CN110124691A - A kind of preparation method of pollen carbon skeleton load growth rhenium disulfide photoelectric material - Google Patents
A kind of preparation method of pollen carbon skeleton load growth rhenium disulfide photoelectric material Download PDFInfo
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- CN110124691A CN110124691A CN201910373634.4A CN201910373634A CN110124691A CN 110124691 A CN110124691 A CN 110124691A CN 201910373634 A CN201910373634 A CN 201910373634A CN 110124691 A CN110124691 A CN 110124691A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- USWJSZNKYVUTIE-UHFFFAOYSA-N bis(sulfanylidene)rhenium Chemical compound S=[Re]=S USWJSZNKYVUTIE-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- 238000000137 annealing Methods 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 230000008439 repair process Effects 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
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- 239000000047 product Substances 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229960004756 ethanol Drugs 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000009656 pre-carbonization Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000009418 renovation Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 238000004094 preconcentration Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract 2
- GGCJLWBMJYGIRE-UHFFFAOYSA-N ethanol;formaldehyde Chemical compound O=C.CCO GGCJLWBMJYGIRE-UHFFFAOYSA-N 0.000 abstract 1
- 230000031700 light absorption Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 230000003321 amplification Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000003199 nucleic acid amplification method Methods 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910052702 rhenium Inorganic materials 0.000 description 7
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 5
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229940038481 bee pollen Drugs 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
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- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
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- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 244000170916 Paeonia officinalis Species 0.000 description 1
- 235000006484 Paeonia officinalis Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 241000238370 Sepia Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- 238000009341 apiculture Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
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- 239000000470 constituent Substances 0.000 description 1
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- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
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- 230000003834 intracellular effect Effects 0.000 description 1
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- 238000012423 maintenance Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- -1 transition Metal sulfide Chemical class 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/33—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
Abstract
The invention discloses the preparation method that a kind of pollen carbon skeleton loads growth rhenium disulfide, the preparation method of the pollen carbon skeleton load growth rhenium disulfide includes: to weigh pollen to be cleaned by ultrasonic in ethanol；Formaldehyde repairs pollen pattern；The concentrated sulfuric acid is carbonized pollen in advance；Weigh precursors hydro-thermal reaction synthetic product；Product separates drying and annealing.The pollen carbon skeleton load growth rhenium disulfide of preparation method preparation provided by the invention has the advantages that pattern dense uniform, is layered porous, bigger serface, three-dimensional appearance structure, pollen carbon skeleton after being carbonized simultaneously has the characteristics that good electric conductivity, rhenium disulfide have good light absorption, therefore material of the invention has excellent photoelectric properties.Raw material pollen of the invention is cheap and easy to get, and all raw materials are safe and non-toxic, environmental-friendly and easy to industrialized production.
Description
Technical field
The invention belongs to bionic nano material technical fields, and in particular to a kind of pollen carbon skeleton load growth rhenium disulfide
The preparation method of photoelectric material.
Background technique
Grapheme material was separated for the first time in 2004, obtained the Nobel Prize to 2010.Then, graphene special two
Dimension structure makes it have excellent electric conductivity, is concerned.However, zero band gap disadvantage of graphene keeps it standby in application aspect
It is restricted.Therefore, sight is gathered in by researcher equally has the characteristics that the non-zero band gap material of two-dimensional structure, such as black squama, transition
Metal sulfide, transition metal carbide etc..
Recently, transient metal sulfide (TMDs) makes it in electronics, photoelectricity because of its special structure and excellent band gap
Sub-, spintronics, paddy electronics and catalytic field have all obtained extensive concern.Rhenium disulfide vulcanizes as transition metal
Object family a member shows more unique excellent photoelectric characteristic.Rhenium disulfide is usually in the octahedron of distortion (1T) crystal knot
It is crystallized in structure, there is triclinic symmetry.Rhenium atom in single layer forms the cluster of four Re atoms, they are with rhomboid chain (DS chain) phase
It connects, and generates sizable anisotropy in electrical and optical properties.The uncommon anisotropy of rhenium disulfide is special
Property, it is similar to black phosphorus, assigns its great potential of the following new device application.In addition, it is different from tungsten disulfide and molybdenum disulfide,
Since the Peierls distortion in the 1T structure of rhenium disulfide prevents ordered stacks and the interlayer of wave function is made to be overlapped minimum
Change, therefore charge decouples rhenium disulfide layer each other.Therefore, from body mutually to single layer, rhenium disulfide is still direct band-gap semicondictor
(1.5-1.6 eV).This unique optical characteristics makes rhenium disulfide obtain extensive concern in field of semiconductor materials,
Recently, existing research personnel are using rhenium disulfide thin layer as field effect transistor, photoelectrocatalysielectrode electrode and photodetector.
