CN108380169A - Remove active nucleus U (VI) laminated metal sulfide NaInS2And it prepares - Google Patents
Remove active nucleus U (VI) laminated metal sulfide NaInS2And it prepares Download PDFInfo
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- CN108380169A CN108380169A CN201810142574.0A CN201810142574A CN108380169A CN 108380169 A CN108380169 A CN 108380169A CN 201810142574 A CN201810142574 A CN 201810142574A CN 108380169 A CN108380169 A CN 108380169A
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
Abstract
The invention belongs to cation-exchanger preparing technical fields, more particularly to remove active nucleus U (VI) laminated metal sulfide NaInS2And it prepares.It is melting salt system with NaCl, using indium powder, high purity sulphur, Sodium Sulphate Nine Hydroxide as presoma, at 825 DEG C, roasting obtains porous metal sulfide NaInS2.This method is simple and quick, environmentally protective, presoma is cheap；Obtained NaInS2Because interlayer contains a large amount of tradable Na+, quick adsorption ability and higher adsorption capacity are shown to radioactivity uranyl, and there is wider pH opereating specifications, have higher tolerance to high salt concentration；The laminated metal sulfide NaInS that preparation method of the present invention obtains2It has broad application prospects in terms of being enriched with uranyl.
Description
Technical field
The invention belongs to cation-exchanger preparing technical fields, more particularly to remove active nucleus U (VI) stratiform gold
Belong to sulfide NaInS2And it prepares.
Background technology
Due to fossil fuel the extensive environmental pollution for utilizing and its bringing the problems such as so that increasingly pay attention to opening in various countries
Hair utilizes economic, efficient and clean nuclear energy.Over the last couple of decades, 9 nuclear power stations that China has put into operation are often produced per year
Raw 4,700,000 tons of spentnuclear fuels, it is contemplated that arrive the year two thousand twenty, China's spentnuclear fuel quantity has reached 10,000 tons, and with annual more than 1000 tons of speed
Degree continues growing.Uranium (235U) is the main fuel of China or even world nuclear, and various forms of uranium salts are the main of nuke rubbish
Ingredient, simultaneous fission generate a series of non-actinium series isotopes.Currently, the reserves of URANIUM IN SEAWATER are about 4 × 1012Kg,
About in 3ppb, the nuclear fuel that it is capable of providing more than one thousand years uses concentration.Currently, the ion Na coexisted in seawater+、Mg2+、Ca2+、
Cl-、、Type complexity and the unfavorable factors such as content height, constrain the efficiency and cost of the extraction of uranium from seawater.
Absorption method is one of optimum method of the extraction of uranium from seawater, and the sorbing material that selectivity is good and adsorption efficiency is high is from sea
The optimal material of uranium is extracted in water.However, physical surface adsorptions and precipitation reduction are limited by surface process, it is easy to by oxidant
Oxidation, pollutant hinder and inhibit.The suction-operated of inorganic ion exchanger depends on the bulk property of material, and suction-operated is not
There are the limitations of sufacing, and inorganic ion exchanger has better heat resistance, radioresistens, mechanical strength etc., makes
Obtain it has original advantage in the processing of radioactive waste.Traditional ion exchange material based on oxide such as covers
There is the problem of selective not high, protonation is easy under low ph value in de- soil, zeolite, resin etc., hold to the absorption of radionuclide
It measures limited.According to software-hardware co-design, sulphur atom is soft base, andWithBe considered as hard cation, theoretically these
Cation is easier to combine with sulphur atom, forms strong covalent bond, chalcogenide can effectively adsorb U (VI) and Sr (II).Mesh
Before, only sulfide mineral such as FeS, this soft with physical efficiency removal uranyl, the dominant mechanism of removal uranyl is reduction sexavalence uranyl
Form precipitation U3O8, however, to ensure that its efficient removal rate, needs constantly to polish the adsorbent surface of the type
Processing, thus its practical application is restricted.
In recent years, there is the laminated metal chalcogenide A of ion-exchange performancexMQ2, wherein A be alkali metal ion, M 4,
5,6 subgroup early stage transition metal, Q S, Se, Te stablize in aqueous solution because it is at low cost, and pH is applied widely, inhales
The advantages that attached capacity is high, anti-interference ion energy is strong and separation and concentration and the safe disposal research for being used for radionuclide, so
And these materials are not particularly suited for practical application due to unstable facile hydrolysis.The laminated metal sulfide KMS-1 formerly reported
(K2xMnxSn3-xS6And KMS-2 (K (x=0.5-0.95))2xMgxSn3-xS6(x=0.5-1)) it is complicated, complicated that there are raw materials,
And active site is only exposed to surface, the technical problem relatively low to the adsorption capacity of U (VI).
