CN103990472A - Stable and efficient hydrogen production co-catalyst and preparation method thereof - Google Patents

Stable and efficient hydrogen production co-catalyst and preparation method thereof Download PDF

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CN103990472A
CN103990472A CN201410253260.XA CN201410253260A CN103990472A CN 103990472 A CN103990472 A CN 103990472A CN 201410253260 A CN201410253260 A CN 201410253260A CN 103990472 A CN103990472 A CN 103990472A
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catalyst
hydrogen manufacturing
mos
stable
high efficiency
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向斌
杨雷
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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    • 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

Abstract

The invention relates to a stable and efficient hydrogen production co-catalyst and a preparation thereof. The hydrogen production co-catalyst is formed by performing metallic nano-particle modification on the surface of a semi-conductor thin film hydrogen production co-catalyst. When the hydrogen production co-catalyst is used in a photocatalytic water decomposition experiment, the catalytic efficiency of the hydrogen production co-catalyst is far greater than that of a pure semi-conductor thin film hydrogen production co-catalyst.

Description

A kind of stable, high efficiency hydrogen manufacturing co-catalyst and preparation method thereof
Technical field
The invention belongs to technical field of nano material, relate in particular to stable, high efficiency hydrogen manufacturing co-catalyst and its production and use.
Background technology
Due to the unsustainable property of fossil fuel itself, and a large amount of SO of combustion of fossil fuels release 2deng meeting, to environment, the renewable new forms of energy such as development is clean, non-fossil fuel become the focus of paying close attention to recent years.Solar energy is a kind of inexhaustible energy.But the problems such as energy density is low, dispersion, difficult storage that solar energy exists.Hydrogen Energy has, and unique product clean, pollution-free and hydrogen burning is water, not nontoxic not the polluting the environment of the odorless of hydrogen own, thereby be considered to the most promising energy carrier of one.Therefore the method decomposition water that utilizes solar energy catalysis is method (Khaselev et al., Science, 1998,280, the 425-427 of the clean hydrogen energy source of a kind of ideal, very attracting generation; Mor et al., Nano Lett., 2005,5,191-195; Lin et al., Nano Lett., 2013,13,5615-5618; Osterloh et al., Chem.Mater., 2008,20,35-54).
The catalyst decomposition water of based semiconductor mainly contains three steps: 1) semiconductor light-catalyst absorbs light generation electron hole pair; 2) electronics separates and transfers to the surface of catalyst with hole: 3) photo-generated carrier completes relevant redox reaction (Yang et al., Acc.Chem.Res., 2012,46,1900-1909) on the surface of catalyst.In the time that these three steps all complete, catalytic reaction is just calculated end.In the past few years, scientists has been done certain research to the photochemical catalyst of based semiconductor and has been obtained many breakthrough new progresses, but especially before heavy industrialization application, still needs light-catalysed three steps to optimize further before photocatalysis is widely accepted.Especially how the problem of pendulum in face of researcher has: 1) how to strengthen the absorption of photocatalyst material to light, photocatalyst material is expanded to the absorption to visible ray to the absorption of ultraviolet light wave band.Measure wherein comprises: yin, yang ion doping, (Choi et al., J.Phys.Chem., 1994,98, the 13669-13679 such as the modification of metal phasmon to semi-conducting material; Asahi et al., Science, 2001,293,269-271; Linic et al., Nat.Mater., 2011,10,911-921); Compound to some the absorption visible rays of photocatalyst surface sensitization that absorb ultraviolet band can be expanded its spectral absorption scope (Nazeeruddin et al., Chem.Commun.2003,0,1456-1457); 2) how to increase the catalytic efficiency of catalyst.Measure wherein comprises the finishing certain cocatalysts nano particle to photochemical catalyst, can strengthen the absorption to reactant; Thereby crystal face more intense photocatalyst activity is exposed to the catalytic activity (Yang et al., Nature, 2008,453, the 638-641 that in reactant around, strengthen catalyst; He et al., Chem.Commun., 2011,47,10797-10799); 3) how to reduce the recombination probability of photo-generated carrier.Measure wherein comprises the concentration and the crystal boundary that reduce defect in catalyst, because defect and crystal boundary can produce impurity energy level and surface state energy level at interband, thereby therefore the recombination probability of increase photo-generated carrier has reduced light-catalysed efficiency.(Hoffmann?et?al.,Chem.Rev.,1995,95,69-96；)。The another kind of approach that reduces the recombination probability of carrier is in catalyst, to add co-catalyst, when the valence band of catalyst and co-catalyst and conduction band are during in certain suitable position, light induced electron can separate with hole under the effect of the built in field of both intersections, thereby has greatly reduced the recombination probability of photo-generated carrier.
