CN106492800B - Pt/Au-BiVO4The preparation method of Z- type visible light nano piece photochemical catalyst - Google Patents
Pt/Au-BiVO4The preparation method of Z- type visible light nano piece photochemical catalyst Download PDFInfo
- Publication number
- CN106492800B CN106492800B CN201611051029.8A CN201611051029A CN106492800B CN 106492800 B CN106492800 B CN 106492800B CN 201611051029 A CN201611051029 A CN 201611051029A CN 106492800 B CN106492800 B CN 106492800B
- Authority
- CN
- China
- Prior art keywords
- bivo
- photochemical catalyst
- visible light
- preparation
- nano piece
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 94
- 238000005286 illumination Methods 0.000 claims abstract description 22
- 239000011941 photocatalyst Substances 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000002135 nanosheet Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 6
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 131
- 229910052697 platinum Inorganic materials 0.000 claims description 21
- 230000001699 photocatalysis Effects 0.000 abstract description 28
- 238000007146 photocatalysis Methods 0.000 abstract description 18
- 238000006555 catalytic reaction Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 49
- 239000010931 gold Substances 0.000 description 43
- 238000000151 deposition Methods 0.000 description 21
- 230000008021 deposition Effects 0.000 description 17
- 238000012986 modification Methods 0.000 description 16
- 230000004048 modification Effects 0.000 description 14
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 12
- 229940012189 methyl orange Drugs 0.000 description 12
- 229910052737 gold Inorganic materials 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000002256 photodeposition Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 235000012149 noodles Nutrition 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to Pt/Au-BiVO4The preparation method of Z- type visible light nano piece photochemical catalyst, comprising the following steps: by Au-BiVO4Nanosheet photocatalyst ultrasonic disperse forms unit for uniform suspension in ethanol water；Chloroplatinic acid aqueous solution is added in suspension；Further it is passed through N2It is after protection and system is closed, illumination is carried out in LED light；Gained precipitating alcohol wash, wash after filter, vacuum drying to get efficient stable Pt/Au-BiVO4Z- type visible light nano piece photochemical catalyst.The beneficial effects of the present invention are: synthetic method operates very simple, it is not necessary that various organic surface active agents, additive etc. is added.Entire reaction process equipment requirement is low simultaneously, has many advantages, such as that being easy to high-volume synthesizes, the catalysis material of preparation has high visible light photocatalysis performance.
Description
Technical field
The present invention relates to BiVO4The pattern modification of particle, BiVO4The surface of particle is modified, is specifically related to a kind of efficiently steady
Determine Pt/Au-BiVO4The preparation method of Z- type visible light nano piece photochemical catalyst.
Background technique
In recent years, the multiphase photocatalysis based on semiconductor material is a kind of economically and efficiently solution environmental pollution and energy
The new technology of source crisis and receive significant attention.By the research of decades, Photocatalitic Technique of Semiconductor is solving environment and energy
There is biggish development in terms of source problem.However, due to most of reported its visible absorption narrow range of catalysis material,
Quantum efficiency is lower, and photocatalytic activity and stability is not high, causes photocatalysis technology that cannot be widely applied.In order to be widely applied
Photocatalitic Technique of Semiconductor, there is an urgent need to design new and effective stabilization and with the catalysis material of wider visible absorption.
