CN106186206A - A kind of G@LDHs is combined BiVO4optoelectronic pole and preparation method thereof - Google Patents

A kind of G@LDHs is combined BiVO4optoelectronic pole and preparation method thereof Download PDF

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CN106186206A
CN106186206A CN201610567739.XA CN201610567739A CN106186206A CN 106186206 A CN106186206 A CN 106186206A CN 201610567739 A CN201610567739 A CN 201610567739A CN 106186206 A CN106186206 A CN 106186206A
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项顼
王瑞瑞
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Beijing University of Chemical Technology
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
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    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2305/10—Photocatalysts

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Abstract

The invention discloses a kind of complex metal hydroxide with lamellar graphite alkene composite growth at pucherite optoelectronic pole and preparation method thereof.It is expressed as: G@LDHs/BiVO4, wherein BiVO4Being grown in conductive glass surface, G@LDHs represents the complex of metal hydroxides and Graphene；It is grown directly upon BiVO4On, wherein G@LDHs is the flower-like structure that two-dimensional nano sheet assembles, and its a diameter of 3～5 μm, lamellar spacing is 10～100nm；G represents Graphene；LDHs represents complex metal hydroxide.The preparation method of this optoelectronic pole is: put into by pucherite electrode in the mixed solution containing bivalence, trivalent metal salt, urea, ammonium fluoride and Graphene, and hydro-thermal reaction obtains G@LDHs and is combined BiVO4Optoelectronic pole.The density of photocurrent of this optoelectronic pole reaches original BiVO4More than 4 times of electrode, oxidation efficiency is up to more than 80% in wide potential range, greatly improves catalytic efficiency.And electrode preparation method is easy, low cost, prepared by applicable scale.

Description

A kind of G@LDHs is combined BiVO4Optoelectronic pole and preparation method thereof
Technical field
The invention belongs to electrode material preparation field, be specifically related to lamellar graphite alkene raw with layered composite metal hydroxides Long at pucherite optoelectronic pole and preparation method thereof, and the photoelectrocatalysis water decomposition reaction driven for sunlight.
Background technology
Along with conventional fossil fuel (coal, oil, natural gas etc.) is constantly consumed, the demand of the energy is also being continued by people Increasing, energy problem is following, and energy shortage has been increasingly becoming the major issue threatening human social development.Meanwhile, Conventional fossil fuel uses the environmental pollution caused to arrive the stage that can not be ignored in a large number.In consideration of it, countries in the world are all Actively finding green reproducible new forms of energy, including solar energy, biomass energy, wind energy, geothermal energy and ocean energy etc..Wherein, Solar energy due to its safety height, low cost, life-time service, have a very wide distribution and can automatically the advantage such as work and closed by emphasis Note.
The feature of photocatalytic water splitting: the process of photochemical catalyzing is, after light is absorbed by catalyst material, at catalyst Surface produces light induced electron and hole, and light induced electron reductive water generates hydrogen, and photohole oxidation water generates oxygen.
Inorganic semiconductor material is as the feature of optoelectronic pole: raw material is easy to get, stablizes, to visible light-responded, and pucherite conduct The advantage of optoelectronic pole: band gap is only 2.4eV, is a kind of optoelectronic pole material with good visible light-responded ability, at 420nm Photoelectric transformation efficiency reach 29%, bismuth resource, vitriol aboundresources, the bismuth resource reserve of China ranks first in the world, and reserves are about 240000 tons, accounting for the 75% of world's gross reserves, therefore development bismuth oxo-compound optoelectronic pole material has sufficient resource guarantee.But vanadium Charge transport properties and higher surface reaction barrier that acid bismuth is more weak limit its performance and improve.With catalyst is compound or surface changes Property be improve pucherite optoelectronic pole Surface reaction kinetics important channel.But, at optoelectronic pole surface recombination catalyst or enter Row modification often affects optical absorption property or the stability of electrode, thus causes the visible absorption ability of electrode to reduce or stable Property decline.Therefore, the overall performance how improving optoelectronic pole remains a need for developing new approach.Graphene is that one is by monolayer or few The Two-dimensional Carbon material that layer graphite is formed, has the charge-conduction character of excellence, is commonly applied to photoelectric material.Layered bi-metal hydrogen-oxygen Compound (layered double hydroxides, LDHs) is also a kind of two-dimensional layered-structure material, and transition metal ions can Being uniformly distributed and stable bond on LDHs laminate, therefore, LDHs has good catalytic performance.