The existing optimization to light-catalysed three steps is faced with the problems such as cost is high, complicated process of preparation.
Summary of the invention
The present invention has covered many metal nanoparticles by simple chemical solution synthetic method on semiconductive thin film hydrogen manufacturing co-catalyst surface, forms metal semiconductor junction.Using the semiconductive thin film hydrogen manufacturing co-catalyst of covering metal nano particle when the co-catalyst of photochemical catalyst carries out photochemical catalyzing, the catalytic efficiency that catalytic efficiency will be when using semiconductive thin film hydrogen manufacturing co-catalyst self.
Concrete, the present invention relates to every as follows:
1. stable, a high efficiency hydrogen manufacturing co-catalyst, described hydrogen manufacturing co-catalyst forms by metal nanoparticle modifying semiconductor film hydrogen manufacturing co-catalyst.
2. according to stable, high efficiency hydrogen manufacturing co-catalyst described in 1, metal nanoparticle is positioned at the surface of conventional hydrogen manufacturing co-catalyst, and forms metal semiconductor junction.
3. according to stable, high efficiency hydrogen manufacturing co-catalyst described in 1 or 2, wherein said metal nanoparticle comprises Cr, Ag, Fe, Co or Ni.
4. according to stable, high efficiency hydrogen manufacturing co-catalyst described in 1 or 2, wherein said semiconductive thin film hydrogen manufacturing co-catalyst comprises MoS 2, WS 2or MoSe 2.
According to described in 1 or 2, high efficiency hydrogen manufacturing co-catalyst, preferably it has M-MoS 2the chemical composition representing, wherein M=Cr or Ag.
Stable, high efficiency hydrogen manufacturing co-catalyst described in 6.1-5 any one is used for the purposes of the photochemical catalyzing of catalyst.
7. according to the purposes described in 6, wherein, described catalyst comprises CdS or TiO 2, preferably CdS.
8. a preparation method for stable, high efficiency hydrogen manufacturing co-catalyst, said method comprising the steps of:
(1) by a certain amount of CTAB ((C 16h 33(CH 3) 3) NBr) and the nitrate (M (NO of metal 3) x) be dissolved in order in a certain amount of deionized water, continue to stir a period of time, until they dissolve completely, wherein;
(2) semiconductive thin film hydrogen manufacturing co-catalyst is put into above-mentioned solution, under lasting stirring, then by certain density ascorbic acid (C 6h 8o 6) solution and NaOH solution joins respectively in above-mentioned mixed liquor;
(3) stir after a period of time, reacted suspension is taken out, centrifugal, by absolute ethyl alcohol and washed with de-ionized water, and the precipitation after cleaning is dried, thereby obtain product.
9. according to the preparation method described in 8, wherein the ascorbic acid solution in step (2) and NaOH solution dropwise drip lentamente with liquid-transfering gun, and drop rate is between 0.5 drop/sec to 2 drops/sec, and the stirring that will continue in the process dripping; Mixing time in step (3) is 10 minutes to 1 hour; And in step (3), use respectively the number of times of absolute ethyl alcohol and washed with de-ionized water between 3 to 6 times.
10. according to the preparation method described in 8 or 9, wherein M is selected from Cr, Ag, Fe, Co or Ni, preferably Cr or Ag, and described semiconductive thin film hydrogen manufacturing co-catalyst comprises MoS 2, WS 2or MoSe 2, be preferably MoS 2nanometer sheet.
Below technical scheme of the present invention is elaborated further.It should be pointed out that each embodiment of the present invention can combine as required by any way.
First aspect of the present invention, provides a kind of stable, high efficiency hydrogen manufacturing co-catalyst.
In a preferred embodiment, described stable, high efficiency hydrogen manufacturing co-catalyst is the semiconductive thin film hydrogen manufacturing co-catalyst that surfaces of metal nanoparticles is modified, at semiconductive thin film hydrogen manufacturing co-catalyst surface coverage metal nanoparticle.
In a preferred embodiment, described semiconductive thin film hydrogen manufacturing co-catalyst includes but not limited to MoS 2, WS 2or MoSe 2, preferably MoS 2.
