ultrasound successively are impregnated with 20 mL ethyl alcohol, water, it is then centrifuged, is repeated 5 times, until pH=7, Obtained khaki sediment is placed in 80 DEG C of drying box after drying and is ground to get Fe-MoS is arrived2/CdS。
Electro-conductive glass (ITO) is cut to the size cm of 1 cm × 2, is pre-processed, at normal temperature first respectively ethyl alcohol, Acetone and distilled water are ultrasonically treated 20min；Solution (the H that percentage is 30% for being then 1:1 by FTO placement 50mL volume ratio2O2 With dense H2SO4Mixed liquor) in impregnate 30min, ultrasonic 20min；Successively it is cleaned by ultrasonic again with dehydrated alcohol and distilled water after taking-up 5min is repeated twice, it is ensured that the pollutant and pickling solution of FTO conductive glass surface are fully erased clean, kept dry.Weigh 10 mg Fe-MoS2/ CdS catalyst sample is scattered in 1 mL distilled water, and 5 μ L Nafion solutions (5 wt%) are added and surpass afterwards 1 min of sonication is fully dispersed.Take the uniform drop coating of catalyst mixed solution of 100 μ L to ITO conduction glass every time with liquid-transfering gun On glass, and controlling drop coating area is the cm of 1 cm × 1, and test use can be carried out after spontaneously drying.At this point, being urged in light anode The load capacity of agent is 1 mgcm-2.By the Fe-MoS of obtained modification2/ CdS electrode connects with dual-pulse power supply anode, and Pt Electrode connects with dual-pulse power supply cathode, selects the H-type electrolytic cell of cationic membrane diaphragm, 50 mL 0.1 are respectively added in two Room of yin, yang mol·L-1 Na2SO40.1 molL of solution and 10mL-1Lactic acid solution is -0.7 V to changing in potential window as electrolyte The Fe-MoS of property2/ CdS electrode carries out photoelectrocatalysis and decomposes the performance test of elutriation hydrogen, and test result shows 11.18 mmol h-1g-1Evolving hydrogen reaction rate.
Embodiment 7:(Co-MoS2The preparation method and application of/CdS composite material)
By 0.9995 g Cd (NO3)2·4H2O is dissolved in 60mL distilled water, stirring 30 min wait for that solution is uniform, according to Cd (NO3)2·4H2O molar ratio is that 10:3 weighs 0.6942 g thiocarbamide, is added in above-mentioned solution, 3 h of magnetic agitation, ultrasound 0.5 h.Then mixed solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining, 160 DEG C of 16 h of hydro-thermal, hydro-thermal After be cooled to room temperature, successively impregnate 1h, 30 min of ultrasound with 20 mL ethyl alcohol, water, be then centrifuged, be repeated 5 times, up to nothing Cl-Until detection, it will obtain grinding after golden yellow precipitate object is dried in 80 DEG C of drying box to get CdS is arrived.