Report is to BiVO at present4Modification improves having of optoelectronic pole material property, document 1:D.K.Zhong, S.Choi, D.R.Gamelin.J.Am.Chem.Soc., 2011,133,18370-18377, it is to make catalyst modification tungsten (W) with Co-Pi to mix Miscellaneous BiVO4, under the conditions of illumination AM 1.5G, when 1.23V versus RHE (reversible hydrogen electrode electromotive force), electric current density is 1.4mA/cm2.Document 2:M.F.Lichterman, M.R.Shaner, S.G.Brunschwig, H.B.Gray, N.S.Lewis, J.M.Spurgeon.J.Phys.Chem.Lett., 2013,4,4188-4191, it is with cobalt/cobalt oxide (CoOx) modify BiVO4Light Anode, at 1.23V versus RHE, density of photocurrent is 1.49mA/cm2.Document 3:F.F.Abdi, R.vandeKrol.J. Phys.Chem.C., 2012,116,9398-9404, it is to be grown in undoped p BiVO with Co catalysts4, at 1.23V versus Under RHE, density of photocurrent is 1.7mA/cm2。
Table 1 BiVO4The Optical Electro-Chemistry water oxidation susceptibility of optoelectronic pole compares
Note: test light source: AM1.5G, light intensity: 100mW cm-2.RHE represents reversible hydrogen electrode.
Graphene itself has good electric conductivity, can as the receptor of good light induced electron, by with graphite Alkene recombination energy effectively strengthens the transmission of electric charge, improves electric charge utilization ratio；And Graphene has absorption in visible region, it is possible to Increase the utilization to solar visible light wave band energy, add the distinctive good catalytic performance of LDHs.Based on this, we will Lamellar graphite alkene and stratiform LDHs are combined by chemical reaction and are grown in pucherite optoelectronic pole, significantly improve the light of pucherite Electricity water decomposition performance.
Summary of the invention
It is an object of the invention to provide layered composite metal hydroxides with lamellar graphite alkene composite growth at pucherite light Electrode and preparation method thereof, the method is obviously enhanced the PhotoelectrocatalytiPerformance Performance of pucherite optoelectronic pole.
A kind of G@LDHs that the present invention provides is combined BiVO4Optoelectronic pole, is expressed as: G@LDHs/BiVO4, wherein BiVO4Raw Long at conductive glass surface, crystal formation is monocline, and interparticle distance is 50～120nm, and particle size is 200～300nm；G@ LDHs represents the complex of metal hydroxides and Graphene；It is grown directly upon BiVO4On, wherein G@LDHs is two-dimensional nano sheet The flower-like structure assembled, its a diameter of 3～5 μm, lamellar spacing is 10～100nm；LDHs represents complex metal hydroxide, its Chemical formula is: M2+ 1-xM3+ x(OH)2]x+(AN-)x/n·mH2O, wherein M2+Represent bivalent metal ion, M2+For Ni2+、Co2+In One or both；M3+Represent trivalent metal ion, M3+For Al3+、Fe3+In one or both, AN-For interlayer anion, it is nitre One or both in acid group, sulfate radical, carbonate, m is moisture subnumber, m=5～15, x=1/3～1；G represents Graphene.
The preparation method of this complex light electrode is: put into pucherite electrode containing bivalence, trivalent metal salt, urea, fluorination In the mixed solution of ammonium and Graphene, hydro-thermal reaction obtains G@LDHs and is combined BiVO4Optoelectronic pole.