The Nature gives us colourful life form, and the formation of each life structure is all by 1 years
The optimal form evolved.Among the constituent of life, carbon is one of most important element, various biological tissues
It is all to be constituted based on carbon skeleton with organic principle.Using the carbon skeleton that comes in every shape naturally occurred, as template
Growth material can be all many-sided as specific surface area, growthform construct new function material.Pollen is that the male of plant is raw
Cell colonization, wherein containing hereditary information and nutriment necessary to pollen existence is multiplied.In various biomaterials, pollen
Pollen with uniform carbon skeleton is applied to various necks due to its macropore appearance, high surface area and unique three-dimensional net structure
Domain.In document report in recent years, it is in the common method of material of pollen carbon skeleton template growth: the direct carbon of high temperature noble gas
After changing processing pollen, pollen after processing is synthesized with presoma mixing progress hydro-thermal method, sol-gel method, product is mostly colored
The nano material adhered on powder wall.However, method before these all causes pollen there is the control of pollen Carbonization Conditions is improper
Pattern is damaged, carbonizing degree is not high leads to that impurity is excessive, skeleton untight problem in conjunction with material.Moreover, previously reported
Material in, there has been no pollen carbon skeleton growth rhenium disulfide method.
Summary of the invention
It is an object of the invention to overcome the problems of the prior art, a kind of pollen carbon skeleton load two sulphur of growth are provided
Change the preparation method of rhenium photoelectric material.
Pollen carbon skeleton pattern is able to good holding by control pollen Carbonization Conditions by this patent method, is fitted simultaneously
The hydrothermal system of conjunction makes the growth of rhenium disulfide have the advantages that bigger serface, layering are porous, uniformly intensive.
The purpose of the present invention is achieved by the following technical programs:
A kind of preparation method of pollen carbon skeleton load growth rhenium disulfide photoelectric material, includes the following steps:
Step 101, pollen is weighed to be cleaned by ultrasonic in ethanol；
Step 102, formaldehyde repairs pollen pattern；
Step 103, the concentrated sulfuric acid is carbonized pollen in advance；
Step 104, precursors ammonium perrhenate, thiocarbamide, hydroxylamine hydrochloride are weighed；
Step 105, hydro-thermal reaction synthetic product, wherein the condition of hydro-thermal reaction are as follows: 22 ~ 25h of hydro-thermal reaction at 200 ~ 230 DEG C；
Step 106, product separates drying and annealing.
In step 105, the pre- concentration that pollen is added in hydro-thermal reaction system that is carbonized is 1 ~ 3mg/mL.
Preferably, in the step 101: the pollen is non-broken pollen.
Preferably, it is cleaned by ultrasonic are as follows: mixed using 5 ~ 10g pollen with 50 ~ 100ml dehydrated alcohol, ultrasonic power item
Part is to handle 1 ~ 1.5 hour under 50 ~ 75W.
Preferably, in the step 102: repairing pollen pattern, pattern renovation agent using pattern renovation agent are as follows: 25 ~
50ml dehydrated alcohol is mixed with 25 ~ 50ml, the formalin that concentration is 36% ~ 40%.
Preferably, in the step 103: the concentrated sulfuric acid concentration is 12mol/L, and usage amount is 50ml ~ 100ml.
Preferably, in the step 103, pre- carbonization is heated 4 ~ 4.5 hours for 75 ~ 85 DEG C of stirring in water bath.
It after pre- carbonization, is dried, drying operation are as follows: dried 10 ~ 14 hours at 70 ~ 75 degrees Celsius.
Preferably, in the step 104: the molar ratio of ammonium perrhenate, thiocarbamide and hydroxylamine hydrochloride is 1:1:1.