In another preferred embodiment, described metal nanoparticle includes but not limited to Cr, Ag, Fe, Co or Ni, preferably Cr or Ag.
In a more preferred embodiment, described hydrogen manufacturing co-catalyst has M-MoS 2the chemical composition representing, wherein M=Cr or Ag, M covers MoS 2the superficial layer of nanometer sheet forms metal semiconductor junction.
In a preferred embodiment, the size of M is preferably between 10nm-100nm.
In a further embodiment, described stable, high efficiency hydrogen manufacturing co-catalyst have Cr-MoS 2the chemical composition representing, in the time of co-catalyst as photochemical catalyst CdS, the Mean Speed of catalyzing manufacturing of hydrogen reaches 38000 μ molg -1h -1, be greater than pure MoS 218000 μ molg during as co-catalyst -1h -1average hydrogen manufacturing speed.
In another further embodiment, described stable, high efficiency hydrogen manufacturing co-catalyst have Ag-MoS 2the chemical composition representing, and CdS is while combining as co-catalyst, the Mean Speed of catalyzing manufacturing of hydrogen reaches 107000 μ molg -1h -1, much larger than pure MoS 218000 μ molg during as co-catalyst -1h -1average hydrogen manufacturing speed.
Second aspect of the present invention provides described stable, the high efficiency hydrogen manufacturing co-catalyst of first aspect for the purposes of the photochemical catalyzing of catalyst.
The 3rd aspect of the present invention provides a kind of to be stablized, the preparation method of high efficiency hydrogen manufacturing co-catalyst.
In a preferred embodiment, described hydrogen manufacturing co-catalyst has M-MoS 2the chemical composition representing, wherein M=Cr or Ag, said method comprising the steps of:
(1) by a certain amount of CTAB ((C 16h 33(CH 3) 3) NBr) and the nitrate (M (NO of metal 3) x) be dissolved in a certain amount of deionized water, continue to stir a period of time until they all dissolve;
(2) by MoS 2powder is put into above-mentioned mixed solution, under lasting stirring, then by certain density ascorbic acid (C 6h 8o 6) solution and NaOH solution joins respectively in above-mentioned mixed liquor;
(3), after a period of time, reacted suspension is taken out, centrifugal, by absolute ethyl alcohol and washed with de-ionized water, and the precipitation after cleaning is dried, thereby obtain product.
In sum, the present invention relates to a kind of stable, high efficiency hydrogen manufacturing co-catalyst, preferably, there is M-MoS 2the chemical composition representing, wherein M=Cr or Ag.Measure their fluorescence Spectra, finding does not have peak, and pure MoS 2powder has certain fluorescence peak, and the M-MoS that the present invention is synthetic is described 2there is a built in field in the metal semiconductor junction forming, this electric field can effectively stop the compound of photo-generated carrier.This is also co-catalyst M-MoS 2with CdS in conjunction with time hydrogen production efficiency be greater than pure MoS 2reason during as co-catalyst.
Brief description of the drawings
Fig. 1 is MoS 2the TEM picture of nanometer sheet;
Fig. 2 is Cr-MoS 2tEM picture;
Fig. 3 is Cr-MoS 2cross section HRTEM picture;
Fig. 4 is MoS 2, Cr-MoS 2and Ag-MoS 2fluorescence spectrum figure;
Fig. 5 is MoS 2, Cr-MoS 2and Ag-MoS 2during respectively as the co-catalyst (mass fraction is 1%) of CdS, H 2the graph of a relation of output and time;
Fig. 6 is Cr-MoS 2during as the co-catalyst (mass fraction is 1%) of CdS, H under several circulations 2the graph of a relation of output and time.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is further illustrated.
Embodiment 1
Hydrogen manufacturing co-catalyst Cr-MoS 2preparation, sign and catalytic property
A kind of stable, high efficiency hydrogen manufacturing co-catalyst Cr-MoS 2preparation method, comprise the following steps:
(1) by the CTAB ((C of 1.6mmol 16h 33(CH 3) 3) NBr) (traditional Chinese medicines group analyzes pure) and 0.04mmol Cr (NO 3) 3(traditional Chinese medicines group analyzes pure) is added in order in the deionized water of 80ml under the effect of magnetic stirrer;
(2) stir a period of time until CTAB and Cr (NO 3) 3after all dissolving, by the MoS of 2mg 2(hydro-thermal method is synthetic) powder is put in above-mentioned solution;
(3) under the slow stirring of magnetic stirring apparatus, then be 50mM by concentration, the C that volume is 3.2ml 6h 8o 6(traditional Chinese medicines group analyzes pure) solution and concentration are 0.5M, and NaOH (traditional Chinese medicines group the analyzes pure) solution that volume is 3.2ml joins in above-mentioned suspension successively;
(4) stir after 1h, the suspension that above-mentioned reaction is obtained is centrifugal with centrifuge, centrifugal 10min in the situation that rotating speed is 6000rpm, and precipitation is cleaned respectively 3 times by ethanol and deionized water;
