CN108525699A - A kind of ultra-thin 2D WO3/g-C3N4Z-type heterojunction photocatalyst and preparation method thereof - Google Patents
A kind of ultra-thin 2D WO3/g-C3N4Z-type heterojunction photocatalyst and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000243 solution Substances 0.000 claims description 16
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 108091003079 Bovine Serum Albumin Proteins 0.000 claims description 3
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229940098773 bovine serum albumin Drugs 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims 1
- 238000000338 in vitro Methods 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 239000008107 starch Substances 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 10
- 238000007146 photocatalysis Methods 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000725 suspension Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002525 ultrasonication 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
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of ultra-thin 2D WO3/g‑C3N4The preparation method of Z-type heterojunction photocatalyst, includes the following steps：S1 prepares ultra-thin 2D WO3Nanometer sheet；S2 prepares ultra-thin 2D g C3N4Nanometer sheet；And S3, pass through 2D WO3Nanometer sheet and 2D g C3N4Nanometer sheet prepares ultra-thin 2D WO3/g‑C3N4Z-type heterojunction photocatalyst.The present invention also provides a kind of ultra-thin 2D WO3/g‑C3N4Z-type heterojunction photocatalyst, including 2D WO3With 2D g C3N4, wherein 2D WO3With 2D g C3N4Mass ratio be 13：10.2D WO provided by the invention3/g‑C3N4The Z-type band structure of heterojunction photocatalyst improves light-catalysed efficiency, the 2D/2D hetero-junctions contacted face-to-face simultaneously can show big interfacial contact area and smaller interface resistance, charge transfer effciency is improved, light-catalysed performance and stability are thus further increased.
Description
Technical field
The present invention relates to environmental protection and energy field of functional materials to be particularly related to a kind of ultra-thin 2D WO3/g-C3N4Z-type is different
Matter knot photochemical catalyst and preparation method thereof.
Background technology
Photocatalyzed Hydrogen Production has been considered as converting the solar energy of low-density to directly available chemical energy most promising
One of approach.However, single semiconductor light-catalyst due to the high recombination probability of photo-generated charge carriers be extremely difficult to it is high
Photocatalytic activity.It is to solve the problems, such as one of this effective way to build suitable Heterojunction System.In general, efficiently heterogeneous
The design of knot photochemical catalyst is concentrated mainly in two key points.First, the suitable energy band of two semiconductor light-catalysts is interlocked
Arrangement, the other is ideal interface is used as high efficiency charge transfer/separation between two semiconductors.
Since Wang et al. first reported g-C3N4For photocatalysis Decomposition aquatic products hydrogen, g-C3N4Photochemical catalyst is due to it
Narrow band gap, it is seen that photoresponse, relatively negative conduction band positions, the synthetic method of simple possible and special two dimension (2D) stratiform knot
Structure has received extensive research.However, pure g-C3N4Photocatalysis performance also reach actual requirement far away.A series of and g-C3N4Tool
There is the semiconductor equalizing of energy band cross structure to be used to and g-C3N4Compound structure g-C3N4Base heterojunction structure photochemical catalyst.Such as
TiO2/g-C3N4, ZnO/g-C3N4, WO3/g-C3N4, CdS/g-C3N4, ZnIn2S4/g-C3N4, BiOI/g-C3N4.In these II types
The interface of hetero-junctions, light induced electron will be transferred to the CB of corrigendum from more negative valence band (CB), and photohole will be from corrigendum
Valence band (VB) is transferred to more negative VB.In this g-C3N4In base II type hetero-junctions, this typical electric charge transfer mode drops significantly
The low reduction-oxidation ability of electrons and holes, then reduces photocatalytic activity from thermodynamics.In recent years, a kind of direct
Z-type charge transfer mechanism has been used for photogenerated charge between explaining hetero-junctions and detaches.In brief, two and half are respectively to lead
The hole of the electronics of the calibration conduction band positions of body and relatively negative valence band location occurs compound at heterojunction boundary.To more negative
The remaining photohole in remaining light induced electron and corrigendum VB in CB remains simultaneously, they have best reduction-oxidation
Ability participates in photocatalytic redox reaction and promotes its performance.It is known that the semiconductor light with the relatively negative positions CB is urged
Agent can be considered as good reduced form photochemical catalyst, and the semiconductor light-catalyst with the positions calibration VB can be considered as
Good oxidized form photochemical catalyst.Both reduced form and oxidized form photochemical catalyst are combined into Z-type hetero-junctions, can make full use of
High reduction and oxidability, to greatly promote photocatalysis performance.As described above, g-C3N4It is typical reduced form photocatalysis
Agent is found suitably and g-C3N4Staggeredly the oxidation type semiconductor photochemical catalyst of band arrangement is designed based on g-C3N4Direct Z
Type heterojunction photocatalyst is still to be of great significance.