Weigh 0.6048 g Na2MoO4·2H2O, according to Na2MoO4·2H2O molar ratio is that 10:0.5:50 claims respectively Take 0.0120 g CoCl2、0.9244 g thiocarbamide is added to 6 h of magnetic agitation in above-mentioned solution, 0.5 h of ultrasound.It then will mixing Solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining, 210 DEG C of 24 h of hydro-thermal, is cooled to after hydro-thermal Room temperature successively impregnates 1 h, 30 min of ultrasound with 20 mL ethyl alcohol, water, is then centrifuged, is repeated 5 times, until pH=7, will It is ground after being dried in 80 DEG C of drying boxes to black precipitate to get Co-MoS is arrived2。
By 0.05 g Co-MoS2Catalyst is placed in 20 mL and goes in DMF to be ultrasonically treated 5 h, is filled to catalyst sample After dividing removing continue that 1g CdS catalyst is added thereto, continues 3 h of ultrasound.Then mixed solution centrifugation washing is obtained into the colour of loess Color sediment, and 1 h, 30 min of ultrasound successively are impregnated with 20 mL ethyl alcohol, water, it is then centrifuged, is repeated 5 times, until pH=7 are Only, obtained khaki sediment is placed in 80 DEG C of drying boxes after drying and is ground to get Co-MoS is arrived2/CdS。
Electro-conductive glass (ITO) is cut to the size cm of 1 cm × 2, is pre-processed, at normal temperature first respectively ethyl alcohol, Acetone and distilled water are ultrasonically treated 20 min；FTO is then placed the solution that 50 mL volume ratios are 1:1, and (percentage is 30% H2O2With dense H2SO4Mixed liquor) in impregnate 30 min, 20 min of ultrasound；Again successively with dehydrated alcohol and distilled water ultrasound after taking-up 5min is cleaned, is repeated twice, it is ensured that the pollutant and pickling solution of FTO conductive glass surface are fully erased clean, kept dry.Claim Take 10 mg Co-MoS2/ CdS catalyst sample is scattered in 1 mL distilled water, and 5 μ L Nafion solutions (5 wt%) are added After be ultrasonically treated 1 min with fully dispersed.Take the uniform drop coating of catalyst mixed solution of 100 μ L to ITO every time with liquid-transfering gun On electro-conductive glass, and controlling drop coating area is the cm of 1 cm × 1, and test use can be carried out after spontaneously drying.At this point, light is positive The load capacity of extremely upper catalyst is 1 mgcm-2.By the Co-MoS of obtained modification2/ CdS electrode and dual-pulse power supply anode phase It connecing, Pt electrodes connect with dual-pulse power supply cathode, the H-type electrolytic cell of cationic membrane diaphragm is selected, two Room of yin, yang is respectively added 50 mL 0.1 mol·L-1Na2SO40.1 molL of solution and 10mL-1Lactic acid solution as electrolyte, in potential window is- 0.7 V is to modified Co-MoS2/ CdS electrode carries out photoelectrocatalysis and decomposes the performance test of elutriation hydrogen, and test result is shown 10.03 mmol·h-1g-1Evolving hydrogen reaction rate.
Embodiment 8:(Ni-MoS2The preparation method and application of/CdS composite material)
By 0.0235 g Cd (NO3)2·4H2O is dissolved in 60 mL distilled water, stirring 30min wait for that solution is uniform, according to Cd (NO3)2·4H2O molar ratio is that 10:3 weighs 0.6942 g thiocarbamide, is added in above-mentioned solution, 3 h of magnetic agitation, ultrasound 0.5 h.Then mixed solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining, 160 DEG C of 16 h of hydro-thermal, hydro-thermal After be cooled to room temperature, successively impregnate 1 h, 30 min of ultrasound with 20 mL ethyl alcohol, water, be then centrifuged, be repeated 5 times, up to nothing Cl-1Until detection, it will obtain grinding after golden yellow precipitate object is dried in 80 DEG C of drying box to get CdS is arrived.