(5) after cleaning, product is dried under 60 DEG C, the environment of vacuum, after 6h, take out, obtain dry Cr-MoS 2powder;
(6) characterize synthetic Cr-MoS with the TEM that Japanese JEOL company produces 2, to find, Cr nano particle covers MoS 2the surface of nanometer sheet, as shown in Figure 1 and Figure 2; Characterize Cr-MoS with HRTEM 2cross section, also find that synthetic Cr nano particle is positioned at MoS 2the surface of nanometer sheet, as shown in Figure 3; Use Britain R eni sh awthe Raman spectrometer that company produces is measured its fluorescence spectrum, with respect to pure MoS 2nanometer sheet, fluorescence peak disappears, as shown in Figure 4.Illustrate by chemical solution method and form Cr-MoS 2after composite construction, greatly reduce the recombination probability of photo-generated carrier, to such an extent as to the efficiency of producing hydrogen while greatly having improved its co-catalyst catalytic decomposition water as CdS.By the Cr-MoS of 10mg 2-CdS and MoS 2-CdS photochemical catalyst sample (Cr-MoS 2and MoS 2mass fraction be 1%) be 0.25M Na with concentration respectively 2s, 0.35M Na 2sO 3mixed liquor mix, and ultrasonic 10 minutes.Suspension after ultrasonic is put into the flask of 50ml, then with nitrogen, the air in bottle is drained.At normal temperatures, the xenon lamp irradiation flask with 300w with UV filter, and use the generation speed of surveying hydrogen with the gas chromatography apparatus of thermal conductivity sensor.Found that Cr-MoS 2be 38000 μ molg as the Mean Speed of co-catalyst catalyzing manufacturing of hydrogen -1h -1, be greater than pure MoS 218000 μ molg during as co-catalyst -1h -1average hydrogen manufacturing speed, as shown in Figure 5; Fig. 6 has provided in the case of different cycle periods, Cr-MoS 2h during as the co-catalyst of CdS 2the relation that is all directly proportional of output and time, and the speed of producing hydrogen do not reduce, and Cr-MoS is described 2can effectively resist photoetch.
Embodiment 2
Hydrogen manufacturing co-catalyst Ag-MoS 2preparation, sign and catalytic property
A kind of stable, high efficiency hydrogen manufacturing co-catalyst Ag-MoS 2preparation method, comprise the following steps:
(1) by the CTAB ((C of 1.6mmol 16h 33(CH 3) 3) NBr) (traditional Chinese medicines group analyzes pure) and 0.08mmol AgNO 3(traditional Chinese medicines group analyzes pure) is added in order in the deionized water of 80ml under the effect of magnetic stirrer;
(2) stir a period of time until CTAB and AgNO 3all dissolve, by the MoS of 2mg 2powder (hydro-thermal method is synthetic) is put in above-mentioned solution;
(3) under the slow stirring of magnetic stirring apparatus, then be 50mM by concentration, the C that volume is 0.64ml 6h 8o 6(traditional Chinese medicines group analyzes pure) solution and concentration are 0.5M, and NaOH (traditional Chinese medicines group the analyzes pure) solution that volume is 0.064ml joins in above-mentioned suspension successively;
(4) under agitator continues to stir, the NaBH that is 100mM by 0.5ml concentration 4(traditional Chinese medicines group analyzes pure) frozen water solution joins in suspension above;
(5) stir after 10min, the suspension that above-mentioned reaction is obtained is centrifugal with centrifuge, centrifugal 10min in the situation that rotating speed is 6000rpm, and will precipitate use ethanol and washed with de-ionized water 6 times;
(6) after cleaning, product is dried under 60 DEG C, the environment of vacuum, after 6h, takes out,
Obtain dry Ag-MoS 2powder;
(7) measure its fluorescence spectrum with the Raman spectrometer that Renishaw company of Britain produces, with respect to pure MoS 2nanometer sheet, fluorescence peak disappears, as shown in Figure 4.Illustrate by chemical solution method and form Ag-MoS 2after composite construction, greatly reduce the combined efficiency of photo-generated carrier, to such an extent as to the efficiency of hydrogen manufacturing while greatly having improved its co-catalyst catalytic decomposition water as CdS.By the Ag-MoS of 10mg 2-CdS and MoS 2-CdS photochemical catalyst sample (Ag-MoS 2and MoS 2mass fraction be 1%) be 0.25M Na with concentration respectively 2s, 0.35M Na 2sO 3mixed liquor mix, and ultrasonic 10 minutes.Suspension after ultrasonic is put into the flask of 50ml, then with nitrogen, the air in bottle is drained.At normal temperatures, the xenon lamp irradiation flask with 300w with UV filter, and use the generation speed of surveying hydrogen with the gas chromatography apparatus of thermal conductivity sensor.Found that Ag-MoS 2be 107000 μ molg as the Mean Speed of co-catalyst catalyzing manufacturing of hydrogen -1h -1, much larger than pure MoS 218000 μ molg during as co-catalyst -1h -1average hydrogen manufacturing speed, as shown in Figure 5.