WO3, since its suitable band gap (about 2.6eV) (visible light responsive photocatalyst) and the positions VB positive enough are (high
Oxidability), have been considered to promising production oxide-semiconductor.WO3One is typical oxidation type semiconductor photocatalysis
Agent.
Invention content
The present invention provides a kind of ultra-thin 2D WO to improve the efficiency of Photocatalyzed Hydrogen Production3/g-C3N4Z-type hetero-junctions light
The preparation method of catalyst, includes the following steps：
S1 prepares ultra-thin 2D WO3Nanometer sheet；
S2 prepares ultra-thin 2D g-C3N4Nanometer sheet；With
S3 passes through 2D WO3Nanometer sheet and 2D g-C3N4Nanometer sheet prepares ultra-thin 2D WO3/g-C3N4Z-type hetero-junctions light is urged
Agent.
In ultra-thin 2D WO of the present invention3/g-C3N4In the preparation method of Z-type heterojunction photocatalyst, step S1 packets
Include following steps：
Step S11 prepares body phase WO3；With
Step S12 prepares ultra-thin 2D WO3Nanometer sheet.
In ultra-thin 2D WO of the present invention3/g-C3N4In the preparation method of Z-type heterojunction photocatalyst, step S11 packets
Include following steps：
S111, by Na2WO4·2H2O is dispersed in HNO3In solution, stirring is abundant, is then centrifuged for collecting sediment, water is used in combination
Sediment is washed to pH=7；
Gained sediment is dried 12h, then calcines 3h at 500 DEG C again, obtain body phase WO by S112 in an oven3。
In ultra-thin 2D WO of the present invention3/g-C3N4In the preparation method of Z-type heterojunction photocatalyst, step S12 tools
Body is to remove body phase WO by ultrasound3。
In ultra-thin 2D WO of the present invention3/g-C3N4In the preparation method of Z-type heterojunction photocatalyst, it is preferable that with
Bovine serum albumin(BSA) is remover, and assisting ultrasonic removes body phase WO3。
In ultra-thin 2D WO of the present invention3/g-C3N4In the preparation method of Z-type heterojunction photocatalyst, step S2 packets
Include following steps：
Urea is fitted into crucible and is capped by S21, calcines 2h at 550 DEG C with the rate of heat addition of 5 DEG C/min, obtains body phase-g-
C3N4；With
S22, the body phase-g-C that will be obtained in S213N4It grinds and is fitted into crucible with the rate of heat addition of 5 DEG C/min at 550 DEG C
It carries out second step and calcines 2h, obtain ultra-thin 2D g-C3N4Nanometer sheet.
In ultra-thin 2D WO of the present invention3/g-C3N4In the preparation method of Z-type heterojunction photocatalyst, step S3 packets
Include following steps：
By ultra-thin 2D g-C3N4Nanometer sheet is distributed in lactic acid solution, then by 2D WO3Nanometer sheet is added to above-mentioned solution
In, the pH=4 of mixed solution is controlled, 2h is continuously stirred, precipitation is collected after being then centrifuged for, and clean drying.
The present invention also provides a kind of ultra-thin 2D WO3/g-C3N4Z-type heterojunction photocatalyst, including 2D WO3With 2D g-
C3N4。
In ultra-thin 2D WO provided by the invention3/g-C3N4In Z-type heterojunction photocatalyst, 2D WO3With 2D g-C3N4's
Mass ratio is 1-3：10.
Advantageous effect：Due to g-C3N4And WO3Between staggeredly band arrangement make WO3/g-C3N4Heterojunction structure is to improving
Photocatalysis performance is highly effective.Ideal interface plays vital work in electric charge transfer and separation between two components
With.Moreover, the 2D/2D hetero-junctions contacted face-to-face can show big interfacial contact area and smaller interface resistance, carry
High charge transfer effciency, thus further increases light-catalysed performance and stability.
