CN109894138A - A kind of N doping cuprous oxide catalysis material and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of N doping cuprous oxide catalysis materials and preparation method thereof.The present invention restores copper sulphate-urea admixture method by hydrazine hydrate under alkaline condition and obtains N doping cuprous oxide photocatalyst material, it is easy to operate, it is low in cost, there is higher photocatalysis performance to the photocatalytic degradation of organic pollutant, a low cost, the approach of high repayment are provided for the improvement of organic dye waste water.

Description

A kind of N doping cuprous oxide catalysis material and preparation method thereof

Technical field

The invention belongs to catalysis material technical fields, and in particular to a kind of N doping cuprous oxide catalysis material and its Preparation method.

Background technique

The Faced In Sustainable Development of today's society population expansion, shortage of resources, the problems such as environmental degradation, environment protect Shield is more and more all paid attention to by everybody.Limited resource is reasonably developed, take measures the deterioration for controlling environment, and effectively benefit With existing resource, realizes the industrial structure transformation of " low energy consumption, low pollution, high benefit ", alleviate resource environmental pressure, promote people With natural harmonious development.

Physical partition method, biological degradation method and change are broadly divided into the processing mode of the comparative maturity of waste water, exhaust gas at present Credit solution etc..Wherein common physical separation method includes sedimentation, flocculence, filtration method, absorption method and air- extraction etc.. Although the development and implementation of these current techniques are very mature, but still having some limitations property.Physical partition method is only Concentration is carried out to pollutant, is not removed from environment completely, or be to shift pollutant from a kind of object phase It is gone to another object Xiangli, is easy to generate secondary pollution in this way.For biological treatment, temperature, pH value and pollutant The factors such as type can have a huge impact biodegrade, and treatment effect is not satisfactory；The method that traditional chemical decomposes is logical Cross and add some chemical reagent, by with pollutant occur chemically react and bring it about degradation or be converted into environment without Other harmful substances, due to the invertibity of chemical reaction, still cannot decompose completely pollutant although there is certain advantage. In addition, these types of method also has energy consumption big, it is hard to understand that the device is complicated, is easy the disadvantages of bringing secondary pollution.In contrast, Semiconductor multiphase photocatalysis pollution control technology has apparent advantage, without secondary pollution because this method is easy to operate, and It, can be efficiently by organic pollutant decomposition and inversion at H with characteristic energy-efficient, that cleaning is nontoxic₂O, CO₂, SO₄ ^2-, NO^3-, PO₄ ^3-And X^-Equal inorganic molecules or ion, to realize the purpose of the complete inorganic mineralising of organic matter.

In solar spectrum, the range proportion of ultraviolet region will be lower than 5%, and visible range accounts for 43%, if It is that can effectively utilize sunlight, the practical application value of catalysis material is very huge, thus, cheap, environmental protection and high property The preparation of the visible-light photocatalysis material of energy will further push photocatalysis research and development to move towards practical.Cu₂O is a kind of typical P The semiconductor material of type, forbidden bandwidth are approximately 2.0eV, this can make Cu₂O is excited with being highly susceptible to visible light generates photoproduction electricity Son.And as photocatalyst material, Cu₂O is not only nontoxic, cheap, can remove photoelectricity with strong adsorption molecular oxygen Son achievees the effect that inhibit photo-generate electron-hole to compound.A large amount of related Cu₂O solar photocell research shows that Cu₂O tool There are good visible light catalytic characteristic and good stability.Based on the above result of study, Cu₂O can be in the irradiation of sunlight Lower carry out light-catalyzed reaction is a kind of environment-friendly type catalyst material for having very much commercial exploitation prospects, and in organic pollutant Good utilization is also obtained in terms of degradation treatment, importance is outstanding day by day.

Although Cu₂O can directly absorb visible light, also there is very high incident photon-to-electron conversion efficiency, but Cu₂O photoelectric conversion performance is not Easy to control, there are unstable factors.In addition, Cu₂O is easy to happen photoetch phenomenon, and photocatalytic activity is greatly affected.

Summary of the invention

It is an object of the invention to: in view of the above problems, providing a kind of N doping cuprous oxide catalysis material and its system Preparation Method, by the N of nonmetalloid doping and with to Cu₂O is modified, in the hope of improving Cu₂The photocatalytic activity of O.