Concrete preparation process is as follows:
A. M is used2+Salt, M3+Salt, urea and NH4F prepares mixing salt solution, and wherein total concentration of metal ions is 15～50mmol/ L, M2+Ion and M3+The mol ratio of ion is 2～4:1, and the concentration of urea is 30～80mmol/L, with the ratio of total metal ion It is 1～4:1；NH4The concentration of F is 15～50mmol/L, is 1～3:1 with the ratio of total metal ion；Anion in solution is One or both in nitrate anion, sulfate radical, carbonate；Adding concentration again in above-mentioned mixing salt solution is 0.5～3mg/mL Graphene dispersing solution, is 0.01～0.1:1 addition by the volume ratio of graphene dispersing solution Yu mixing salt solution, makes Graphene mixed The content closed in solution is 0.01～0.4mg/mL, and ultrasonic, stirring is to being mixed to form uniform solution.Ultrasonic power 40～100W, Time 10～30min, temperature 20～40 DEG C
Described M2+Salt is Ni2+Salt, Co2+One or both in salt, M3+Salt is Al3+Salt, Fe3+One in salt or two Kind；
Described graphene dispersing solution be the solid content that graphene dispersion is prepared in water be 0.5～3mg/mL dispersion Liquid, Graphene used is monolayer or few layer graphite flake layer, and thickness about 0.3～1nm, surface area is 700～800m2/g。
B. by BiVO4The conducting surface of electrode is upwards swayed and is placed in water heating kettle inner bag, and inclination angle is 30～60 °, and adds step The mixed solution of rapid A configuration, makes growth on electrode have BiVO4Part be totally submerged in solution, with the power of 40～100W Ultrasonic 10～30min；It is warming up to 100～180 DEG C of hydro-thermal reactions 2～20 hours again, after natural cooling, takes out electrode, first use Washing with acetone 1～4 times, each 10～50mL；The most afterwards with alcohol flushing 1～4 times, each 10～50mL；Finally use deionized water Rinse, be dried 1～10 hour in 70～100 DEG C, obtain G@LDHs and be combined BiVO4Optoelectronic pole.
Described BiVO4Electrode is to prepare by the method in patent 2015102390209, wherein BiVO4Particle diameter A size of 200～300nm.
Fig. 1 is BiVO used by embodiment 14X-ray powder diffraction (XRD) result of electrode, occurs corresponding to BiVO in figure4 (011), (121), (004) diffraction maximum, with the BiVO of monoclinic form scheelite phase4Diffraction maximum (JCPDS No.75-1866) one Cause.
Fig. 2 is that the G@LDHs of embodiment 1 preparation is combined BiVO4X-ray powder diffraction (XRD) result of optoelectronic pole.In figure Except BiVO4Outside the diffraction maximum of FTO electro-conductive glass sheet, (003), (006), (009) of LDHs, (018) characteristic peak also occur, Illustrate that successfully preparing G LDHs is combined BiVO4Optoelectronic pole.
G@LDHs is combined BiVO4Optoelectronic pole is for the performance test of photoelectricity water decomposition, and this optoelectronic pole of result is at 1.23V electricity Density of photocurrent under gesture is 2.5～3.5mA/cm2, this value is simple BiVO4More than 4 times of electrode.Improve than same type BiVO4 electrode density of photocurrent (1.7mA/cm under electromotive force 1.23V2) improve 0.8～1.8mA/cm2.Water oxidation initiation potentials It is reduced to 0.2～0.3V (versus RHE), compares BiVO4Electrode is negative moves 200～300mV.
The present invention has a following remarkable result:
(1) using Graphene and LDHs composite growth on optoelectronic pole, method simplicity, abundant raw material source, economy are high, It is a kind of green, environmental protection, nontoxic, economic optoelectronic pole construction method.
(2) density of photocurrent of complex light electrode reaches original BiVO4More than 4 times of electrode, oxidation efficiency is up to 80% Above, energy conversion efficiency is greatly enhanced.
(3) Graphene is realized by gentle hydro-thermal reaction with the compound of LDHs, BiVO4Electrode area is the most adjustable, the party Method is suitable for high-performance, prepared by the scale of low cost optical electrode, has clear and definite Commercial Prospect.
Accompanying drawing explanation
BiVO used by Fig. 1: embodiment 14The XRD figure of electrode.
The G@LDHs of Fig. 2: embodiment 1 preparation is combined BiVO4The XRD figure of optoelectronic pole.