Preferably, in the step 105: weighing the pollen after being carbonized, be allowed to equal after 20 ~ 30 min are stirred by ultrasonic in water
Even dispersion；Then presoma is added and carries out hydro-thermal reaction.
Preferably, hydro-thermal reaction is carried out in 50ml polytetrafluoroethyllining lining reaction kettle.
Preferably, in the step 106: obtained crude product is in 60 ~ 80 DEG C of oven dryings, then in inert gas atmosphere
With 5 DEG C/mins heating rate in 600 ~ 900 DEG C of annealing 2h in enclosing.
Compared with prior art, the present invention has following technical effect that
The material that the present invention is prepared has unique porous network structure, from a wealth of sources, cheap, environmentally protective, has
It is produced conducive to industrialization metaplasia, and equipment is simple, convenient operating maintenance, strong flexibility subtracts using hydro-thermal reaction one-step synthesis
Preparation cost is lacked；Pollen carbon skeleton/rhenium disulfide large specific surface area of preparation, the intensive uniform, good conductivity of growth, have and divide
Layer three-dimensional structure, and photoelectrocatalysis efficiency with higher.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method of the pollen carbon skeleton growth rhenium disulfide material of the embodiment of the present invention.
Fig. 2 is the pretreated obtained pollen SEM(scanning electron microscope of the method for the present invention) (amplification factor is enlarged drawing
1500 times).
Fig. 3 is the pretreated obtained pollen SEM(scanning electron microscope of the method for the present invention) (amplification factor is enlarged drawing
3170 times).
Fig. 4 is the HR-SEM(high magnification numbe scanning electron microscope of powder carbon skeleton load growth rhenium disulfide material) amplification
Figure, amplification factor are 90000 times.
Fig. 5 is pollen carbon skeleton load growth rhenium disulfide material, two sulphur with identical hydrothermal method, without template growth
Change the XRD diagram (X ray diffracting spectrum) of rhenium.
Fig. 6 is pollen carbon skeleton load growth rhenium disulfide material, two sulphur with identical hydrothermal method, without template growth
Change the Raman Spectrum(Raman spectrum analysis of rhenium) map.
Fig. 7 is the different content pollen carbon skeleton of the present invention load growth linear voltammetric scan figure of rhenium disulfide.
Fig. 8 is the SEM scanning electron microscope (SEM) photograph for growing molybdenum disulfide in comparative example 1 in pollen carbon skeleton template, it is seen that is compared
In rhenium disulfide, molybdenum disulfide fails to grow on pollen carbon skeleton.
Fig. 9 is scanning electron microscope diagram of the comparative example 2 without pretreatment direct carbonization pollen, and amplification factor is 3000 times.
Figure 10 is scanning electron microscope diagram of the comparative example 2 without pretreatment direct carbonization pollen, amplification factor 20000
Times.
Specific embodiment
It to make the object, technical solutions and advantages of the present invention clearer, combined with specific embodiments below will be to the present invention
Technical solution be described in detail.Obviously, described embodiments are only a part of the embodiments of the present invention, rather than complete
The embodiment in portion.Based on the embodiments of the present invention, those of ordinary skill in the art are in the premise for not making creative work
Under obtained all other embodiment, belong to the range protected of the present invention.
Except specified otherwise, equipment used in the present embodiment is routine experiment equipment, and reagent used is that analysis is pure
Reagent.
Embodiment 1
Choose non-broken wall bee pollen form cole (the non-broken pollen of other types also can be used, such as the lotus flower powder, peony pollen) river 10g(
Western Ganzhou Shicheng County Kang Huang apiculture Co., Ltd), it immerses 100ml dehydrated alcohol (AR, Chengdu Cologne Chemical Company) and sets
In 250mL beaker, mixed liquor is then subjected to ultrasonic treatment 1 hour, ultrasonic power 75W, frequency 40KHz, is then used
Deionized water is rinsed 3 times.Ethyl alcohol can penetrate pollen shell and enter core, and substance, which is dissolved, in pollen surface and core cleans.
Then one of exemplary three key steps of this implementation are carried out: measuring 50mL dehydrated alcohol and 50mL formalin
(AR, 37-40%, Chengdu Cologne Chemical Company) after being sufficiently mixed uniformly, is added the pollen cleaned in above-mentioned steps, makes
It is stirred 10 minutes with magnetic agitation instrument, then using deionized water washing filter 23.The table of pollen can be repaired and be reinforced to formaldehyde
Face pattern is allowed to pattern and is maintained in a subsequent step.