Description of the drawings
Fig. 1 is the ultra-thin 2D/2D WO described in the embodiment of the present invention3/g-C3N4The preparation method of Z-type heterojunction photocatalyst
Schematic diagram；
Fig. 2 is body phase WO3, WO3Nanometer sheet and g-C3N4Zet (ζ) potential energy diagram of nanometer sheet in pH=4；
Fig. 3 a-3b are body phase WO3FESEM images, Fig. 3 c be g-C3N4The FESEM images of nanometer sheet, Fig. 3 d are second real
Apply the 15%WO prepared in example3/g-C3N4FESEM images；
Fig. 4 is the performance map of Photocatalyzed Hydrogen Production rate in different embodiments；
Fig. 5 is the 15%WO prepared in second embodiment3/g-C3N4Photocatalysis stability；
Fig. 6 a show WO3Nanometer sheet and g-C3N4Between Z-type charge transfer mechanism schematic diagram, Fig. 6 b be 2D/2D it is heterogeneous
Electric charge transfer figure between knot.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Although the step in the present invention is arranged with label, it is not used to limit the precedence of step, unless
Based on the execution of the order or certain step that specify step needs other steps, otherwise the relative rank of step is
It is adjustable.It is appreciated that term "and/or" used herein be related to and cover in associated Listed Items one
Person or one or more of any and all possible combinations.
As shown in Figure 1, the present invention provides a kind of ultra-thin 2D/2D WO3/g-C3N4The preparation of Z-type heterojunction photocatalyst
Method specifically comprises the following steps：
S1 prepares ultra-thin 2D WO3Nanometer sheet；
S2 prepares ultra-thin 2D g-C3N4Nanometer sheet；With
S3 passes through 2D WO3Nanometer sheet and 2D g-C3N4Nanometer sheet prepares ultra-thin 2D/2D WO3/g-C3N4Hetero-junctions light is urged
Agent.
Specifically, step S1 further includes:
Step S11 prepares body phase WO3；With
Step S12 prepares ultra-thin 2D WO3Nanometer sheet.
Wherein, step S11 is specifically included：
S111, by Na2WO4·2H2O is dispersed in HNO3In solution, stirring is abundant, is then centrifuged for collecting yellow mercury oxide (WO3·
2H2O), and it is washed with water to pH=7；
In one embodiment of the invention, by the Na of 500mg2WO4·2H2O is dispersed in the 4.8M HNO of 200mL3Solution
In, stir 36h.
S112, by gained WO3·2H2O dries 12h in an oven, then calcines 3h at 500 DEG C again, obtains body phase WO3。
Step S12 by ultrasound specifically, remove body phase WO3Prepare ultra-thin 2D WO3Nanometer sheet；
In one embodiment of the invention, in step S12, with bovine serum albumin(BSA) (BSA) for remover, assisting ultrasonic
Remove body phase WO3.Because of in acid condition, the abundant-NH in the surfaces BSA2Group can be with WO3Strong electrostatical binding occurs.
Under ultrasonication, this strong electrostatic force can be from body phase WO3Surface on tear ultra-thin 2D WO3Nanometer sheet, and significantly
Improve WO3The dispersibility of nanometer sheet in the solution.
In one embodiment of the invention, 10mg BSA are dissolved in 100mL H2In O, with 1M HNO3Mixture is molten
The pH of liquid is adjusted to 4.By 50mg body phases WO3Powder is dispersed in above-mentioned solution, and is ultrasonically treated 3h.Obtained milky white solution
30min is centrifuged at 4500rpm.After removing extra BSA solution, sediment is dispersed in the 100mL H of pH=4 again2O
In, intense ultrasonic handles 3h again.Finally, milky ultra-thin 2D WO are obtained3Nanometer sheet suspension, and the concentration of suspension
For 0.5mg/mL.
Step S2 is specifically included：
Urea is fitted into crucible and is capped by S21, calcines 2h at 550 DEG C with the rate of heat addition of 5 DEG C/min, obtains yellowish
Color powder (body phase-g-C3N4)；
It is capped for crucible and with the gaseous volatilization that higher heating rate is reduction in order to prevent, improves g-C3N4Yield.
And S22, the pale yellow powder obtained in S21 is ground and is fitted into crucible with the rate of heat addition of 5 DEG C/min 550
Second step is carried out at DEG C and calcines 2h, obtains ultra-thin 2D g-C3N4Nanometer sheet.It is removed, can be surpassed by secondary clacining thermal oxide
Thin 2D g-C3N4Nanometer sheet.
Step S3 is specifically included：
By ultra-thin 2D g-C3N4Nanometer sheet is distributed in lactic acid solution, by WO3Nanometer sheet suspension instills in above-mentioned solution,
In the pH=4 of mixed solution, 2h is continuously stirred, precipitation is collected after being then centrifuged for, and clean drying.