Detailed description of the invention
Embodiment 1
A. 0.3056gCo (NO is weighed3)2·6H2O、0.1313gAl(NO3)3·9H2O, 0.2102g urea, 0.0519gNH4F, in the beaker of 250mL, adds 70mL deionized water, and mix homogeneously, adding 1mL concentration is 1mg/mL stone Ink alkene dispersion liquid, ultrasonic, stirring to being mixed to form uniform solution, ultrasonic power 40W, time are 10min, temperature 20 DEG C, preparation Mixing salt solution.
B. it is the BiVO of 200nm by grain size4The conducting surface of electrode upwards sways 45 °, puts in water heating kettle inner bag, and Add the mixed solution of the step A configuration of 6mL, make growth have BiVO4Part be totally submerged in solution, ultrasonic power 40W, Time 20min, is sufficiently mixed uniformly, and hydro-thermal reaction 4h at 100 DEG C, after natural cooling, is taken out electrode, first used washing with acetone Three times, every time with 10mL, then use alcohol flushing 3 times, every time with 10mL, finally with after deionized water rinsing, be placed on 60 DEG C of bakings Case is dried 1 hour, obtains G@LDHs and be combined BiVO4Optoelectronic pole.
Test above-mentioned G@LDHs and be combined BiVO4Performance as optoelectronic pole: in the electrolyzer of three electrode configurations, with G@ LDHs is combined BiVO4Photoelectricity extremely working electrode, Ag/AgCl is reference electrode, and platinum filament is to electrode, and electrolyzer is single chamber or double Cell structure；Irradiating optoelectronic pole front with the xenon source (simulated solar irradiation) of assembling AM 1.5G optical filter, light intensity is 100mW/ cm2；Utilizing electrochemical workstation (CHI 660E) to apply voltage, electrolyte is the phosphate buffered solution (biphosphate of pH=7 Potassium-dipotassium hydrogen phosphate), concentration is 0.1mol/L；Cyclic voltammetry (CV) is used to test, the wherein scanning of cyclic voltammetry Speed is 0.01V/s.Electromotive force (the E that test obtainsAg/AgCl) it is converted into the electromotive force (E to reversible hydrogen electrodeRHE): ERHE=EAg/AgCl+ 0.197+0.059×pH.Result: its photoelectric current take-off potential is 0.2V, under electromotive force is 1.23V, density of photocurrent is 2.8mA/ cm2.Water oxidation initiation potentials 0.26V (versus RHE)
Embodiment 2
A. 0.3667g Co (NO is weighed3)2·6H2O、0.1576g Al(NO3)3·9H2O, 0.2522g urea, 0.0622gNH4F, in the beaker of 250mL, adds 70mL deionized water, is sufficiently mixed, and adding 2mL concentration is 0.5mg/mL Graphene, ultrasonic, stirring to being mixed to form uniform solution, ultrasonic power 50W, time are 20min, temperature 30 DEG C, preparation mixing Saline solution.
B. it is the BiVO of 220nm by grain size4The conducting surface of electrode upwards sways 45 °, is placed in water heating kettle inner bag, and Add the mixed solution of the step A configuration of 5mL, make growth have BiVO4Part be totally submerged in solution, ultrasonic, ultrasonic merit Rate 50W, time 10min, be sufficiently mixed uniformly, and hydro-thermal reaction 2h at 100 DEG C, after natural cooling, takes out electrode, first with third Ketone washes twice, and every time with 20mL, then uses alcohol flushing twice, every time with 20mL, and, finally with after deionized water rinsing, put 70 DEG C of baking ovens are dried 2 hours, obtains G@LDHs and be combined BiVO4Optoelectronic pole.
Use with embodiment 1 evaluation methodology, evaluation result: photoelectric current take-off potential is 0.24V, under electromotive force is 1.23V Density of photocurrent is 2.5mA/cm2, water oxidation initiation potentials 0.29V (versus RHE).
Embodiment 3
A. 0.2037gCo (NO is weighed3)2·6H2O、0.1018gNi(NO3)2·6H2O、0.1313gAl(NO3)3·9H2O、 0.1050g urea, 0.0370gNH4F, in the beaker of 250mL, adds 70mL deionized water, is sufficiently mixed, adds 3mL concentration For 1.5mg/mL Graphene, ultrasonic, stirring is to being mixed to form uniform solution, and ultrasonic power 60W, time are 30min, temperature 25 DEG C, prepare mixing salt solution.