Claims (10)

1. stable, a high efficiency hydrogen manufacturing co-catalyst, described hydrogen manufacturing co-catalyst forms by metal nanoparticle modifying semiconductor film hydrogen manufacturing co-catalyst.
2. stable, high efficiency hydrogen manufacturing co-catalyst according to claim 1, metal nanoparticle is positioned at the surface of semiconductive thin film hydrogen manufacturing co-catalyst, and forms metal semiconductor junction.
3. stable, high efficiency hydrogen manufacturing co-catalyst according to claim 1 and 2, wherein said metal nanoparticle comprises Cr, Ag, Fe, Co or Ni.
4. stable, high efficiency hydrogen manufacturing co-catalyst according to claim 1 and 2, wherein said semiconductive thin film hydrogen manufacturing co-catalyst comprises MoS 2, WS 2or MoSe 2.
5. according to claim 1 and 2, high efficiency hydrogen manufacturing co-catalyst, preferably it has M-MoS 2the chemical composition representing, wherein M=Cr or Ag.
6. stable, the high efficiency hydrogen manufacturing co-catalyst described in claim 1-5 any one is used for the purposes of the photochemical catalyzing of catalyst.
7. purposes according to claim 6, wherein, described catalyst comprises CdS or TiO 2, preferably CdS.
8. a preparation method for stable, high efficiency hydrogen manufacturing co-catalyst, said method comprising the steps of:
(1) by a certain amount of CTAB ((C 16h 33(CH 3) 3) NBr) and metal nitrate (M (NO 3) x) be dissolved in order in a certain amount of deionized water, continue to stir a period of time, until they dissolve completely, wherein;
(2) semiconductive thin film hydrogen manufacturing co-catalyst is put into above-mentioned solution, under lasting stirring, then by certain density ascorbic acid (C 6h 8o 6) solution and NaOH solution joins respectively in above-mentioned mixed liquor;
(3) stir after a period of time, reacted suspension is taken out, centrifugal, by absolute ethyl alcohol and washed with de-ionized water, and the precipitation after cleaning is dried, thereby obtain product.
9. preparation method according to claim 8, wherein the ascorbic acid solution in step (2) and NaOH solution dropwise drip lentamente with liquid-transfering gun, drop rate is between 0.5 drop/sec to 2 drops/sec, and the stirring that will continue in the process dripping; Mixing time in step (3) is 10 minutes to 1 hour; And in step (3), use respectively the number of times of absolute ethyl alcohol and washed with de-ionized water between 3 to 6 times.
10. preparation method according to claim 8 or claim 9, wherein M is selected from Cr, Ag, Fe, Co or Ni, preferably Cr or Ag, described semiconductive thin film hydrogen manufacturing co-catalyst comprises MoS 2, WS 2or MoSe 2, be preferably MoS 2nanometer sheet.
CN201410253260.XA 2014-06-09 2014-06-09 Stable and efficient hydrogen production co-catalyst and preparation method thereof Pending CN103990472A (en)