Weigh 0.6048 g Na2MoO4·2H2O, according to Na2MoO4·2H2O molar ratio is that 10:0.5:50 claims respectively Take 0.0157 g NiCl2, 0.9244g thiocarbamide, be added to 6 h of magnetic agitation in above-mentioned solution, 0.5 h of ultrasound.It then will mixing Solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining, 210 DEG C of 24 h of hydro-thermal, is cooled to after hydro-thermal Room temperature successively impregnates 1 h, 30 min of ultrasound with 20 mL ethyl alcohol, water, is then centrifuged, is repeated 5 times, until pH=7, will It is ground after being dried in 80 DEG C of drying boxes to black precipitate to get Ni-MoS is arrived2。
By 0.05 g Ni-MoS2Catalyst is placed in 20 mL and goes to be ultrasonically treated 5h in DMF, obtains sufficiently to catalyst sample Continue that 1 g CdS catalyst is added thereto after removing, continues 3 h of ultrasound.Then mixed solution centrifugation washing is obtained into the colour of loess Color sediment, and 1 h, 30 min of ultrasound successively are impregnated with 20 mL ethyl alcohol, water, it is then centrifuged, is repeated 5 times, until pH=7 are Only, obtained khaki sediment is placed in 80 DEG C of drying boxes after drying and is ground to get Ni-MoS is arrived2/CdS。
Electro-conductive glass (ITO) is cut to the size cm of 1 cm × 2, is pre-processed, at normal temperature first respectively ethyl alcohol, Acetone and distilled water are ultrasonically treated 20min；Solution (the H that percentage is 30% for being then 1:1 by FTO placement 50mL volume ratio2O2 With dense H2SO4Mixed liquor) in impregnate 30 min, 20 min of ultrasound；Successively it is cleaned by ultrasonic again with dehydrated alcohol and distilled water after taking-up 5 min, are repeated twice, it is ensured that the pollutant and pickling solution of FTO conductive glass surface are fully erased clean, kept dry.It weighs 10 mg Ni-MoS2/ CdS catalyst sample is scattered in 1 mL distilled water, and after 5 μ L Nafion solutions (5 wt%) of addition 1 min is ultrasonically treated with fully dispersed.The uniform drop coating of catalyst mixed solution of 100 μ L is taken to lead to ITO every time with liquid-transfering gun On electric glass, and controlling drop coating area is the cm of 1 cm × 1, and test use can be carried out after spontaneously drying.At this point, light anode The load capacity of upper catalyst is 1 mgcm-2.By the Ni-MoS of obtained modification2/ CdS electrode connects with dual-pulse power supply anode, Pt electrodes connect with dual-pulse power supply cathode, select the H-type electrolytic cell of cationic membrane diaphragm, 50 mL are respectively added in two Room of yin, yang 0.1 mol·L-1Na2SO40.1 molL of solution and 10mL-1Lactic acid solution is -0.7 V in potential window as electrolyte To modified Ni-MoS2/ CdS electrode carries out photoelectrocatalysis and decomposes the performance test of elutriation hydrogen, and test result shows 10.47 mmol· h-1g-1Evolving hydrogen reaction rate.
If Fig. 3 (a-c) is the Cu-MoS by flaky nanometer structure2It is evenly distributed on the transmission electron microscope of CdS nanorod surfaces Figure, and Cu-MoS2Appearance transparent, Cu-MoS2Piece number of layers is few, and lamella packing phenomenon, MoS do not occur2It can expose as far as possible More active sites improves the catalytic hydrogen evolution performance of composite material.Fig. 3 (d-f) passes through high magnification transmission electron microscope(TEM) (HR- TEM) further look at, 0.36 nm of lattice fringe size, 0.61 nm and 0.27 nm respectively correspond CdS(100 crystal face), MoS2 (002 crystal face) and (101 crystal face).Because of hydrothermal synthesis process, part Cu2+Doping enters MoS2In, cause between the lattice fringe of part Away from size be slightly expanded to 0.78 nm, the expansion of " S-Mo-S " interlamellar spacing will lead to interlayer Van der Waals force and die down, promote it is compound The raising of material catalytic performance.
Fig. 5 shows, Cu2+Doping % when, Cu-MoS2/ CdS composite material reaches highest photoelectrocatalysis liberation of hydrogen speed Rate: 12.78 mmolh-1g-1, it is CdS and MoS respectively260 times of/CdS and 3.1 times.Because of suitable concentration Cu2+Adulterate MoS2, 1. reducing composite material forbidden bandwidth, widening optical response range；2. improving MoS2The conductivity of material accelerates light induced electron to exist MoS2The delivery rate on surface, improves PhotoelectrocatalytiPerformance Performance；3. activating MoS2It is lazy that catalysis is in other than nanoscale twins marginal position The reasons such as catalytic activity of S atom, improve photoelectrocatalysis liberation of hydrogen rate in property region.