For a conductor photocatalysis system, to high visible light photocatalysis active and stability, it is necessary to
There are high visible light utilization efficiency and quantum efficiency, on the one hand to widen the visible absorption range of photochemical catalyst, on the other hand
It reduces the compound probability of electrons and holes and accelerates interfacial catalysis reaction.Nearest research discovery carries out crystal face work to photochemical catalyst
Journey modification is to improve the effective way of the visible light photocatalysis active and stability of catalysis material.Its reason is to difference
The modification of catalysis material progress crystal face engineering (such as BiVO4Nanometer sheet) after, light induced electron can be orientated and be transferred to catalysis material
Electron rich face, photohole, which can be orientated, is transferred to hole-rich face, can thus greatly reduce answering for electrons and holes
Close probability.Then selective modification auxiliary agent (such as Pt, Au) in particular crystal plane, can further speed up interfacial charge transfer and
Interfacial catalysis reaction.With Au-BiVO4For, on the one hand the selective deposition of Au can accelerate interfacial charge transfer；On the other hand
Since the local plasmon resonance effect of Au nano particle can construct Au-BiVO4Z- type conductor photocatalysis system, thus
Improve its redox ability.According to above-mentioned expection, Au-BiVO4Photochemical catalyst should be with respect to BiVO4Photochemical catalyst has aobvious
The performance of work improves.However our result of study shows: the selective modification of Au is only capable of limitedly improving BiVO4Photocatalysis
Activity.The activity for grinding the interfacial catalysis oxygen reduction reaction for the mainly Au that traces it to its cause is not strong.And further increase Au-BiVO4
The effective way of photocatalyst activity is on Au in the efficient oxygen reduction catalyst of selective deposition (such as Pt).
As far as we know, there is presently no Pt/Au-BiVO4It the preparation of Z- type visible light nano piece photochemical catalyst and mentions
High BiVO4The photocatalytic activity of photochemical catalyst and the report of stability.
Summary of the invention
The technical problem to be solved by the present invention is to be directed to the above-mentioned prior art, a kind of simple and effective efficient stable is proposed
Pt/Au-BiVO4The preparation method of Z- type visible light nano piece photochemical catalyst, passes through BiVO4The crystal face engineering modification of particle and boundary
Face auxiliary agent selective modification, prepared Pt/Au-BiVO4Z- type visible light nano piece photochemical catalyst has higher photocatalysis
Stability and photocatalytic activity.
The technical proposal adopted by the invention to solve the above technical problems is that: Pt/Au-BiVO4Z- type visible light nano piece
The preparation method of photochemical catalyst, it is characterised in that the following steps are included:
1) by Au-BiVO4Nanosheet photocatalyst ultrasonic disperse forms unit for uniform suspension in ethanol water；
2) chloroplatinic acid aqueous solution is added in suspension；
3) further it is passed through N2It is after protection and system is closed, illumination is carried out in LED light；
4) gained precipitating alcohol wash, wash after filter, vacuum drying to get efficient stable Pt/Au-BiVO4Z- type visible light
Nanosheet photocatalyst.
According to the above scheme, it is Au-BiVO that step 2), which controls the content of wherein platinum,4Nanometer sheet mass percentage content
0.01%-10%.
According to the above scheme, the light intensity of the LED light is 10-80mW/cm2。
According to the above scheme, the light application time 0.1-2h of the LED light.
Present invention proposition synthesizes BiVO by hydro-thermal method first4Nanometer sheet, then by Photodeposition in BiVO4Nanometer sheet
(110) face on uniform deposition Au particle, finally by further Photodeposition on Au particle uniform deposition Pt particle, from
And prepare efficient stable Pt/Au-BiVO4Z- type visible light nano piece photochemical catalyst.By to BiVO4Catalysis material crystal face work
Journey modification increases BiVO with interfacial additive (Pt, Au modification) selective modification4The photocatalytic activity and stabilization of catalysis material
The basic principle of property is: (1) working as BiVO4After nanometer sheet absorbs photon, light induced electron can be orientated the electricity for being transferred to catalysis material
Sub- enrichment face (110) face, hole, which can be orientated, is transferred to hole-rich face (101) face；(2)BiVO4(110) on face electrons through Au
Particle is quickly transferred on Pt particle to react with the oxygen in solution again, and BiVO at this time4Hole on nanometer sheet (101) face is high
Oxidation of organic compounds is imitated, BiVO is improved4Visible light photocatalysis performance；(3) when specific wavelength light excitation Au particle generate etc. from
Daughter resonance effects makes it have stronger absorption to visible light, to widen Pt/Au-BiVO4Nanosheet photocatalyst is to visible
The utilization rate and photocatalytic activity of light；(4) in addition, the crystallized ability that this metal is contacted with semiconductor contact and metal with metal
It is relatively strong, so that the metal promoter in multiple degradation of organic substances is not easy to be desorbed, be conducive to be repeatedly circulated, enhance Pt/Au-
BiVO4Photocatalysis stability.