The technical solution adopted by the invention is as follows:

A kind of preparation method of N doping cuprous oxide catalysis material, comprising the following steps:

S1. to CuSO₄·5H₂CO (NH is added in O solution₂)₂, it is uniformly mixed；

S2. it obtains that NaOH is added in mixed liquor into step S1, stirs, until becoming blackish green precipitating；

S3. N is added into blackish green precipitating obtained in step S2₂H₄·H₂O, stirring are hanged until becoming rufous completely Turbid；

S4. suspension obtained in step S3 is filtered, then precipitating is washed；

S5. to drying is deposited in obtained in step S4, grinding obtains finished product.

Restore the N doping Cu of copper sulphate-urea admixture method acquisition under alkaline condition by hydrazine hydrate₂O light is urged The introducing of agent material, N can change Cu₂O causes band gap can increase the absorption characteristic of light, effectively photoproduction can be promoted to carry The separation of son is flowed, the recombination probability of photo-generate electron-hole pair is reduced, so N mixes Cu₂O can be obtained than simple Cu₂O is higher Photocatalytic activity.

Further, CuSO₄·5H₂O、CO(NH₂)₂, NaOH and N₂H₄·H₂The molar ratio of O is 4.5-5.5:0.002- 0.028:8-12:3-8.

Further, CuSO₄·5H₂O、CO(NH₂)₂, NaOH and N₂H₄·H₂The molar ratio of O is 5.0:0.016:10:5, The catalysis material prepared using the molar ratio, good catalytic activity.

Further, drying process is to be dried under nitrogen protection in S5 step.

The N doping cuprous oxide catalysis material prepared by the preparation method, including cuprous oxide and it is entrained in the oxygen Change the nitrogen in cuprous.

In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:

1, in the present invention, according to the analysis of UV-Vis DRS as a result, N doping Cu₂The Absorption edge of O has occurred obviously Blue shift, and the absorption of the light of 400~500nm range is also enhanced, illustrates that N doping can result in Cu₂The forbidden band of O is wide Degree increases；

2, in the present invention, by photoluminescence spectra test result, each sample occurs near 470nm under excitation wavelength One stronger glow peak, and N doping Cu₂The purer Cu of luminous peak intensity of O material₂O is weak, illustrates that N adulterates Cu₂After O, it can promote Make efficiently separating for photo-generated carrier (light induced electron and photohole), to improve its photocatalytic activity；

3, in the present invention, when N is doped to Cu₂After O semiconductor material, the intensity of diffraction maximum can be clearly observed It reduces, and there are widthization phenomenons, and then explain the incorporation of nitrogen, can reduce Cu₂The crystallization degree of O, the sample that nitrating is 0.8% The average grain diameter of product is 15.7nm, distortion coefficient of crystal lattice 0.1951, the Cu that nitrating is 1.6%₂The average grain diameter of O is 15.1nm, distortion coefficient of crystal lattice 0.2036.This is because N mixes Cu₂After O, the position of N substitution O causes Cu₂O distortion of lattice and Affect the crystallization behavior of material；

4, in the present invention, Cu₂Suitable foreign ion is mixed in O catalysis material can be improved the separation of photo-generated carrier Effect improves its photocatalysis effect to reduce the photo-generate electron-hole recombination rate of Cu2O material surface, and excessively mixes Miscellaneous foreign ion can also become the complex centre of photo-generate electron-hole in a suitable case, once Cu₂O material surface is answered Conjunction rate increases, and carrier will be obstructed to the transmit process at interface, inhibits Cu instead₂The photocatalysis performance of O；

5, in the present invention, after materials'use 7 times, the percent of decolourization of methyl orange is declined, by 94.7% original drop To 73.9%, and TOC removal rate also drops to 58.5% by original 75.6%, but still maintains certain photocatalytic activity, because This has good reusability.

Detailed description of the invention

In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this A little attached drawings obtain other relevant attached drawings.