Claims (10)

1. a kind of metal-doped MoS2The preparation method of/CdS base complex light electrode material, it is characterised in that include the following steps:
The first step, by the Cd (NO of 2-5mmol3)2·4H2The thiocarbamide of O and 6-10mmol is dissolved in 30-60mL decentralized medium, is stirred Mix 20-120 min to solution be uniformly mixed, by the mixed solution under the conditions of 150-220 DEG C solvent-thermal process 14-48 h, it is molten After agent thermal synthesis, it is cooled to room temperature, after then impregnating 1 h with 20-50 mL ethyl alcohol, 30 min of ultrasound, then with 20-50 mL After water impregnates 1 h, 30 min of ultrasound are then centrifuged for, and are repeated 3-5 times, until pH=5-8, are obtained golden yellow precipitate object, will The golden yellow precipitate object is ground after drying under the conditions of 50-120 DEG C, and obtaining golden yellow powder is CdS；
Second step, by 2-5mmol Na2MoO4·2H2O and 6-10mmol thiocarbamide are placed in 30-60 ml decentralized medium, are then pressed According to source metal: the molar ratio of Mo is the ratio of 0.1:10-1:10, weighs source metal and is added in solution, after stirring 3-5 h, is surpassed Sound 0.5-1 h, obtains mixed solution；
By the mixed solution under the conditions of 150-220 DEG C solvent-thermal process 14-48 h, after solvent-thermal process, be cooled to room Temperature, then with 20-50 mL ethyl alcohol impregnate 1 h after, 30 min of ultrasound, then with 20-50 mL water immersion 1 h after, 30 min of ultrasound, It is then centrifuged for, repeats 3-5 times, until pH=5-8, black precipitate is obtained, by the black precipitate in 50-120 DEG C of item It is ground after being dried under part, obtains black powder, the as MoS of metal source doping2；
Third step weighs the MoS of 0.05-0.1 g second step metal source doping2Catalyst is scattered in the decentralized medium of 10-60 mL In, it is ultrasonically treated 3-8 h in ultrasonic washing instrument, obtains the metal-doped MoS by abundant lift-off processing2Catalyst, Then it weighs the CdS catalyst that the 0.5-1 g first step prepares to be added in above-mentioned decentralized medium mixed solution, continues to be ultrasonically treated 1-3 h is then centrifuged for separating, and after isolate is transferred to impregnating 1 h in 20-50 mL ethanol solution, 30 min of ultrasound, then After impregnating 1 h with 20-50 mL water, 30 min of ultrasound, centrifugal treating repeats 3-5 times, until pH=5-8, obtains khaki Sediment；
It is ground after the khaki sediment is dried under the conditions of 50-120 DEG C, obtains khaki powder, as modified metal The MoS of doping2And the compound catalyst with CdS；
It is big to be cut to the cm size of 1 cm × 4 by the 4th step for the sheet metal that ITO or FTO electro-conductive glass or purity are 99% or more It is small, as electrode matrix, 1 h is impregnated in the inorganic acid solution that 100 DEG C of mass fractions are 30%, then takes out, uses deionization Water repeated flushing；It is ultrasonically treated 1 h in the acetone soln of 25 mL, take out and is rinsed with deionized water；In the anhydrous second of 25 mL It is ultrasonically treated 1 h in alcohol, then uses deionized water repeated flushing；Impregnated in the inorganic acid of 25 mL take out after 20 min and according to It is ultrasonically treated in the secondary dehydrated alcohol for being transferred to 25 mL and deionized water 2-3 times, 10 min, is made electrode matrix every time, dry It saves.