It is because of the ultra-thin 2D WO after stripping that the pH of mixed solution, which is controlled 4 or so,3Nanometer sheet surface in pH=4
It is negatively charged.And in pH=4, ultra-thin 2D g-C3N4Surface it is positively charged, to which Electrostatic Absorption between the two constructs ultra-thin 2D/
2D WO3/g-C3N4Heterojunction photocatalyst.
Embodiment 1
By the ultra-thin 2D g-C of 50mg3N4Nanometer sheet is distributed in the lactic acid solution of the 20vol% of 80mL, by 10mL WO3
Nanometer sheet suspension instills in above-mentioned solution, controls the pH of mixed solution close to 4.It is heavy by being collected by centrifugation after continuously stirring 2h
It forms sediment and is cleaned up with deionized water.Products therefrom is denoted as 10%WO3/g-C3N4。
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, the difference is that WO3The additive amount of nanometer sheet suspension is 15mL, together
When, obtained product is denoted as 15%WO3/g-C3N4。
Embodiment 3
Embodiment 3 is substantially the same manner as Example 1, the difference is that WO3The additive amount of nanometer sheet suspension is 20mL, together
When, obtained product is denoted as 20%WO3/g-C3N4。
Embodiment 4
Embodiment 4 is substantially the same manner as Example 1, the difference is that WO3The additive amount of nanometer sheet suspension is 30mL, together
When, obtained product is denoted as 30%WO3/g-C3N4。
Experimental data
As shown in Fig. 2, the body phase WO in pH=43, WO3Nanometer sheet and g-C3N4(Zeta) zeta potential figure of nanometer sheet.In pH
When=4, body phase WO3Show the negative zeta potential of -9.7mV.WO3Nanometer sheet also shows that negative zeta potential is -22.8mV.In pH=4
When, Zeta electric potential value is higher to show WO3The dispersibility of nanometer sheet is than body phase WO3More preferably.Stripping process brings more surface bases
Group, and then improve WO3The dispersibility of nanometer sheet.In pH=4, g-C3N4Nanometer sheet shows the positive zeta potential of 10.3mV.Phase
Anti- zeta potential value can bring WO3Nanometer sheet and g-C3N4Strong electrostatic attraction between nanometer sheet, while being also beneficial to them
Between electric charge transfer.Stable 2D/2D WO3/g-C3N4Hetero-junctions can be acted on by electrostatic attraction and be obtained.
As illustrated in figs. 3 a-3d, Fig. 3 a show body phase WO3FESEM images, can be observed in figure about 500nm sizes and
The uniform sheet structure of 50nm thickness.WO after stripping3The thickness of nanometer sheet becomes very thin.As shown in Figure 3b, it is observed that
The thin WO of many tilings3Nanometer sheet.In addition WO3The size of nanometer sheet also becomes than body phase WO3It is much smaller.This result proves
Body phase WO is removed by BSA electrostatic assisting ultrasonics3Ultra-thin WO can successfully be obtained3Nanometer sheet.Fig. 3 c show g-C3N4Nanometer
The FESEM images of piece, it is observed that the layer structure with crimped edge.With WO3Nanometer sheet is compared, g-C3N4Nanometer sheet
Size bigger, this is because g-C3N4Nanometer chip architecture have more flexibility, and WO3It is fragile material.It is real that Fig. 3 d illustrate second
Apply the 15%WO prepared in example3/g-C3N4FESEM images, all nanometer sheets flock together, it is difficult to distinguish g-C3N4With
WO3Nanometer sheet, illustrate it is compound after material fusion degree very it is high very uniformly.
Fig. 4 is the performance map of Photocatalyzed Hydrogen Production rate in different embodiments.Made using the 20vol% lactic acid aqueous solutions of 80mL
For sacrifice agent.The Pt of 2wt% is supported on sample surfaces as production hydrogen co-catalyst using the method for photo-reduction deposition.Use full light
The 350W xenon lamps of spectrum are as light source.As can be seen from Figure 4 WO3Nanometer sheet does not produce hydrogen activity significantly, this is attributed to WO3
The positions CB it is improper.Pure g-C3N4Show 583 μm of ol h-1g-1Production hydrogen activity.With WO3/g-C3N4Middle WO3Nanometer sheet
The increase of content, hydrogen-producing speed also step up.Work as WO3When the ratio of nanometer sheet reaches 15%, hydrogen-producing speed reaches highest
(982μmol h-1g-1).It is worth noting that, 20%WO3/g-C3N4And 30%WO3/g-C3N4It shows and compares 15%WO3/g-
C3N4Lower hydrogen-producing speed.This is results showed that WO3/g-C3N4There are WO in composite material3The optimal proportion of nanometer sheet.Too
High WO3Nanometer sheet content can make WO3/g-C3N4The oxidability of composite material enhances, and reduces reproducibility photochemical catalyst g-
C3N4Content to make WO3/g-C3N4The reducing power of composite material reduces.