Fig. 1 is sample UV-Vis DRS spectrogram；

Fig. 2 is sample photoluminescence spectra figure；

Fig. 3 is sample F T-IR spectrogram；

Fig. 4 is sample XRD diagram；

The SEM that Fig. 5 is N doping Cu2O schemes；

Fig. 6 is the SEM grain size distribution of N doping Cu2O；

Fig. 7 is the EDX element spectrogram of N doping Cu2O；

Fig. 8 is sample XPS spectrum figure；

Fig. 9 is influence diagram of the itrogen content of getter with nitrogen doped to percent of decolourization；

Figure 10 is influence diagram of the itrogen content of getter with nitrogen doped to TOC removal rate；

Figure 11 is influence diagram of the dosage to percent of decolourization；

Figure 12 is influence diagram of the dosage to TOC removal rate；

Figure 13 is influence diagram of the initial concentration to percent of decolourization；

Figure 14 is influence diagram of the initial concentration to TOC removal rate；

Figure 15 is that material circulation uses the influence diagram to percent of decolourization and TOC removal rate；

Figure 16 is visible light catalytic kinetics matched curve figure.

Specific embodiment

In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not For limiting the present invention, i.e., described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is logical The component for the embodiment of the present invention being often described and illustrated herein in the accompanying drawings can be arranged and be designed with a variety of different configurations.

Therefore, the detailed description of the embodiment of the present invention provided in the accompanying drawings is not intended to limit below claimed The scope of the present invention, but be merely representative of selected embodiment of the invention.Based on the embodiment of the present invention, those skilled in the art Member's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.

It should be noted that the relational terms of term " first " and " second " or the like be used merely to an entity or Operation is distinguished with another entity or operation, and without necessarily requiring or implying between these entities or operation, there are any This actual relationship or sequence.Moreover, the terms "include", "comprise" or its any other variant be intended to it is non-exclusive Property include so that include a series of elements process, method, article or equipment not only include those elements, but also Further include other elements that are not explicitly listed, or further include for this process, method, article or equipment it is intrinsic Element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that including described There is also other identical elements in the process, method, article or equipment of element.

Feature and performance of the invention are described in further detail with reference to embodiments.

Embodiment 1

A kind of N doping cuprous oxide catalysis material and preparation method thereof that present pre-ferred embodiments provide.The light is urged Change material preparation method the following steps are included: to 50mL 0.1mol/L CuSO₄·5H₂0.4ml0.01mol/L is added in O solution CO(NH₂)₂, it is uniformly mixed using magnetic stirrer；10mL 1mol/L NaOH is added, continues to stir, solution is by blue Become blue-green flocculent deposit, until becoming blackish green precipitating；Add 5mL 1mol/L N₂H₄·H₂O is restored, magnetic force Blender stirs lower solution and quickly becomes light green color, then becomes yellow green, continues stirring until solution becomes rufous completely Suspension；It filters and washs precipitating, precipitating is dried under nitrogen protection, it is polished to get product.

Embodiment 2

A kind of N doping cuprous oxide catalysis material and preparation method thereof that present pre-ferred embodiments provide.The light is urged Change material preparation method the following steps are included: to 50mL 0.1mol/L CuSO₄·5H₂0.8ml0.01mol/L is added in O solution CO(NH₂)₂, it is uniformly mixed using magnetic stirrer；10mL 1mol/L NaOH is added, continues to stir, solution is by blue Become blue-green flocculent deposit, until becoming blackish green precipitating；Add 5mL 1mol/L N₂H₄·H₂O is restored, magnetic force Blender stirs lower solution and quickly becomes light green color, then becomes yellow green, continues stirring until solution becomes rufous completely Suspension；It filters and washs precipitating, precipitating is dried under nitrogen protection, it is polished to get product.

Embodiment 3

A kind of N doping cuprous oxide catalysis material and preparation method thereof that present pre-ferred embodiments provide.The light is urged Change material preparation method the following steps are included: to 50mL 0.1mol/L CuSO₄·5H₂1.4ml0.01mol/L is added in O solution CO(NH₂)₂, it is uniformly mixed using magnetic stirrer；10mL 1mol/L NaOH is added, continues to stir, solution is by blue Become blue-green flocculent deposit, until becoming blackish green precipitating；Add 5mL 1mol/L N₂H₄·H₂O is restored, magnetic force Blender stirs lower solution and quickly becomes light green color, then becomes yellow green, continues stirring until solution becomes rufous completely Suspension；It filters and washs precipitating, precipitating is dried under nitrogen protection, it is polished to get product.