2. a kind of metal-doped CdS/MoS2The preparation method of base complex light electrode material, it is characterised in that include the following steps:
The first step, by 2-5 mmol Na2MoO4·2H2O and 6-10mmol thiocarbamide are placed in 40-60 ml decentralized medium, are stirred After 3-5 h, ultrasonic 0.5-1 h obtains mixed solution；
By the mixed solution under the conditions of 150-220 DEG C solvent-thermal process 14-48 h, after solvent-thermal process, be cooled to room Temperature, then with 20-50 mL ethyl alcohol impregnate 1 h after, 30 min of ultrasound, then with 20-50 mL water immersion 1 h after, 30 min of ultrasound, It is then centrifuged for, repeats 3-5 times, until pH=5-8, black precipitate is obtained, by the black precipitate in 50-120 DEG C of item It is ground after being dried under part, obtains black powder, as MoS2；
Second step, by the Cd (NO of 2-5mmol mmol3)2·4H2The thiocarbamide of O and 6-10mmol mmol is dissolved in 30-60 dispersion In medium, stirring 20-120 min is uniform to solution, according to source metal: the molar ratio of CdS is 0.1:10-1:10 ratio, is weighed Source metal is simultaneously added in solution, and after stirring 3-5 h, ultrasonic 0.5-1 h obtains mixed solution；
By the mixed solution under the conditions of 150-220 DEG C solvent-thermal process 14-48 h, after solvent-thermal process, be cooled to room Temperature, then with 20-50 mL ethyl alcohol impregnate 1 h after, 30 min of ultrasound, then with 20-50 mL water immersion 1 h after, 30 min of ultrasound, It is then centrifuged for, repeats 3-5 times, until pH=5-8, obtain golden yellow precipitate object；
It is ground after the golden yellow precipitate object is dried under the conditions of 50-120 DEG C, obtains golden yellow powder, as metal source doping CdS；
Third step, the CdS for weighing the metal source doping that 0.5-1 g second step is produced are scattered in 10-60 mL decentralized medium, add Enter in 10-60 mL decentralized medium, 10 min are ultrasonically treated in ultrasonic washing instrument, obtains uniform mixed solution；
Then according to Na2MoO4·2H2Na is added in the ratio that O:M-CdS is 0.1:10-1:102MoO4·2H2O and magnetic agitation, 6 Thiocarbamide (Na is added after h2MoO4·2H2O: the molar ratio of thiocarbamide is 1:5), it is stirred for 1 h, then ultrasound 0.5-1 h, is mixed Close solution, by the mixed solution under the conditions of 150-220 DEG C solvent-thermal process 14-48 h, after, be cooled to room temperature；
Then after impregnating 1 h with 20-50 mL ethyl alcohol, 30 min of ultrasound, then with after 1 h of 20-50 mL water immersion, ultrasonic 30 Min, centrifugation repeat 3-5 times, until pH=7, obtain green precipitate object；
It is ground after the green precipitate object is dried under the conditions of 50-120 DEG C, obtains green powder, as modified is metal-doped CdS and MoS2Composite catalyst；
It is big to be cut to the cm size of 1 cm × 4 by the 4th step for the sheet metal that ITO or FTO electro-conductive glass or purity are 99% or more It is small, as electrode matrix, 1 h is impregnated in the inorganic acid solution that 100 DEG C of mass fractions are 30%, then takes out, uses deionization Water repeated flushing；It is ultrasonically treated 1 h in the acetone soln of 25 mL, take out and is rinsed with deionized water；In the anhydrous second of 25 mL It is ultrasonically treated 1 h in alcohol, then uses deionized water repeated flushing；Impregnated in the inorganic acid of 25 mL take out after 20 min and according to It is ultrasonically treated in the secondary dehydrated alcohol for being transferred to 25 mL and deionized water 2-3 times, 10 min, is made electrode matrix every time, dry It saves.
3. the preparation method of complex light electrode material according to claim 1 or 2, it is characterised in that: the source metal Metal is any one in Cu, Fe, Co or Ni, and the source metal is CuCl2、CuSO4、FeCl2、FeSO4、CoCl2、Co (NO3)2Or Ni (NO3)2In any one.