Therefore, the novel lamellar metal sulfide that synthesis is stablized with superior structural and surface nature is to realize complicated ring
The key of radionuclide in water body is rapidly and efficiently removed under border.
Invention content
The purpose of the present invention is to provide removal active nucleus U (VI) laminated metal sulfide NaInS2And it prepares, tool
Body technique scheme is as follows：
A kind of removal active nucleus U (VI) uses laminated metal sulfide NaInS2By the InS with stratiform octahedral structure2 -
The Na that can be exchanged with interlayer+Composition, it is simple in structure, 863.94mg g can be reached to the saturated extent of adsorption of U (VI)-1。
A kind of layered metal sulfide NaInS2Preparation method, with nine water after indium powder, sulphur powder and vacuum drying
Conjunction vulcanized sodium is that raw material roasts under an inert atmosphere using sodium chloride fuse salt as solid solvents；Specifically include following steps：
(1) it is dried in vacuo Sodium Sulphate Nine Hydroxide, natural cooling, and is preserved under an inert atmosphere；
(2) under an inert atmosphere, the Sodium Sulphate Nine Hydroxide that step (1) obtains mixed with indium powder, sulphur powder and sodium chloride, ground
Mill, dry, roasting；
(3) solid powder after washing roasting, and be dried in vacuo.
The vacuum drying temperature of Sodium Sulphate Nine Hydroxide is 100-120 DEG C, drying time 6-12h.
The Sodium Sulphate Nine Hydroxide, indium powder, sulphur powder and sodium chloride molar ratio are (1~2):1:(2~4):4.
The calcination temperature is 825-900 DEG C, roasting time 4-6h.
Detergent is deionized water, ethyl alcohol in the step (3), and drying temperature is 40-60 DEG C, drying time 6-12h.
The inert atmosphere is by Ar, N2Or He is provided.
Beneficial effects of the present invention are：
(1) sulfide NaInS in laminated metal provided by the invention2Fuse salt synthetic method, only with indium powder, simple substance sulphur powder
With vulcanized sodium as presoma, using fuse salt sodium chloride as solid solvents, in inert atmosphere high-temperature roasting can be completed；With biography
The wet chemistry methods of system are compared, and molte-salt synthesis is not limited by water and organic solvent；It is inhaled compared to the U (VI) in other seawater
Preparing for enclosure material is simpler, quick, effective, it is only necessary to which single step reaction can be obtained that size is uniform, absorption U of favorable dispersibility
(VI) material there is easy to operate, raw material to be easy to get, the advantage of low production cost, be conducive to industrialization promotion；
(2) the laminated metal sulfide NaInS that method produced according to the present invention is prepared2For nano particle it is uniform, point
The pure laminated metal sulfide that property is good, crystallinity is high and simple in structure is dissipated, interlayer contains abundant tradable Na+, to putting
Penetrating property U (VI) has efficient capture adsorption capacity.
(3) sulfide NaInS in laminated metal provided by the invention2Big, pH ranges are measured with high selectivity, absorption U (VI)
Extensively, not by high concentration Ca2+The advantages that interfering, is easy to operate and control is suitable for drinking water, seawater and other Complex water body systems
The efficient quick adsorption of middle U (VI)；Solve the pH operations that absorption property is low, narrow existing for existing absorption U (VI) material
The problems such as range, high concentration brine poor resistance.
Description of the drawings
Fig. 1 is the laminated metal sulfide NaInS that the embodiment of the present invention 1 is prepared2The characterization collection of illustrative plates of solid powder；Its
In, a) it is scanning electron microscope (SEM) photograph, b) be transmission electron microscope picture, c) it is X-ray energy dispersion spectrum；
Fig. 2 is the laminated metal sulfide NaInS that the embodiment of the present invention 1 is prepared2Solid powder adsorbs N2Absorption etc.
Warm line and graph of pore diameter distribution, wherein 2-a are adsorption isotherm collection of illustrative plates, and 2-b is graph of pore diameter distribution；
The laminated metal sulfide NaInS that Fig. 3 embodiment of the present invention 1 is prepared2Solid powder adsorbs before and after U (VI)
X ray diffracting spectrum and infrared spectrum collection of illustrative plates, wherein 3-a are X ray diffracting spectrum, and 3-b is infrared spectrum collection of illustrative plates.
