CN103977821A - Cu3SnS4-graphene composite visible-light-driven photocatalyst and preparation method thereof - Google Patents

Abstract

The invention relates to a Cu3SnS4-graphene composite visible-light-driven photocatalyst and a preparation method thereof. The preparation method comprises: adding 0.060 g of CuAc2.H2O, 0.030 g of thioacetamide (TAA) and 0.035 g of SnCl4.5H2O into 45 mL of N,N-dimethylformamide (DMF), stirring at room temperature to complete dissolved; ultrasonically dispersing 0.015 g of graphite oxide into 10 mL of anhydrous ethanol, so as to obtain a suspension of graphene oxide; slowly dropwise adding the graphene oxide suspension into the above solution, and continuing to stirring for 1 h; transferring the obtained mixture into a high-pressure reaction vessel with a teflon liner, and performing a crystallization reaction at 180-200 DEG C for 12 h; and performing filtering, washing and drying on the obtained solid product, so as to obtain the Cu3SnS4-graphene composite visible-light-driven photocatalyst. The preparation method is environment-friendly and simple in technology. The prepared composite catalyst has extremely high visible-light catalytic activity, and has potential application value to technologies for photocatalytically decomposing organic pollutants by utilizing solar energy.

Description

A kind of Cu 3snS 4/ Graphene composite visible light catalyst and preparation method thereof

Technical field

The present invention relates to a kind of Cu ₃snS ₄/ Graphene composite visible light catalyst and preparation method thereof, belongs to photocatalysis and environmental technology field.

Background technology

Current environment problem and energy crisis become two large bottlenecks of restriction human development.Photocatalysis technology is expected to become the effective means that solves environment and energy problem; because will thoroughly solve the crisis of fossil energy exhaustion by converting solar energy into the photodissociation water technology of clean Hydrogen Energy, and photocatalytic degradation is removed the approach that cheapness is feasible that toxic organic pollutant will become solution environmental problem.Traditional TiO ₂photochemical catalyst forbidden band wider (Eg=3.2 eV), only can be by the ultraviolet excitation in sunshine (accounting for 3.8 % of solar energy), can not utilize visible ray in sunshine (account for solar energy 45%), make its solar energy utilization ratio low, seriously hindered the large-scale commercial of photocatalysis technology and promoted.Therefore, the novel photocatalysis material of exploitation high-performance visible light response has become one of the most popular current research direction, is also inexorable trend and developing direction that photocatalysis technology further moves towards industrialization.

Cu ₃snS ₄belonging to I-IV-VI family ternary compound, is a kind of important semiconductor and nonlinear optical material, has outstanding optics, calorifics and mechanical performance.Cu ₃snS ₄in fields such as solar cell, photocatalysis, there is potential using value.Recently, the discoveries such as Chen, Cu ₃snS ₄in sunlight catalytic hydrolytic hydrogen production, there is good photocatalytic activity (F. K. Chen, J. T. Zai, M. Xu, X. F. Qian, J. Mater. Chem. A, 2013, Isosorbide-5-Nitrae 316 – 4323), in addition, there is not yet Cu ₃snS ₄report for other light-catalyzed reactions.Pure Cu ₃snS ₄absorption wavestrip narrower, quantum efficiency is lower, in order to be better suitable for practical application, is necessary further to improve its photocatalysis performance.

Graphene is by sp ²the material with carbon element tightly packed one-tenth of hydridization carbon atom, that have monoatomic layer thickness, basic structural unit is benzene hexatomic ring the most stable in organic material.As catalyst carrier, Graphene stability is high, specific area is large, light transmission is good, not only can meet the requirement of chemical absorption of surface, also for condition has been created in fixing, separated, the recovery of catalyst.As electron acceptor, graphene nanometer sheet has good electron mobility, can improve the transfer of interface charge and the combination again of inhibition electron-hole pair.Therefore, by Graphene and Cu ₃snS ₄carry out compound its photocatalysis performance of further raising being had to positive effect.Up to now, there is not yet Cu ₃snS ₄the report of/graphene complex.

Summary of the invention

Object of the present invention aims to provide a kind of Cu ₃snS ₄/ Graphene composite visible light catalyst and preparation method thereof.

A kind of Cu of the present invention ₃snS ₄/ Graphene composite visible light catalyst, is characterized in that having following composition: Cu ₃snS ₄75.0 wt. %, Graphene 25.0 wt.%.

A kind of Cu for preparing of the present invention ₃snS ₄the method of/graphene composite photocatalyst, is characterized in that, has following preparation process and step:

A. by 0.060 g CuAc ₂h ₂the SnCl of the thioacetamide of O, 0.030 g (TAA), 0.035 g ₄5H ₂o is added to 45 ml n, nin-dimethyl formamide (DMF), be at room temperature stirred to completely and dissolve;

B. be dispersed in 10 ml absolute ethyl alcohols 0.015 g graphite oxide is ultrasonic, obtain the suspension of graphene oxide;

C. graphene oxide suspension is slowly added drop-wise in step (a) gained solution, and continues to stir 1 h;

D. step (c) gained mixture is transferred in the autoclave of teflon gasket to crystallization 12 h at 180-200 ℃;

E. the solid product obtaining after filtration, washs, and after being dried, obtaining Graphene content is the Cu of 25.0 % ₃snS ₄/ Graphene composite visible light catalyst.