B. it is the BiVO of 230nm by grain size4The conducting surface of electrode upwards sways 45 °, is placed in water heating kettle inner bag, and Add the mixed solution of the step A configuration of 7mL, make growth have BiVO4Part be totally submerged in solution, ultrasonic, ultrasonic merit Rate 60W, time 30min, be sufficiently mixed uniformly, and hydro-thermal reaction 6h at 100 DEG C, after natural cooling, takes out electrode, first with third Ketone washs 3 times, every time with 20mL, then uses alcohol flushing 3 times, every time with 20mL, finally with after deionized water rinsing, is placed on 50 DEG C baking oven is dried 3 hours, obtains G@LDHs and be combined BiVO4 optoelectronic pole.
Use with embodiment 1 evaluation methodology, evaluation result: photoelectric current take-off potential is 0.23V, under electromotive force is 1.23V Density of photocurrent is 2.65mA/cm2, water oxidation initiation potentials 0.30V (versus RHE).
Embodiment 4
A. 0.3056g Co (NO is weighed3)2·6H2O、0.1018gNi(NO3)2·6H2O、0.1313gAl(NO3)3· 9H2O, 0.2102g urea, 0.0519gNH4F, in the beaker of 250mL, adds 70mL deionized water, is sufficiently mixed, adds 4mL Concentration is 2mg/mL Graphene, ultrasonic, stirring to being mixed to form uniform solution, ultrasonic power 60W, time are 10min, temperature 40 DEG C, prepare mixing salt solution.
B. it is the BiVO of 240nm by grain size4Electrodes conduct towards on sway 45 °, be placed in water heating kettle inner bag, and add Enter the mixed solution of the step A configuration of 8mL, make growth have BiVO4Part be totally submerged in solution, ultrasonic, ultrasonic power 30W, time 30min, be sufficiently mixed uniformly, and hydro-thermal reaction 10h at 100 DEG C, after natural cooling, takes out electrode, first with third Ketone washs 1 time, every time with 20mL, then uses alcohol flushing 2 times, every time with 20mL, finally with after deionized water rinsing, is placed on 40 DEG C baking oven is dried 1 hour, obtains G@LDHs and be combined BiVO4 optoelectronic pole.
Use with embodiment 1 evaluation methodology, evaluation result: photoelectric current take-off potential is 0.27V, under electromotive force is 1.23V Density of photocurrent is 2.7mA/cm2, water oxidation initiation potentials 0.28V (versus RHE).
Embodiment 5
A. 0.2181g Ni (NO is weighed3)2·6H2O、0.1010g Fe(NO3)3·9H2O, 0.1501g urea, 0.0370gNH4F, in the beaker of 250mL, adds 70mL deionized water, is sufficiently mixed, and adding 5mL concentration is 2.5mg/mL Graphene, ultrasonic, stirring to being mixed to form uniform solution, ultrasonic power 60W, time are 25min, temperature 25 DEG C, preparation mixing Saline solution.
B. by grain size 250nm BiVO4The conducting surface of electrode upwards sways 45 °, is placed in water heating kettle inner bag, and adds Enter the mixed solution of the step A configuration of 7mL, make growth have BiVO4Part be totally submerged in solution, ultrasonic, ultrasonic power 50W, time 15min are sufficiently mixed uniformly, hydro-thermal reaction 12h at 120 DEG C, after natural cooling, take out electrode, first use acetone Wash 1 time, every time with 10mL, then use alcohol flushing 3 times, every time with 10mL, finally with after deionized water rinsing, be placed on 70 DEG C Baking oven is dried 2 hours, obtains G@LDHs and be combined BiVO4Optoelectronic pole.
Use with embodiment 1 evaluation methodology, evaluation result: photoelectric current take-off potential is 0.25V, under electromotive force is 1.23V Density of photocurrent is 2.6mA/cm2, water oxidation initiation potentials 0.27V (versus RHE).