Fig. 4 is the laminated metal sulfide NaInS that the embodiment of the present invention 1 is prepared2To the absorption effect of radionuclide U
Fruit collection of illustrative plates, wherein 4-a are NaInS2To the curve of adsorption kinetics of U (VI), 4-b is PH to NaInS2Adsorb the shadow of U (VI) effect
It rings, 4-c Ca2+Concentration is to Kd U(mg/L) influence of breadth coefficient, 4-d are under different temperatures, and U (VI) is in NaInS2On absorption
Thermoisopleth；
Fig. 5 is the laminated metal sulfide NaInS that the embodiment of the present invention 1 is prepared2Radionuclide U (VI) is adsorbed
Thermodynamics matched curve；
Fig. 6 is the laminated metal sulfide NaInS that the embodiment of the present invention 1 is prepared2To radioactive nucleus in different water systems
The absorption property of plain U (VI).
Specific implementation mode
The present invention provides removal active nucleus U (VI) laminated metal sulfide NaInS2And prepare, with reference to attached
The present invention is described further with embodiment for figure.
Embodiment 1
Prepare laminated metal sulfide NaInS2, it is as follows：
(1) Sodium Sulphate Nine Hydroxide for weighing 0.48g, using vacuum drying chamber after 100 DEG C of dry 12h, natural cooling
To the Na for losing the crystallization water2S is placed in glove box, is preserved at Ar；
(2) Na for obtaining step (1)2S is with 0.126g indiums powder, 0.128g high purity sulphurs, 0.234g sodium chloride in argon gas gas
Grinding stirs evenly in glove box under atmosphere, H in glove box2O、O2The equal ＜ 1ppm of concentration；Mixture is placed in the ceramic earthenware of 7mL
In crucible,
(3) it in tube furnace, is heated up with 5 DEG C/min heating rates, and 4h is persistently roasted under 825 DEG C, Ar protections；
(4) it after the solid powder natural cooling for obtaining step (3), is respectively washed three times to supernatant with deionized water, ethyl alcohol
Liquid is close to neutrality, to remove impurity；Dry 12h is subsequently placed in 60 DEG C of vacuum drying chamber to get to faint yellow laminated metal
Sulfide NaInS2Solid powder.
Fig. 1-a, 1-b are respectively the metal sulfide NaInS being prepared2Scanning electron microscope (SEM) photograph, the transmission electricity of solid powder
Mirror figure, from Fig. 1-a, 1-b it is found that prepared NaInS2It is uniformly dispersed, does not show block structure.Fig. 1-c are absorption U
(VI) NaInS afterwards2X-ray energy dispersion spectrum, it can be deduced that NaInS2In most Na+Replaced by U (VI), explanation
NaInS2The Na of interlayer+Ion-exchange reactions has occurred with U (VI).
Fig. 2-a are the metal sulfide NaInS being prepared2The N of solid powder2Adsorption isothermal curve can be obtained from 2-a
Go out, metal sulfide NaInS2The specific surface area of solid powder is 12m2/ g is far longer than business NaInS2Specific surface area (<
1.0m2/ g), it is more advantageous to and improves NaInS2With the contact area of U (VI), promote ion-exchange reactions, enhances absorption property；Figure
2-b is the metal sulfide NaInS being prepared2The graph of pore diameter distribution of solid powder, it can be seen from the figure that NaInS2Solid
Powder pore-size distribution is between 10nm-100nm, i.e., with the presence of mesoporous and macropore, the presence in this compound aperture improves
NaInS2The probability for colliding and contacting with U (VI), to and then into InS2 -Interlayer, and and Na+Carry out ion exchange.
Fig. 3-a, 3-b are NaInS before and after absorption U (VI)2The X ray diffracting spectrum and infrared spectrum collection of illustrative plates of solid powder.
By Fig. 3-a it is found that the NaInS being prepared2Crystallinity is relatively good, free from admixture peak；U (VI) is adsorbed afterwards it can be found that (003) is brilliant
Interplanar distance becomes larger, and illustrates that U (VI) ion enters NaInS2Interlayer；And in 924cm from infared spectrum 3-b-1Place can observe
To [O=UVI=O]2+Antisymmetric vibration peak illustrates that there is only NaInS by U (VI)2Interlayer has also been adsorbed on NaInS2Surface.