Fig. 5 presents the 15%WO prepared in second embodiment3/g-C3N4Photocatalysis stability.On the whole, 15%
WO3/g-C3N4Photocatalytic activity is not decreased obviously after being recycled at 4, shows 15%WO3/g-C3N4Have under irradiation high
Photocatalysis stability.
Fig. 6 a show WO3Nanometer sheet and g-C3N4Between Z-type charge transfer mechanism schematic diagram.In interface built in field
With the help of, photo-generated carrier, which can be better achieved, to be spatially separating and shifts.WO3Conduction (CB) in light induced electron can be with
It is transferred to g-C3N4Valence band (VB) and compound with its photohole.As a result, the light induced electron of higher reducing power can be retained in
g-C3N4CB on, and the photohole of more high oxidative capacity may remain in WO3VB on.These electronics and sky for retaining
Cave can show stronger re-oxidation ability.Fig. 6 b further display the electric charge transfer between 2D/2D hetero-junctions.Clearly
It is that 2D/2D structures provide more contact areas, this is beneficial for electric charge transfer.In addition, WO3And g-C3N4Between
Close contact also brings smaller interface resistance, leads to easier interfacial charge transfer.
Ultra-thin 2D/2D WO provided by the invention3/g-C3N4The preparation method of Z-type heterojunction photocatalyst is simple, makes simultaneously
Standby ultra-thin 2D/2D WO3/g-C3N4Z-type heterojunction photocatalyst structure novel, planar structure and Z-type electric charge transfer can be big
The big efficiency and photocatalysis stability for improving Photocatalyzed Hydrogen Production.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent substitution, improvement and etc. done should be included within the scope of protection of the invention god.
Claims (9)
1. a kind of ultra-thin 2D WO3/g-C3N4The preparation method of Z-type heterojunction photocatalyst, which is characterized in that including walking as follows
Suddenly：
S1 prepares ultra-thin 2D WO3Nanometer sheet；
S2 prepares ultra-thin 2D g-C3N4Nanometer sheet；With
S3 passes through 2D WO3Nanometer sheet and 2D g-C3N4Nanometer sheet prepares ultra-thin 2D WO3/g-C3N4Z-type heterojunction photocatalyst.
2. preparation method as described in claim 1, which is characterized in that step S1 includes the following steps：
Step S11 prepares body phase WO3；With
Step S12 prepares ultra-thin 2D WO3Nanometer sheet.
3. preparation method as claimed in claim 2, which is characterized in that step S11 includes the following steps：
S111, by Na2WO4·2H2O is dispersed in HNO3In solution, stirring is abundant, is then centrifuged for collecting sediment, is used in combination water that will sink
Starch is washed to pH=7；
Gained sediment is dried 12h, then calcines 3h at 500 DEG C again, obtain body phase WO by S112 in an oven3。
4. preparation method as claimed in claim 3, which is characterized in that step S12 is specifically by ultrasound stripping body phase WO3。
5. preparation method as claimed in claim 4, which is characterized in that using bovine serum albumin(BSA) as remover, assisting ultrasonic stripping
In vitro phase WO3。
6. preparation method as described in claim 1, which is characterized in that step S2 includes the following steps：
Urea is fitted into crucible and is capped by S21, calcines 2h at 550 DEG C with the rate of heat addition of 5 DEG C/min, obtains body phase-g-C3N4；
With
S22, the body phase-g-C that will be obtained in S213N4It grinds and is fitted into crucible and carried out at 550 DEG C with the rate of heat addition of 5 DEG C/min
Second step calcines 2h, obtains ultra-thin 2D g-C3N4Nanometer sheet.
7. preparation method as described in claim 1, which is characterized in that step S3 includes the following steps：
By ultra-thin 2D g-C3N4Nanometer sheet is distributed in lactic acid solution, then by 2D WO3Nanometer sheet is added into above-mentioned solution,
The pH=4 for controlling mixed solution, continuously stirs 2h, precipitation is collected after being then centrifuged for, and clean drying.
8. a kind of ultra-thin 2D WO3/g-C3N4Z-type heterojunction photocatalyst, which is characterized in that including 2D WO3With 2D g-C3N4。
9. ultra-thin 2D WO as claimed in claim 83/g-C3N4Z-type heterojunction photocatalyst, which is characterized in that 2D WO3And 2D
g-C3N4Mass ratio be 1-3：10.
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