The beneficial effects of the present invention are: BiVO is synthesized by hydro-thermal method first4Then nanometer sheet is existed by Photodeposition
BiVO4Uniform deposition Au particle on (110) face of nanometer sheet, finally by further Photodeposition on Au particle uniform deposition
Pt particle, to prepare efficient stable Pt/Au-BiVO4Z- type visible light nano piece photochemical catalyst.Synthetic method operation ten
Divide simply, it is not necessary that various organic surface active agents, additive etc. is added.The glass that entire reaction process only needs beaker etc. common simultaneously
Glass instrument, equipment requirement is low, without reaction units such as expensive various processing synthesis devices and high temperature and pressure, has and is easy to large quantities of
The advantages that amount synthesis.The catalysis material of preparation has high visible light photocatalysis performance, is expected to generate good society and warp
Ji benefit.
Detailed description of the invention
Fig. 1 is (a) BiVO in embodiment 14(b) Pt/Au-BiVO4The FESEM of photochemical catalyst schemes；
Fig. 2 is Pt/Au-BiVO in embodiment 14First vegetarian noodles of photochemical catalyst sweeps figure；
Fig. 3 is (a) BiVO in embodiment 14(b) Pt/Au-BiVO4The XRD spectrum of photochemical catalyst (put by embedded elliptic region
Big figure)；
Fig. 4 is (a) BiVO in embodiment 14(b) Pt/Au-BiVO4(A is full spectrum, B Au to the XPS spectrum figure of photochemical catalyst
4f and C is Pt 4f high score rate spectrum)；
Fig. 5 is (a) BiVO in embodiment 14(b) Pt/Au-BiVO4UV-vis map (embedded a, the b sample of photochemical catalyst
Real figure)；
Fig. 6 is (a) BiVO in embodiment 14(b) Pt/Au-BiVO4Degradation rate constant k of the photochemical catalyst to methyl orange；
Fig. 7 is Pt/Au-BiVO in embodiment 14The rate constants k that photochemical catalyst Pyrogentisinic Acid repeatedly degrades；
Fig. 8 is that the degree of Pt is deposited in embodiment 5 to Pt/Au-BiVO4Degradation speed of the photochemical catalyst to methyl orange
Rate constant k (additional amount for wherein corresponding to chloroplatinic acid aqueous solution is respectively 1.4 μ L, 6.7 μ L, 13.4 μ L, 67.0 μ L, 134.0 μ L,
268.0μL)；
Fig. 9 is intensity of illumination in embodiment 3 to Pt/Au-BiVO4The FESEM of Pt deposition schemes (wherein in photochemical catalyst
a:10mW/cm2, b:20mW/cm2, c:40mW/cm2, d:80mW/cm2)；
Figure 10 is light application time in embodiment 4 to Pt/Au-BiVO4The FESEM of Pt deposition schemes (its in photochemical catalyst
Middle a:0.1h, b:0.5h, c:1.0h, d:2h)；
Specific embodiment
Below with reference to embodiment, the present invention will be further described in detail, but this explanation will not be constituted to of the invention
Limitation.