Then carry out the exemplary another committed step of this implementation: the configuration 100mL 12mol/L concentrated sulfuric acid first takes above-mentioned step
Suddenly the pollen being disposed is added to form yellowish brown suspension, is transferred in hydro-thermal warm table with rear suspension liquid.80 DEG C waters
Bath agitating and heating 4 hours.Pollen color is then washed with deionized by xanthochromia sepia to neutrality, is separated by filtration (middling speed filter
Paper, Whatman Corporation) after, it is transferred to 70 degrees Celsius of baking oven and dries 12 hours.This operation is pre- carbonization treatment step
Suddenly, pre- carbonization treatment can make pollen carbon skeleton be enhanced to some extent reinforcing, be allowed to high temperature high pressure reverse next
It answers under environment, is able to maintain good pattern and structure, imagine effect to reach expected, as shown in Figure 2.
50 ~ 100mg of pollen that above-mentioned steps pre-process is weighed, and 30mL deionized water is added in beaker,
It is stirred by ultrasonic 30 minutes under 150W power, is allowed to be uniformly dispersed.Then 1:1:1 successively weighs 268mg ammonium perrhenate in molar ratio
(99.999%, Alfa Aesar), 208.5mg hydroxylamine hydrochloride (AR, 98.5%, Aladdin reagent), 342.5mg thiocarbamide (AR, 99%,
Aladdin reagent), it is added in the dispersed phase of water and pollen, continuing stirring dissolves presoma sufficiently in 30 minutes.This operation can be with
It is sufficiently impregnated pollen with precursor liquid, is uniformly mixed, so that rhenium disulfide is grown to obtain dense uniform, as shown in Figure 3.
The dispersed phase of pollen and precursor solution that above-mentioned steps are handled is transferred to 50mL polytetrafluoroethyllining lining
Hydrothermal reaction kettle in (the close instrument of Hefei section), baking oven is heated to 220 DEG C water thermal response 24 hours.After the reaction was completed, it scrapes
The black solid of lower kettle wall, taking-up obtain black suspension, are respectively washed twice with water and ethyl alcohol respectively, stand liquid separation, filtering point
From rear, it is transferred to the drying 12 hours of 70 degrees Celsius of baking oven.Washing and separation drying can remove the waste liquid for reacting extra, and purification produces
Object.
It is finally the last one exemplary committed step of this implementation: the crude pollen that will be obtained after above-mentioned steps reaction treatment
Carbon skeleton load rhenium disulfide is transferred in 10*1.5*1.5 cm corundum boat, is put into vacuum tube furnace, after being evacuated to vacuum, is led to
Enter 100 sccm argon gas, with 5 centigrade per minute heating rates, is warming up to 800 degrees Celsius and anneals two hours, subsequent natural cooling
To room temperature.Annealing operation can remove remaining impurity in pollen, enhancing skeleton electric conductivity, enhancing rhenium disulfide crystallinity etc., such as
Shown in Fig. 4.
As shown in Figure 1, being the specification of the specific embodiment of the invention, 6 steps are shared, respectively take pollen in ethanol
Ultrasonic cleaning；Formaldehyde repairs pollen pattern；The concentrated sulfuric acid is carbonized pollen in advance；Weigh precursors ammonium perrhenate, thiocarbamide, hydrochloric acid hydroxyl
Amine；Hydro-thermal reaction synthetic product；Product separates drying and annealing.
As shown in Fig. 2, to use the pretreated obtained pollen SEM(scanning electron microscope of the method for the present invention) amplification
Figure, amplification factor are 1500 times.It can be seen that pollen still maintains complete carbon backbone structure, but nuclear material intracellular is basic
Removal is clean.
As shown in figure 3, for a kind of SEM amplification of pollen carbon skeleton load growth rhenium disulfide material of the present invention
Figure, amplification factor are 3170 times.It can be seen that rhenium disulfide pollen carbon skeleton uniformly densely load growth, have it is porous layering,
The characteristics of bigger serface.