4. the preparation method of complex light electrode material according to claim 1 or 2, it is characterised in that: the inorganic acid is The H that mass fraction is 30%2O2With dense H2SO4、 3 mol·L-1Oxalic acid and 6 molL-1Hydrochloric acid, 3mol/L hydrochloric acid and 3mol/L Nitric acid or 6 molL-1Sulfuric acid and 6 molL-1Any one in the mixed liquor of hydrochloric acid, two kinds of solution in mixed liquor Volume ratio is any one in 1:1,2:1,1:2,3:1 or 3:2.
5. the preparation method of complex light electrode material according to claim 1 or 2, it is characterised in that: the decentralized medium For methanol, ethyl alcohol, isopropanol, n-butanol, acetone, N,N-dimethylformamide or N, one of N- diethylformamide or two The mixed liquor of kind.
6. metal-doped MoS made from a kind of preparation method described in claim 12/ CdS base complex light electrode material.
7. metal-doped CdS/MoS made from a kind of preparation method as claimed in claim 22Base complex light electrode material.
8. a kind of application of the complex light electrode material described in claim 6 or 7 in photoelectrocatalysis hydrogen production by water decomposition gas.
9. application according to claim 8, it is characterised in that: by the complex light electrode of metal source doping obtained, select 25 mL electrolyte are respectively added in H-type electrolytic cell with diaphragm, two Room of yin, yang, and impose D.C. regulated power supply, pulse power supply or Any one in dual-pulse power supply, potential window are -1.23-1.23 V；In the cathodic compartment with 2-5 mLs-1Speed It is passed through 30 min N2, then PhotoelectrocatalytiPerformance Performance test is carried out to modified complex light electrode.
10. application according to claim 9, it is characterised in that: the diaphragm of the electrolytic cell is Nafion membrane, cationic membrane Or any one in Bipolar Membrane；The two Room electrolyte of yin, yang is 0.5-6 molL-1Na2CO3Solution, Na2SO4It is molten Liquid, Na2S and Na2SO3Mixed liquor, KOH solution, any one or a few solution in lactic acid solution mixed solution；It is described Power supply is any one in D.C. regulated power supply, pulse power supply or dual-pulse power supply.
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CN111151272A (en) * 2020-01-14 2020-05-15 郑州大学 Cobalt and iron doped molybdenum disulfide based material, preparation method thereof and application of cobalt and iron doped molybdenum disulfide based material in electrocatalytic hydrogen evolution
CN111377482A (en) * 2020-03-20 2020-07-07 苏州科技大学 Application of barium-doped molybdenum sulfide material in self-powered piezoelectricity-enhanced hydrogen production
CN111377479A (en) * 2020-03-20 2020-07-07 苏州科技大学 Application of nickel-doped molybdenum sulfide material in self-powered piezoelectricity-enhanced hydrogen production
CN111937528A (en) * 2020-08-17 2020-11-17 山东胜伟盐碱地科技有限公司 Alfalfa seed treatment method for improving stress resistance
CN112624040A (en) * 2020-12-22 2021-04-09 佛山(华南)新材料研究院 Method for preparing hydrogen
CN113070057A (en) * 2021-03-31 2021-07-06 中南大学 Photoelectric-piezoelectric composite material and preparation method thereof
CN113070057B (en) * 2021-03-31 2022-05-17 中南大学 Photoelectric-piezoelectric composite material and preparation method thereof
CN114100682A (en) * 2021-11-22 2022-03-01 四川启睿克科技有限公司 Feather-shaped leaf heterojunction photocatalyst and preparation method thereof
CN114100682B (en) * 2021-11-22 2023-09-15 四川启睿克科技有限公司 Lupin She Yizhi junction photocatalyst and preparation method thereof

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Application publication date: 20191025