Embodiment 1:
Pt/Au-BiVO4The preparation process of Z- type visible light nano piece photochemical catalyst is as follows: 1) Au-BiVO4Nanometer sheet light is urged
The preparation method of agent is shown in document (Li, R.；Zhang,F.；Wang,D.；Yang,J.；Li,M.；Zhu,J.；Zhou,X.；Han,
H.；Li, C. Nature communications 2013,4,1432.), wherein BiVO4Amount be 0.05g, gold chloride is water-soluble
The concentration of liquid is 0.1 mol/L, and the additional amount of aqueous solution of chloraurate is 37.0 μ L, wherein the degree of gold is 3%；2)
Pt/Au-BiVO4The preparation of nanosheet photocatalyst: the Au-BiVO of 0.05g is taken4Ultrasonic disperse is in 80mL 12.5vol% ethyl alcohol
In aqueous solution, 67 μ L 0.02mol/L chloroplatinic acid aqueous solutions (degree for being wherein converted into platinum is 0.5%), N is added2
It is after protection 30 minutes that system is closed, it is 20mW/cm in intensity of illumination2Illumination 0.5h in the LED light of 420nm, finally precipitating is used
Alcohol is washed three times, and washing is filtered afterwards three times, in 60 DEG C of vacuum drying 2h to get to efficient stable Pt/Au-BiVO4Z- type visible light
Nanosheet photocatalyst.
Pt/Au-BiVO4The Characterization for Microstructure method of Z- type visible light nano piece photochemical catalyst: field emission scanning electron microscope is used
(FESEM) pattern and granular size are observed；(EDAX Genesis S-Twin TEM), which is swept, with high power member vegetarian noodles determines each element
Position；Situation is crystallized with X-ray diffraction (XRD) spectrum analysis；In the photoelectron spectrograph that Mg target K α is X-ray source
(KRATOA XSAM800 XPS) obtains x-ray photoelectron spectroscopy figure, so that it is determined that the composition and valence state of element；Use UV, visible light
The UV, visible light light diffusing reflection absorption spectra of spectrometer (UV-2550) measurement sample.
Fig. 1 is efficient stable Pt/Au-BiVO4The FESEM of Z- type visible light nano piece photochemical catalyst schemes.It can from Fig. 1 a
To find out, the BiVO of decahedron pattern4The size of nanometer sheet is 3.2 μm, with a thickness of 1.4 μm.It is known by pervious document
In eight sides be (101) face, upper and lower two surfaces are (110) face；Through Pt, after the modification of Au particle surface (Fig. 1 b), Pt/Au-
BiVO4There is no significant changes for the size of compound particle, and Pt, Au particle are only modified in BiVO4Two surfaces up and down
(110) on face, illustrate Pt, the low temperature light deposition modification of Au particle can't cause BiVO4The significant change of particle, and have
It is selective.
Fig. 2 is Pt/Au-BiVO4First vegetarian noodles of nanosheet photocatalyst sweeps figure, it can be seen that the nanometer sheet contains
Pt, Au, Bi, V and O element, and the position of Pt, Au element is overlapped, the Pt particle of light deposition has deposited on Au particle after explanation.
Fig. 3 a and 3b are respectively BiVO4And Pt/Au-BiVO4The XRD spectrum (embedded elliptic region enlarged drawing) of photochemical catalyst.
It can be seen from the figure that through Pt, after the modification of Au particle surface, BiVO4XRD characteristic diffraction peak there is no great change, say
The modification of bright Pt, Au particle surface has no effect on BiVO4Crystal phase and crystallization degree.Exist from b known to embedded elliptic region enlarged drawing
2 θ, which are 38.3 °, a characteristic diffraction peak, and through literature search, this is Au (111) region feature diffraction maximum, illustrates that Au particle is deposited on
BiVO4Surface on.Simultaneously as Pt granule content is seldom, corresponding diffraction maximum cannot be shown in XRD diagram.