As shown in figure 4, for a kind of HR-SEM(high power of pollen carbon skeleton load growth rhenium disulfide material of the present invention
Number scanning electron microscope) enlarged drawing, amplification factor is 90000 times.It can be seen that growth structure of the rhenium disulfide in pollen carbon skeleton
For 100nm size fine platy, layer accumulation type, has the characteristics that uniformly intensive, bigger serface, it is anticipated that it has a large amount of
Active site.
As shown in figure 5, for it is of the present invention be a kind of pollen carbon skeleton load growth rhenium disulfide material of the present invention,
With identical hydrothermal method, the XRD diagram (X ray diffracting spectrum) of the rhenium disulfide without template growth.According to standard card
In ICSD PDF#82-1379(attached drawing 5 shown in the black vertical scatter plot of bottom) comparison is 14.534 degree, 29.308 in 2 θ angles
When degree, 32.687 degree, 37.894 degree, material of the present invention and pure rhenium disulfide occur respectively rhenium disulfide (100),
(200), (002), (102) crystal face diffraction maximum.
As shown in fig. 6, for pollen carbon skeleton of the present invention load growth rhenium disulfide material, with identical hydro-thermal side
The Raman Spectrum(Raman spectrum analysis of method, rhenium disulfide without template growth) map, according to documents and materials it is found that carbon
In 2700cm-1Place has a heavy grade and delays peak 2D, 1500cm-1Place has bimodal D and G, bimodal illustrates table wherein asymmetric
The crystallinity of face carbon is not high；ReS2The two different peaks corresponding with (Ag) vibration mode outside face (Eg) occur in respective face
In 161.7 and 209.8 cm-1Place.The two peak values come from low symmetry, and intercouple with basic Raman modes,
It is associated with acoustical phonon.
As shown in fig. 7, being swept for the different content pollen carbon skeleton of the present invention load growth linear volt-ampere of rhenium disulfide
Tracing, test condition is that (electrolyte solution is 0.5M H to three-electrode system2SO4, AgCl/Ag be reference electrode, graphite carbon rod is
It is working electrode to electrode, product of the present invention), the preparation method of working electrode: 5mg catalyst, 50 μ L, 5 ω t% Nafion glue
Water ultrasound 30min is dispersed in 1mL(volume ratio ethyl alcohol: water=1:3) in the mixed solvent, then 100 μ L uniform colloids are applied to
On the carbon cloth of 1*1cm, naturally dry.As seen from Figure 7, the different pollen carbon skeleton addition obtained product electricity of reacting dose are urged
It is different to change H2-producing capacity, when additive amount is greater than 100mg, electro-catalysis H2-producing capacity is more worse than no added pure rhenium disulfide
(it is 0.64V that pure rhenium disulfide corresponds to overpotential at 10mA), when additive amount is 50mg, the electro-catalysis H2-producing capacity of catalyst
Reach maximum: it is 0.55V that overpotential is corresponded under 10mA.
Comparative example 1
In this comparative example, first three items implementation steps are identical as the step in embodiment 1.On the basis of implementation steps, before reaction
Drive body replacement are as follows: 50mg pre-processes pollen, bis- molybdic acid hydrate sodium of 30mg, 60mg thioacetamide, 20ml deionized water, is added extremely
In the hydrothermal reaction kettle of 50ml polytetrafluoroethyllining lining (the close instrument of Hefei section), reaction condition be 200 degrees Celsius 24 hours.It connects down
The remaining step come is identical as the implementation steps of embodiment 1.As a result as shown in figure 8, as seen from Figure 8, pre-processing pollen surface light
It is sliding and flat, it is known that not successfully to grow molybdenum disulfide material in carbonization pollen template.
It is contemplated that at identical conditions, the growth of rhenium disulfide and molybdenum disulfide on pollen has otherness, this
The method of the rhenium disulfide of the pollen carbon skeleton load growth of invention has particular applicability.