Embodiment 2
The laminated metal sulfide NaInS that detection embodiment 1 is prepared2To the adsorption effect of radionuclide U (VI),
Concrete operations are as follows：
(1) successively to NaInS is added in polyethylene centrifuge tube2, U containing radionuclide (VI) UO2(NO3)2·6H2O is molten
Liquid and contain Ca2+,Mg2+,K+And Na+The electrolyte solution of plasma；
(2) NaNO of 0.4mol/L is used3Ionic strength is adjusted, with micro HNO3Or the pH of NaOH solution regulation system is arrived
4.0；
(3) and then by mixed uniformly suspension it fully vibrates on the oscillator, as contact 12h, after absorption reaches balance,
It is centrifuged under 9000rpm rotating speeds so that be separated by solid-liquid separation；
(4) supernatant for taking certain volume, with inductively coupled plasma mass spectrometry measure supernatant in U (VI) it is dense
Degree.
Fig. 4-a are NaInS2To the curve of adsorption kinetics of U (VI)；It can be seen that from Fig. 4-a in pH=4.0, U
(VI) in NaInS2Reach adsorption equilibrium adsorption efficiency within upper 30min and reaches 98%.
Under above-mentioned same operation, the laminated metal sulfide NaInS that embodiment 1 obtains is detected respectively2In different PH, no
Same CaCl2Under concentration, different temperatures, the variation to the absorption behavior of radionuclide U, testing result respectively as Fig. 4-b, 4-c,
Shown in 4-d；
4-b is different PH to NaInS2Adsorb the influence of U (VI) effect；It can be seen that from Fig. 4-b in PH=4.0-9.0
In range, NaInS280% or more is maintained to the adsorption rate of U (VI), compared to traditional oxygen-carrying ion exchanger, NaInS2Contain
There is soft base site S2-Ligand, it is weaker to the hard hydrogen ion compatibility in water body；Therefore, NaInS2It shows in acid condition
Preferable absorption property.
4-c is Ca2+Concentration is to Kd U(mg/L) influence of breadth coefficient；It can be seen that from Fig. 4-c when Ca/U molar ratios are
1.5×103~6 × 104When, NaInS2Show good distribution coefficient Kd UIt is 1.04 × 103-2.32×104, i.e. NaInS2Table
Reveal to Ca2+Higher tolerance.
4-d is under different temperatures, and U (VI) is in NaInS2On adsorption isotherm；From Fig. 4-d can be seen that 293K,
Under 313K, 333K, NaInS2Saturated extent of adsorption to U (VI) is 699.72mg g respectively-1、804.44mg g-1、863.94mg
g-1, that is, increasing temperature can promote U (VI) in NaInS2On ion exchange；In addition, to NaInS in Fig. 4-d2To U's (VI)
Adsorption isotherm carries out models fitting and obtains, NaInS2Langmuir models are met to the absorption of U (VI), that is, illustrate to prove
NaInS2The active site on surface is impartial to the absorption of U (VI), and belongs to monolayer adsorption.
To U (VI) in NaInS2On ion exchange carry out thermodynamics fitting, specifically exist as shown in figure 5, obtaining U (VI)
NaInS2On ion exchange process belong to the spontaneous endothermic reaction, therefore can promote U (VI) in NaInS under hot conditions2On
Ion exchange, give U (VI) and NaInS2Interaction provides thermodynamics foundation.
Therefore, the laminated metal sulfide NaInS being prepared through above-mentioned preparation method2To radionuclide U adsorption rates
Reach 98%, the adsorption rate in wider PH=4.0-9.0 can reach 80% or more, and not by electrolyte in water cation
The higher Ca of content2+Influence, that is, there is significant adsorption effect and applicable environment is extensive, disturbing factor is few.
Embodiment 3
The laminated metal sulfide NaInS that embodiment 1 is prepared2It polluted for radioactive wastewater uranyl ultrapure
The adsorption experiment of water, tap water and seawater.
Wherein, ultra-pure water is by the water system of conductive electrolyte almost all removal, and resistivity reaches 18.25M at 25 DEG C
Ω*cm；Drinking water is derived from drinking water, does not directly apply to adsorption experiment by filtering；It is horizontal that seawater picks up from Zhejiang Province Zhoushan six
Waters near island.Concrete operations are：Above-mentioned solution is polluted by the uranyl of 30ppb respectively, the NaInS of 1.0g/L is added2, stir
It mixes 24 hours, the concentration of U (VI) in supernatant is detected with 1 same method of embodiment.
Wherein the electrolyte cation of ultra-pure water, tap water and seawater and the front and back testing results changed of pH are as shown in table 1：
Table 1 ultra-pure water, pollution drinking water and seawater in U (VI) in NaInS2Upper adsorption experiment
Different aqueous systems are to U (VI) in NaInS2On Adsorption Effect as shown in fig. 6, from fig. 6, it can be seen that containing each
Kind electrolyte cation Na+、K+、Mg2+And Ca2+Complicated water system in, NaInS2Higher adsorbance is still kept to U (VI),
With potential industrial application value.