Fig. 4 a and 4b are respectively BiVO4And Pt/Au-BiVO4(A is that full spectrum, B and C are Au 4f to the XPS spectrum figure of photochemical catalyst
It is composed with Pt 4f high magnification).Compared to pure BiVO4Sample, Pt/Au-BiVO4The XPS spectrum figure of photochemical catalyst in 84.1eV and
87.1eV or so illustrates that Au successfully loads to BiVO evident from the Photoelectron peak (Fig. 4 B-b) of Au 4f out4Photochemical catalyst table
Face；Relative to pure BiVO4Sample P t/Au-BiVO4The XPS spectrum figure of photochemical catalyst is in 69.7eV and 75.0eV or so evident from out
The Photoelectron peak (Fig. 4 C-b) of Pt 4f, illustrates that Pt successfully loads to BiVO4Photocatalyst surface.From 1 XPS analysis (a) of table
BiVO4(b) Pt/Au-BiVO4The load capacity of Au known to the atomic percent (%) of photochemical catalyst difference element is 2.94at%,
The load capacity of Pt is 0.47at%.
Fig. 5 a and 5b are respectively BiVO4And Pt/Au-BiVO4The UV-vis spectrogram of visible-light photocatalyst.In fig 5 a,
BiVO4Visible-range of the sample in 400-530nm has absorption.Work as Pt, Au particle and BiVO4After compound (Fig. 5 b), sample at this time
Color becomes dark-brown from glassy yellow, and has stronger absorption in the visible-range of 400-800nm, this illustrates Pt, and Au
Son can greatly widen BiVO after surface modification4Visible absorption range.
Pt/Au-BiVO4The photocatalytic activity of Z- type visible light nano piece photochemical catalyst is to pass through photo-catalytic degradation of methyl-orange
What solution was characterized.Experimentation is as follows: 0.05g photochemical catalyst is dispersed in equipped with 10mL methyl orange aqueous solution (20mg/L)
Culture dish in (diameter 5cm).Visible light source is the xenon lamp equipped with optical filter (filtering off ultraviolet light of the wavelength less than 400nm),
The average intensity for being radiated at methyl orange liquid level is 40mW/cm2, every 15min, reaction solution is first separated by filtration, and is then surveyed
Methyl orange concentration in quantitative response solution.In degradation solution the concentration of methyl orange by ultraviolet-visible absorption spectroscopy measurement (UV-2550,
SHIMADZU,Japan).Since the methyl orange solution of low concentration meets pseudo-first-order kinetics equation in Photocatalytic Degradation Process:
lnc0/ c=kt, wherein c0It is the concentration of methyl orange in degradation solution before light-catalyzed reaction and when reaction certain time t respectively with c, and
K is the rate constant of methyl orange degradation.Therefore, the light that catalysis material can be evaluated with the rate constants k of methyl orange degradation is urged
Change performance.
Fig. 6 a and 6b are respectively BiVO4And Pt/Au-BiVO4Rate of the visible-light photocatalyst to Photocatalytic Degradation of Methyl Orange
Constant figure.It can be seen from the figure that BiVO4Extremely low rate of photocatalytic oxidation is shown to methyl orange, k is about 0min-1；When
BiVO4After surface Pt, Au particle are modified, resulting Pt/Au-BiVO4The photocatalysis performance of visible-light photocatalyst obtains
It is apparent to improve, k 0.014min-1.The main reason is that Pt, Au particle can be used as BiVO4Effective auxiliary agent of photochemical catalyst,
Promote light induced electron and hole efficiently separates and widens visible absorption range.
In order to prove Pt/Au-BiVO4The photocatalysis stability of compounded visible light photocatalyst, we to photochemical catalyst into
Multiple circulation degradation of phenol is gone, as a result as shown in Figure 7.It can be seen from the figure that light is urged after 5 photocatalysis circular responses
The ability of agent degradation of phenol illustrates the BiVO through Pt, after the modification of Au particle there is no reducing4Photocatalysis with higher is steady afterwards
It is qualitative.
Table 1 is (a) BiVO in XPS analysis in embodiment 14(b) Pt/Au-BiVO4The atom of photochemical catalyst difference element
Percentage (%).