Comparative example 2
As shown in Figure 9 and Figure 10, the scanning electron microscope diagram respectively without pretreatment direct carbonization pollen, amplification factor difference
For 3000 times and 20000 times.Processing method: it is limited to choose the non-Ganzhou broken wall bee pollen form cole 10g(Shicheng County health emperor's apiculture
Company), it immerses 100ml dehydrated alcohol (AR, Chengdu Cologne Chemical Company) and is placed in 250mL beaker, it then will mixing
Liquid carries out ultrasonic treatment 1 hour, ultrasonic power 75W, frequency 40KHz, is then rinsed 3 times with deionized water.Then should
It handles obtained pollen to be directly placed into quartz tube furnace, under 100sccm nitrogen atmosphere, with the heating speed of 5 degree per seconds Celsius
Degree is heated to 600 degrees Celsius and keeps the temperature 2 hours.It can be seen that imperfect irregular pattern is presented in pollen skeleton, cellular structure is received
Contracting avalanche, the whole bonding of reuniting under high temperature action of pollen, shrinks and reunion causes specific surface area to reduce, pattern is poor.
Claims (10)
1. a kind of preparation method of pollen carbon skeleton load growth rhenium disulfide photoelectric material, which is characterized in that including walking as follows
It is rapid:
Step 101, pollen is weighed to be cleaned by ultrasonic in ethanol；
Step 102, formaldehyde repairs pollen pattern；
Step 103, the concentrated sulfuric acid is carbonized pollen in advance；
Step 104, precursors ammonium perrhenate, thiocarbamide, hydroxylamine hydrochloride are weighed；
Step 105, hydro-thermal reaction synthetic product, wherein the condition of hydro-thermal reaction are as follows: 22 ~ 25h of hydro-thermal reaction at 200 ~ 230 DEG C；
Step 106, product separates drying and annealing；
In step 105, the pre- concentration that pollen is added in hydro-thermal reaction system that is carbonized is 1 ~ 3mg/mL.
2. the preparation method of pollen carbon skeleton load growth rhenium disulfide photoelectric material, feature exist according to claim 1
In in the step 101: the pollen is non-broken pollen.
3. the preparation method of pollen carbon skeleton load growth rhenium disulfide photoelectric material, feature exist according to claim 2
In ultrasonic cleaning are as follows: mixed using 5 ~ 10g pollen with 50 ~ 100ml dehydrated alcohol, ultrasonic power conditions are under 50 ~ 75W
Processing 1 ~ 1.5 hour.
4. the preparation method of pollen carbon skeleton load growth rhenium disulfide photoelectric material, feature exist according to claim 1
In in the step 102: using pattern renovation agent repair pollen pattern, pattern renovation agent are as follows: 25 ~ 50ml dehydrated alcohol with
25 ~ 50ml, the formalin that concentration is 36% ~ 40%.
5. the preparation method of pollen carbon skeleton load growth rhenium disulfide photoelectric material, feature exist according to claim 1
In in the step 103: the concentrated sulfuric acid concentration is 12mol/L, and usage amount is 50ml ~ 100ml.
6. the preparation method of pollen carbon skeleton load growth rhenium disulfide photoelectric material, feature exist according to claim 5
In in the step 103, pre- carbonization is heated 4 ~ 4.5 hours for 75 ~ 85 DEG C of stirring in water bath.
7. the preparation method of pollen carbon skeleton load growth rhenium disulfide photoelectric material, feature exist according to claim 1
In in the step 104: the molar ratio of ammonium perrhenate, thiocarbamide and hydroxylamine hydrochloride is 1:1:1.
8. the preparation method of pollen carbon skeleton load growth rhenium disulfide photoelectric material, feature exist according to claim 1
In in the step 105: the pollen after weighing carbonization is allowed to evenly dispersed after 20 ~ 30 min are stirred by ultrasonic in water；With
Presoma is added afterwards and carries out hydro-thermal reaction.
9. the preparation method of pollen carbon skeleton load growth rhenium disulfide photoelectric material according to claim 1 or 8, feature
It is, carries out hydro-thermal reaction in 50ml polytetrafluoroethyllining lining reaction kettle.