Cu provided by the invention ₃snS ₄/ Graphene composite visible light catalyst, by Cu ₃snS ₄form with Graphene, wherein, Cu ₃snS ₄in the form of sheets, be evenly distributed on graphene platelet, the mass percent of Graphene is 25.0 %.

The present invention compared with prior art, has following remarkable advantage:

1, in one-step method solvent heat building-up process, the reduction of graphene oxide and Cu ₃snS ₄the formation of crystal completes simultaneously, and preparation technology is simple;

2, do not need to use other chemical reducing agents, the economic environmental protection of preparation process;

3, in the composite of preparation, Cu ₃snS ₄sheet is evenly dispersed on graphene platelet, and both contact closely, is conducive to the transmission of light induced electron;

4, the Cu of preparation ₃snS ₄/ graphen catalyst has very high visible light catalysis activity, in utilizing solar energy photocatalytic decomposing organic pollutant treatment technology, has potential using value.

Accompanying drawing explanation

Fig. 1 is X-ray diffraction (XRD) figure of embodiment and comparative example.

Fig. 2 is transmission electron microscope (TEM) figure of embodiment and ESEM (SEM) figure of comparative example.

Fig. 3 is the uv-visible absorption spectra of embodiment and comparative example.

Fig. 4 is the photocatalysis performance curve of embodiment and comparative example.

The specific embodiment

Now specific embodiments of the invention are described in detail in rear.

Embodiment

A. by 0.060 g CuAc ₂h ₂the SnCl of the thioacetamide of O, 0.030 g (TAA), 0.035 g ₄5H ₂o is added to 45 ml n, nin-dimethyl formamide (DMF), be at room temperature stirred to completely and dissolve;

B. be dispersed in 10 ml absolute ethyl alcohols 0.015 g graphite oxide is ultrasonic, obtain the suspension of graphene oxide;

C. graphene oxide suspension is slowly added drop-wise in step (a) gained solution, and continues to stir 1 h;

D. step (c) gained mixture is transferred in the autoclave of teflon gasket to crystallization 12 h at 180-200 ℃;

E. the solid product obtaining after filtration, washs, and after being dried, obtaining Graphene content is the Cu of 25.0 % ₃snS ₄/ Graphene composite visible light catalyst.

XRD analysis result (Fig. 1) shows, sample Cu ₃snS ₄28.3,47.2 and 56.0 ^othere is diffraction maximum in place, with the Cu of tetragonal phase structure ₃snS ₄characteristic diffraction peak (the JCPDS card number: 33-0501), do not occur other dephasign peaks in figure, show in product containing CuS, Cu that matches ₂s, SnS, SnS ₂deng impurity, purity is very high.At Cu ₃snS ₄in/Graphene, do not find 2q=10.7 ^othe diffraction maximum of the graphite oxide at place, illustrates that, in solvent heat process, graphene oxide has been reduced into Graphene.The TEM result of Fig. 2 shows, uniform Cu ₃snS ₄sheet is evenly dispersed on ultra-thin graphene film, and both contact closely.The uv-visible absorption spectra of sample (Fig. 3) result shows, Cu ₃snS ₄after compound with Graphene, not only widen the absorption region of visible ray, and increased the absorption intensity of visible ray.The Cu of preparation ₃snS ₄/ graphene composite photocatalyst has very high catalytic activity, under 150 min radiation of visible light, can methyl orange is degradable, can rhodamine B is degradable in 125 min, in 200 min, Pyrogentisinic Acid's Visible Light Induced Photocatalytic rate reaches 88.0 %, and its catalytic activity is higher than pure Cu ₃snS ₄(Fig. 4).

comparative example

In preparation process except not adding graphite oxide, the same embodiment of all the other operating process.

Finally make the not pure Cu of graphene-containing ₃snS ₄photochemical catalyst.

The XRD result of sample is referring to Fig. 1.The SEM result (Fig. 2) of sample shows, pure Cu ₃snS ₄for floriform appearance.The uv-visible absorption spectra result of sample is referring to Fig. 3, and photocatalysis performance is referring to Fig. 4.

Claims (2)

1. a Cu ₃snS ₄/ Graphene composite visible light catalyst, is characterized in that having following composition: Cu ₃snS ₄mass percent be 75.0 %, the mass percent of Graphene is 25.0 %.

2. a Cu ₃snS ₄the preparation method of/Graphene composite visible light catalyst, is characterized in that, has following preparation process and step:

A. by 0.060 g CuAc ₂h ₂the SnCl of the thioacetamide of O, 0.030 g (TAA), 0.035 g ₄5H ₂o is added to 45 ml n, nin-dimethyl formamide (DMF), be at room temperature stirred to completely and dissolve;

B. be dispersed in 10 ml absolute ethyl alcohols 0.015 g graphite oxide is ultrasonic, obtain the suspension of graphene oxide;

C. graphene oxide suspension is slowly added drop-wise in step (a) gained solution, and continues to stir 1 h;

D. step (c) gained mixture is transferred in the autoclave of teflon gasket to crystallization 12 h at 180-200 ℃;

E. the solid product obtaining after filtration, washs, and after being dried, obtaining Graphene content is the Cu of 25.0 % ₃snS ₄/ Graphene composite visible light catalyst.