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Cited By (7)

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CN106423223A (en) * 2016-09-20 2017-02-22 中国计量大学 MoSe2@TiO2 photocatalyst in caky porous structure and preparation method of MoSe2@TiO2 photocatalyst in caky porous structure
CN107670676A (en) * 2017-10-13 2018-02-09 温州大学新材料与产业技术研究院 The preparation method and applications of the cadmium sulfide molybdenum sulfide tungsten sulfide heterojunction photocatalysis composite of one species sea urchin shape structure
CN108421555A (en) * 2018-02-24 2018-08-21 江南大学 A kind of preparation method of cobalt/carboritride hydridization photochemical catalyst
CN109331843A (en) * 2018-10-24 2019-02-15 温州大学 Graininess multicomponent sulfide-platinum heterojunction photocatalysis composite material and preparation method thereof and its production hydrogen application
WO2019150000A1 (en) * 2018-02-02 2019-08-08 Wmz - Nanosurfaces Oy Nanocomposites for photocatalytic water splitting using visible light and method for synthesis thereof
CN111617782A (en) * 2020-06-29 2020-09-04 南京理工大学 Preparation method of FeMoSe two-dimensional nano catalyst similar to natural nitrogenase
CN113952964A (en) * 2021-10-20 2022-01-21 北华大学 Preparation method and application of molybdenum disulfide/indium oxide nanocomposite material with 2D/3D structure

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Publication number Priority date Publication date Assignee Title
CN106423223A (en) * 2016-09-20 2017-02-22 中国计量大学 MoSe2@TiO2 photocatalyst in caky porous structure and preparation method of MoSe2@TiO2 photocatalyst in caky porous structure
CN107670676A (en) * 2017-10-13 2018-02-09 温州大学新材料与产业技术研究院 The preparation method and applications of the cadmium sulfide molybdenum sulfide tungsten sulfide heterojunction photocatalysis composite of one species sea urchin shape structure
WO2019150000A1 (en) * 2018-02-02 2019-08-08 Wmz - Nanosurfaces Oy Nanocomposites for photocatalytic water splitting using visible light and method for synthesis thereof
CN108421555A (en) * 2018-02-24 2018-08-21 江南大学 A kind of preparation method of cobalt/carboritride hydridization photochemical catalyst
CN109331843A (en) * 2018-10-24 2019-02-15 温州大学 Graininess multicomponent sulfide-platinum heterojunction photocatalysis composite material and preparation method thereof and its production hydrogen application
CN111617782A (en) * 2020-06-29 2020-09-04 南京理工大学 Preparation method of FeMoSe two-dimensional nano catalyst similar to natural nitrogenase
CN111617782B (en) * 2020-06-29 2023-03-24 南京理工大学 Preparation method of FeMoSe two-dimensional nano catalyst similar to natural nitrogenase
CN113952964A (en) * 2021-10-20 2022-01-21 北华大学 Preparation method and application of molybdenum disulfide/indium oxide nanocomposite material with 2D/3D structure
CN113952964B (en) * 2021-10-20 2023-11-17 北华大学 Preparation method and application of 2D/3D structured molybdenum disulfide/indium oxide nanocomposite

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Application publication date: 20140820