Embodiment 2:
In order to examine the degree of platinum to Pt/Au-BiVO4Compounded visible light photocatalyst photocatalysis performance influences,
In addition to the additional amount of chloroplatinic acid aqueous solution is different, other reaction conditions such as, intensity of illumination (20mW/cm2), light application time
(0.5h) etc. is same as Example 1, as a result as shown in Figure 8.The result shows that when the additional amount of chloroplatinic acid aqueous solution is 67.0 μ L
When (be converted into platinum degree be 0.5%), resulting Pt/Au-BiVO4Compounded visible light photocatalyst photocatalysis performance
It is best.Main cause is, when the additional amount of chloroplatinic acid aqueous solution is less than 67.0 μ L (degree of platinum is less than 0.5%),
Since the amount of deposition Pt is inadequate, in the photocatalytic process, electron mobility is lower, causes quantum efficiency lower, photocatalytic activity
It is not high；When the additional amount of chloroplatinic acid aqueous solution is greater than 67.0 μ L (degree of platinum is greater than 0.5%), due to deposition Pt's
Amount is excessive, and excessive Pt may be deposited on BiVO4Hole-rich face (101) face on, in the photocatalytic process, excessive Pt
As the complex centre of electron hole, quantum efficiency is caused to reduce, photocatalytic activity reduces；When the additional amount of chloroplatinic acid aqueous solution
When for 67.0 μ L (degree of platinum is 0.5%), the amount for depositing Pt is sufficient, and the Pt selectivity of sufficient amount is deposited on
On Au particle, in the photocatalytic process, electronics is through on Au pellet transportation to Pt particle, and electron mobility highest, quantum efficiency
Highest, photocatalytic activity highest；Therefore, in Pt/Au-BiVO4In the preparation process of compounded visible light photocatalyst, exploration is most
The additional amount of good chloroplatinic acid aqueous solution is 67.0 μ L, and the degree of best platinum is 0.5%.
Embodiment 3:
In order to examine intensity of illumination to Pt/Au-BiVO4The influence of compounded visible light photocatalyst Pt deposition removes light
Other than intensity difference, light application time (0.5h), degree (0.5%) of platinum etc. is same as Example 1, as a result as schemed
Shown in 9.The result shows that when intensity of illumination is less than 20mW/cm2When, since intensity of illumination is too weak, Pt is made to sink before the deadline
Long-pending amount is very little, so cannot be clearly visible the presence (Fig. 9 a) of Pt particle on Au particle.When intensity of illumination is relatively larger than 20mW/
cm2When, since intensity of illumination is stronger, the amount for depositing Pt before the deadline is more, so not only seeing on Au particle
The presence of Pt particle, in BiVO4(110) face on it can be seen that Pt particle presence (Fig. 9 c).When intensity of illumination is even larger than
20mW/cm2When, since intensity of illumination is too strong, the amount for depositing Pt before the deadline is too many, so not only in Au particle and
BiVO4(110) face on it can be seen that Pt particle presence, also can be in BiVO4Hole-rich face (101) face on it can be seen that
The presence (Fig. 9 d) of Pt particle.When intensity of illumination is 20mW/cm2When, since intensity of illumination is suitable for, make Pt in the defined time
The amount of interior deposition is moderate, and the presence (Fig. 9 b) of Pt particle is only seen in Au particle.Therefore, in Pt/Au-BiVO4It is compound visible
In the preparation process of light photochemical catalyst, the optimum illumination intensity for exploring the best Pt of deposition is 20 mW/cm2。
Embodiment 4:
In order to examine light application time to Pt/Au-BiVO4The influence of compounded visible light photocatalyst Pt deposition removes light
Other than time difference, intensity of illumination (20mW/cm2), degree (0.5%) of platinum etc. is same as Example 1, as a result
As shown in Figure 10.The result shows that, since light application time is too short, keeping Pt strong in defined illumination when light application time is less than 0.5h
The amount deposited in degree is very little, is insufficient to allow enough Pt to deposit on Au particle, so only seeing on Au particle a small amount of
There is (Figure 10 a) in Pt particle；When light application time is longer than 0.5h, since light application time is longer, keep Pt strong in defined illumination
The amount deposited in degree is more, so the presence of Pt particle is not only seen on Au particle, in BiVO4(110) face on can also see
To the presence (Figure 10 c) of Pt particle.When light application time is longer than 0.5h, since light application time is too long, make Pt in defined light
It is too many according to the amount deposited in intensity, so not only in Au particle and BiVO4(110) face on it can be seen that Pt particle presence,
It also can be in BiVO4Hole-rich face (101) face on it can be seen that Pt particle presence (Figure 10 d).When light application time is 0.5h
When, since light application time is suitable for, the amount for depositing Pt in defined intensity of illumination is moderate, and only sees Pt particle in Au particle
Presence (Figure 10 b).Therefore, in Pt/Au-BiVO4In the preparation process of compounded visible light photocatalyst, the best of deposition is explored
The optimum illumination time of Pt is 0.5h.