Claims (2)

1. a G LDHs is combined BiVO4Optoelectronic pole, is expressed as: G@LDHs/BiVO4, wherein BiVO4It is grown in electro-conductive glass table Face, crystal formation is monocline, and interparticle distance is 50～120nm, and particle size is 200～300nm；G LDHs represents metal hydrogen-oxygen Compound and the complex of Graphene；It is grown directly upon BiVO4On, wherein G@LDHs is the flower-like structure that two-dimensional nano sheet assembles, Its a diameter of 3～5 μm, lamellar spacing is 10～100nm；LDHs represents complex metal hydroxide, and its chemical formula is: M2+ 1-xM3 + x(OH)2]x+(AN-)x/n·mH2O, wherein M2+Represent bivalent metal ion, M2+For Ni2+、Co2+In one or both；M3+Generation Table trivalent metal ion, M3+For Al3+、Fe3+In one or both, AN-For interlayer anion, it is nitrate anion, sulfate radical, carbon One or both in acid group, m is moisture subnumber, m=5～15, x=1/3～1；G represents Graphene.
2. the G LDHs that a kind is prepared described in claim 1 is combined BiVO4The method of optoelectronic pole, concrete preparation process is as follows:
A. M is used2+Salt, M3+Salt, urea and NH4F prepares mixing salt solution, and wherein total concentration of metal ions is 15～50mmol/L, M2+ With M3+Mol ratio be 2～4:1, the concentration of urea is 30～80mmol/L, is 1～4:1 with the ratio of total metal ion；NH4F's Concentration is 15～50mmol/L, is 1～3:1 with the ratio of total metal ion；Anion in solution be nitrate anion, sulfate radical, One or both in carbonate；Adding concentration again in above-mentioned mixing salt solution is 0.5～3mg/mL graphene dispersing solution, presses Graphene dispersing solution is 0.01～0.1:1 addition with the volume ratio of mixing salt solution, makes Graphene content in mixed solution Be 0.01～0.4mg/mL, ultrasonic, stirring to being mixed to form uniform solution.Ultrasonic power 40～100W, time 10～30min, Temperature 20～40 DEG C；
Described M2+Salt is Ni2+Salt, Co2+One or both in salt, M3+Salt is Al3+Salt, Fe3+One or both in salt；
Described graphene dispersing solution be the solid content that graphene dispersion is prepared in water be 0.5～3mg/mL dispersion liquid, institute Graphene be monolayer or few layer graphite flake layer, thickness about 0.3～1nm, surface area is 700～800m2/g；
B. by BiVO4The conducting surface of electrode is upwards swayed and is placed in water heating kettle inner bag, and inclination angle is 30～60 °, and adds step A and join The mixed solution put, makes growth on electrode have BiVO4Part be totally submerged in solution, the power ultrasonic 10 with 40～100W ～30min；It is warming up to 100～180 DEG C of hydro-thermal reactions 2～20 hours again, after natural cooling, takes out electrode, first wash with acetone Wash 1～4 time, each 10～50mL；The most afterwards with alcohol flushing 1～4 times, each 10～50mL；Finally with deionized water rinsing, in 70～100 DEG C are dried 1～10 hour, obtain G@LDHs and be combined BiVO4Optoelectronic pole.
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Cited By (5)

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CN107324441A (en) * 2017-07-07 2017-11-07 黄河科技学院 Ferronickel oxyhydroxide modification pucherite optoelectronic pole and preparation method thereof, application
CN109078639A (en) * 2018-07-25 2018-12-25 华南师范大学 A kind of BiVO4/ NiCo LDHs porous fibre and its preparation method and application
CN111348728A (en) * 2020-03-25 2020-06-30 浙江工商大学 MOF and HrGO co-modified bismuth vanadate electrode and preparation method and application thereof
CN111431498A (en) * 2020-03-31 2020-07-17 中国科学院宁波材料技术与工程研究所 Conductive polymer solution for crystal resonator and application thereof
CN112095092A (en) * 2020-08-13 2020-12-18 华南理工大学 Method for preparing high-performance super-hydrophobic stainless steel by utilizing nano layered double hydroxide and prepared high-performance super-hydrophobic stainless steel

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