Claims (7)
1. a kind of removal active nucleus U (VI) uses laminated metal sulfide NaInS2, which is characterized in that the NaInS2By having
The InS of stratiform octahedral structure2 -The Na that can be exchanged with interlayer+Composition.
2. a kind of layered metal sulfide NaInS of claim 12Preparation method, which is characterized in that the preparation method
Using the Sodium Sulphate Nine Hydroxide after indium powder, sulphur powder and vacuum drying as raw material, using sodium chloride fuse salt as solid solvents, in indifferent gas
It is roasted under atmosphere；Specifically include following steps：
(1) it is dried in vacuo Sodium Sulphate Nine Hydroxide, and is preserved under an inert atmosphere；
The Sodium Sulphate Nine Hydroxide that step (1) obtains is mixed with indium powder, sulphur powder and sodium chloride (2) under an inert atmosphere, is ground,
Dry, roasting；
(3) solid powder after washing roasting, and be dried in vacuo.
3. preparation method according to claim 2, which is characterized in that the vacuum drying temperature of Sodium Sulphate Nine Hydroxide is
100-120 DEG C, drying time 6-12h.
4. preparation method according to claim 2, which is characterized in that the Sodium Sulphate Nine Hydroxide, indium powder, sulphur powder and chlorination
Sodium molar ratio is (1~2):1:(2~4):4.
5. preparation method according to claim 2, which is characterized in that the calcination temperature is 825-900 DEG C, roasting time
For 4-6h.
6. preparation method according to claim 2, which is characterized in that detergent is deionized water, second in the step (3)
Alcohol, drying temperature are 40-60 DEG C, drying time 6-12h.
7. preparation method according to claim 2, which is characterized in that the inert atmosphere is by Ar, N2Or He is provided.
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| CN201810142574.0A CN108380169B (en) | 2018-02-11 | 2018-02-11 | Layered metal sulfide NaInS for removing radionuclide U (VI)2And preparation thereof |
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| CN201810142574.0A CN108380169B (en) | 2018-02-11 | 2018-02-11 | Layered metal sulfide NaInS for removing radionuclide U (VI)2And preparation thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113713788A (en) * | 2021-07-29 | 2021-11-30 | 中国科学院福建物质结构研究所 | Intercalation type manganese thiophosphite material and preparation method and application thereof |
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| JP2004008922A (en) * | 2002-06-06 | 2004-01-15 | Japan Science & Technology Corp | Visible light responsive sulfide photocatalyst for producing hydrogen from water |
| CN101054198A (en) * | 2007-05-17 | 2007-10-17 | 上海交通大学 | Method for preparing monodisperse ternary sulfide CuInS2 |
| CN102229470A (en) * | 2011-04-15 | 2011-11-02 | 河南大学 | Method of preparing CuInS2 film by wet chemical process |
| CN105271372A (en) * | 2015-10-27 | 2016-01-27 | 南昌航空大学 | Method for preparing one-dimensional disc-shaped nano indium sulfide particles with organic molten salt method |
| CN106145182A (en) * | 2015-03-18 | 2016-11-23 | 陈莹 | A kind of NaInS2nanometer sheet acanthosphere |
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2018
- 2018-02-11 CN CN201810142574.0A patent/CN108380169B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004008922A (en) * | 2002-06-06 | 2004-01-15 | Japan Science & Technology Corp | Visible light responsive sulfide photocatalyst for producing hydrogen from water |
| CN101054198A (en) * | 2007-05-17 | 2007-10-17 | 上海交通大学 | Method for preparing monodisperse ternary sulfide CuInS2 |
| CN102229470A (en) * | 2011-04-15 | 2011-11-02 | 河南大学 | Method of preparing CuInS2 film by wet chemical process |
| CN106145182A (en) * | 2015-03-18 | 2016-11-23 | 陈莹 | A kind of NaInS2nanometer sheet acanthosphere |
| CN105271372A (en) * | 2015-10-27 | 2016-01-27 | 南昌航空大学 | Method for preparing one-dimensional disc-shaped nano indium sulfide particles with organic molten salt method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113713788A (en) * | 2021-07-29 | 2021-11-30 | 中国科学院福建物质结构研究所 | Intercalation type manganese thiophosphite material and preparation method and application thereof |
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