Claims (3)
1.Pt/Au-BiVO4The preparation method of Z- type visible light nano piece photochemical catalyst, it is characterised in that the following steps are included:
1) by Au-BiVO4Nanosheet photocatalyst ultrasonic disperse forms unit for uniform suspension in ethanol water；
2) chloroplatinic acid aqueous solution is added in suspension；The content for controlling wherein platinum is Au-BiVO4Nanometer sheet mass percent contains
The 0.01%-10% of amount；
3) further it is passed through N2It is after protection and system is closed, illumination is carried out in LED light；
4) gained precipitating alcohol wash, wash after filter, vacuum drying to get efficient stable Pt/Au-BiVO4Z- type visible light nano piece
Photochemical catalyst.
2. Pt/Au-BiVO according to claim 14The preparation method of Z- type visible light nano piece photochemical catalyst, feature
The light intensity for being the LED light is 10-80mW/cm2。
3. Pt/Au-BiVO according to claim 14The preparation method of Z- type visible light nano piece photochemical catalyst, feature
It is the light application time 0.1-2h of the LED light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611051029.8A CN106492800B (en) | 2016-11-24 | 2016-11-24 | Pt/Au-BiVO4The preparation method of Z- type visible light nano piece photochemical catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611051029.8A CN106492800B (en) | 2016-11-24 | 2016-11-24 | Pt/Au-BiVO4The preparation method of Z- type visible light nano piece photochemical catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106492800A CN106492800A (en) | 2017-03-15 |
| CN106492800B true CN106492800B (en) | 2019-04-30 |
Family
ID=58328823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611051029.8A Expired - Fee Related CN106492800B (en) | 2016-11-24 | 2016-11-24 | Pt/Au-BiVO4The preparation method of Z- type visible light nano piece photochemical catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106492800B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114405506A (en) * | 2022-01-21 | 2022-04-29 | 武汉理工大学 | Bi-metal PdAu auxiliary agent selectively modified bismuth vanadate photocatalyst and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728355A (en) * | 2011-04-07 | 2012-10-17 | 中国科学院大连化学物理研究所 | A visible light-driven photo catalyst for removing sulfur-containing compounds in fuel oil, a preparation method thereof and application thereof |
-
2016
- 2016-11-24 CN CN201611051029.8A patent/CN106492800B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728355A (en) * | 2011-04-07 | 2012-10-17 | 中国科学院大连化学物理研究所 | A visible light-driven photo catalyst for removing sulfur-containing compounds in fuel oil, a preparation method thereof and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Spatial separation of photogenerated electrons and holes among {010} and {110} crystal facets of BiVO4";Rengui Li et al;《NATURE COMMUNICATIONS》;20130205;第4卷;第2页右栏第3段，图1 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106492800A (en) | 2017-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | A novel step-scheme BiVO4/Ag3VO4 photocatalyst for enhanced photocatalytic degradation activity under visible light irradiation | |
| Zhu et al. | Porous Ag-ZnO microspheres as efficient photocatalyst for methane and ethylene oxidation: Insight into the role of Ag particles | |