10. the preparation method of pollen carbon skeleton load growth rhenium disulfide photoelectric material, feature exist according to claim 1
In in the step 106: obtained crude product in 60 ~ 80 DEG C of oven dryings, then in atmosphere of inert gases with 5 DEG C/
Mins heating rate is in 600 ~ 900 DEG C of annealing 2h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170370A (en) * | 2020-01-19 | 2020-05-19 | 华南师范大学 | Manufacturing method of rhenium disulfide supercapacitor based on biological template growth |
| CN111354935A (en) * | 2020-03-24 | 2020-06-30 | 东华大学 | Defect-rich rhenium sulfide/nitrogen-doped biomass-based carbon fiber composite material and preparation method thereof |
| CN111403707A (en) * | 2020-03-24 | 2020-07-10 | 东华大学 | Rhenium sulfide/nitrogen-doped biomass-based carbon fiber composite material with double-defect structure and preparation method thereof |
| CN113042049A (en) * | 2021-03-17 | 2021-06-29 | 重庆邮电大学 | Semiconductor photocatalyst and preparation method and application thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4727135A (en) * | 1985-11-15 | 1988-02-23 | Exxon Research And Engineering Company | Synthesis of polyquinoline by the catalytical dehydrogenative polymerization of tetrahydroquinoline |
| CN105810447A (en) * | 2016-04-29 | 2016-07-27 | 陕西科技大学 | Preparation method of porous spherical biological carbon and application |
| CN106115688A (en) * | 2016-06-23 | 2016-11-16 | 华中科技大学 | A kind of method that natural cryptogam self-template method prepares Porous hollow activated carbon microballon |
| CN106450226A (en) * | 2016-11-22 | 2017-02-22 | 华南师范大学 | Preparation method of natural pollen-based metal sulfide-carbon composite material and application thereof |
| CN108807957A (en) * | 2018-08-31 | 2018-11-13 | 扬州大学 | Anode material of lithium-ion battery lacks layer rhenium disulfide nanometer sheet/hollow carbon sphere and preparation method thereof |
-
2019
- 2019-05-07 CN CN201910373634.4A patent/CN110124691B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4727135A (en) * | 1985-11-15 | 1988-02-23 | Exxon Research And Engineering Company | Synthesis of polyquinoline by the catalytical dehydrogenative polymerization of tetrahydroquinoline |
| CN105810447A (en) * | 2016-04-29 | 2016-07-27 | 陕西科技大学 | Preparation method of porous spherical biological carbon and application |
| CN106115688A (en) * | 2016-06-23 | 2016-11-16 | 华中科技大学 | A kind of method that natural cryptogam self-template method prepares Porous hollow activated carbon microballon |
| CN106450226A (en) * | 2016-11-22 | 2017-02-22 | 华南师范大学 | Preparation method of natural pollen-based metal sulfide-carbon composite material and application thereof |
| CN108807957A (en) * | 2018-08-31 | 2018-11-13 | 扬州大学 | Anode material of lithium-ion battery lacks layer rhenium disulfide nanometer sheet/hollow carbon sphere and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 夏阳: "生物模板法构筑多级多孔结构电极材料及其储锂性能研究", 《中国优秀博硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (11)
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|---|---|---|---|---|
| CN111170370A (en) * | 2020-01-19 | 2020-05-19 | 华南师范大学 | Manufacturing method of rhenium disulfide supercapacitor based on biological template growth |
| CN111354935A (en) * | 2020-03-24 | 2020-06-30 | 东华大学 | Defect-rich rhenium sulfide/nitrogen-doped biomass-based carbon fiber composite material and preparation method thereof |
| CN111403707A (en) * | 2020-03-24 | 2020-07-10 | 东华大学 | Rhenium sulfide/nitrogen-doped biomass-based carbon fiber composite material with double-defect structure and preparation method thereof |
| CN114317626A (en) * | 2020-09-30 | 2022-04-12 | 北京化工大学 | Method for producing epoxy fatty acid ester by light-enzyme coupling cascade |
| CN114317626B (en) * | 2020-09-30 | 2023-12-15 | 北京化工大学 | Method for producing epoxy fatty acid ester by photo-enzyme coupling cascade |
| CN113042049A (en) * | 2021-03-17 | 2021-06-29 | 重庆邮电大学 | Semiconductor photocatalyst and preparation method and application thereof |
| CN113042049B (en) * | 2021-03-17 | 2022-08-26 | 重庆邮电大学 | Semiconductor photocatalyst and preparation method and application thereof |
| CN114210315A (en) * | 2021-12-31 | 2022-03-22 | 厦门稀土材料研究所 | Preparation and application of rare earth erbium-modified pollen carbon composite photocatalyst |
| CN114210315B (en) * | 2021-12-31 | 2024-02-20 | 厦门稀土材料研究所 | Preparation and application of rare earth erbium modified pollen carbon composite photocatalyst |
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