| Liu et al. | Enhanced photocatalytic activity of Bi4Ti3O12 nanosheets by Fe3+-doping and the addition of Au nanoparticles: photodegradation of phenol and bisphenol A | |
| Wu et al. | Nitrogen-doped anatase nanofibers decorated with noble metal nanoparticles for photocatalytic production of hydrogen | |
| CN103861620B (en) | A kind of carbon quantum dot, noble metal and indium sulfide zinc composite photo-catalyst and preparation method thereof | |
| CN105879887B (en) | A kind of Cu2O@Cu/AgBr composite photo-catalyst and preparation method thereof | |
| Sabzehmeidani et al. | Nanofibers based quaternary CeO2/Co3O4/Ag/Ag3PO4 S-scheme heterojunction photocatalyst with enhanced degradation of organic dyes | |
| Zwara et al. | Shape-dependent enhanced photocatalytic effect under visible light of Ag3PO4 particles | |
| Xiao et al. | Ordered mesoporous CeO2/ZnO composite with photodegradation concomitant photocatalytic hydrogen production performance | |
| Ortiz et al. | Silver oxidation state effect on the photocatalytic properties of Ag doped TiO2 for hydrogen production under visible light | |
| Liu et al. | One-step synthesis of metallic Bi deposited Bi2WO6 nanoclusters for enhanced photocatalytic performance: An experimental and DFT study | |
| Cong et al. | A novel silver-loaded graphitic carbon nitride with structural defect assisted by ascorbic acid for the fast and efficient degradation of sulfamethoxazole | |
| Zhao et al. | Bi4O5Br2 nanoflower and CdWO4 nanorod heterojunctions for photocatalytic synthesis of ammonia | |
| Hu et al. | Biomaterial-assisted synthesis of AgCl@ Ag concave cubes with efficient visible-light-driven photocatalytic activity | |
| Kmetykó et al. | Enhanced photocatalytic H 2 generation on noble metal modified TiO 2 catalysts excited with visible light irradiation | |
| Hanh et al. | Synthesis of Co3O4 coated on N, S doped TiO2 for novel photocatalytic degradation of toxic organic pollutant in aqueous environment | |
| Yu et al. | Tunable photocatalytic selectivity and stability of Ba-doped Ag3PO4 hollow nanosheets | |
| Duan et al. | Synthesis of CuO/Ti-MCM-48 photocatalyst for the degradation of organic pollutions under solar-simulated irradiation | |
| Khudhair et al. | Assembling ZIF-67@ Cd0. 5Zn0. 5S nanocomposites with an enhanced photocatalytic activity | |
| Chen et al. | Facile synthesis of AgBr@ ZIF-8 hybrid photocatalysts for degradation of Rhodamine B | |
| Baluk et al. | MOF/TiO 2 erythrocyte-like heterostructures decorated by noble metals for use in hydrogen photogeneration and pollutant photodegradation | |
| Aksoy et al. | The rational design of gCN/a-WOx/Pt heterostructured nanophotocatalysts for boosting the hydrogen generation from the hydrolysis of ammonia borane under visible light | |
| CN106492800B (en) | Pt/Au-BiVO4The preparation method of Z- type visible light nano piece photochemical catalyst | |
| Jiao et al. | Barium titanate (1 0 1)/silver nanocomposite: preparation, photocatalytic activity, and mechanism based on Density Functional Theory | |
| Zhang | Photocatalytic applications of Au-deposited on TiO2 nanocomposite catalyst in dye degradation via photoreduction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190430 Termination date: 20191124 |