Embodiment 4

A kind of N doping cuprous oxide catalysis material and preparation method thereof that present pre-ferred embodiments provide.The light is urged Change material preparation method the following steps are included: to 50mL 0.1mol/L CuSO₄·5H₂1.6ml0.01mol/L is added in O solution CO(NH₂)₂, it is uniformly mixed using magnetic stirrer；10mL 1mol/L NaOH is added, continues to stir, solution is by blue Become blue-green flocculent deposit, until becoming blackish green precipitating；Add 5mL 1mol/L N₂H₄·H₂O is restored, magnetic force Blender stirs lower solution and quickly becomes light green color, then becomes yellow green, continues stirring until solution becomes rufous completely Suspension；It filters and washs precipitating, precipitating is dried under nitrogen protection, it is polished to get product.

Embodiment 5

A kind of N doping cuprous oxide catalysis material and preparation method thereof that present pre-ferred embodiments provide.The light is urged Change material preparation method the following steps are included: to 50mL 0.1mol/L CuSO₄·5H₂2.6ml0.01mol/L is added in O solution CO(NH₂)₂, it is uniformly mixed using magnetic stirrer；10mL 1mol/L NaOH is added, continues to stir, solution is by blue Become blue-green flocculent deposit, until becoming blackish green precipitating；Add 5mL 1mol/L N₂H₄·H₂O is restored, magnetic force Blender stirs lower solution and quickly becomes light green color, then becomes yellow green, continues stirring until solution becomes rufous completely Suspension；It filters and washs precipitating, precipitating is dried under nitrogen protection, it is polished to get product.

Experimental example 1

As photochemical catalyst, the optical absorptive character of efficient wide-spectrum is the non-abundant item of a necessity for guaranteeing photocatalytic activity Part, therefore the optical absorptive character for analyzing solid photocatalysts is essential.Uv-visible absorption spectra is when wavelength is After the light irradiation material of 200~800nm, the molecular absorption spectrum of the electron transition generation in sample molecule.Ultraviolet-ray visible absorbing Spectra methods is usually used in analyzing inorganic matter, the molecular composition of organic matter, content and molecular structure.

Respectively to pure Cu₂Nitrating Cu made from O and embodiment 1-5₂O carries out UV-Vis DRS characterization, wherein by embodiment Sample made from 1-5 is denoted as NC0.8, NC1.6, NC2.8, NC3.2 and NC5.2 respectively, as a result as shown in Figure 1.

The pure Cu known to Fig. 1,2₂O has very strong absorption, N doping Cu to the visible light between 500~600nm₂The absorption of O Apparent blue shift has occurred in sideband, and is also enhanced the absorption of the light of 400~500nm range, illustrates that N doping can Lead to Cu₂The forbidden bandwidth of O increases.

Experimental example 2

Photoluminescence spectra is a kind of self-excitation phenomenon that material itself is originated from light radiation, comes from insulated with material Electronic state exciton excitation and defect excitation can be observed, photoluminescence spectra spectrum feature can reflect material surface, The information such as impurity level and defect level.

Respectively to pure Cu₂Nitrating Cu made from O and embodiment 1-5₂O carries out photoluminescence spectra test, wherein by implementing Sample made from example 1-5 is denoted as NC0.8, NC1.6, NC2.8, NC3.2 and NC5.2 respectively, as a result as shown in Figure 2.

Fig. 2 is it is found that a stronger glow peak, and N doping occurs near 470nm in each sample under excitation wavelength Cu₂The purer Cu of luminous peak intensity of O material₂O is weak.Under the conditions of identical exciting light, its relatively weaker crystal of the intensity of glow peak is lacked It falls into state level to be relatively low, illustrates that N adulterates Cu₂After O, having for photo-generated carrier (light induced electron and photohole) can be promoted Effect separation, to improve its photocatalytic activity.

Experimental example 3

Infrared spectroscopy is usually used in the surface micro-structure analysis of catalysis material.It is modified by comparative analysis modifying agent and surface The infrared spectroscopy difference of catalysis material, judges the bonding situation of modifying agent Yu catalysis material surface.Infrared spectroscopy is to utilize A kind of spectrum that molecular vibration is analyzed, using the Infrared irradiation measured object of specific frequency, when in the molecule of measured object When special groups vibration frequency is identical as the frequency of light, measured object is absorbed by infrared light, so that the molecule in measured object Excitation state is transitted to from vibration ground state, is depicted as a curve according to the percentage transmission data of the infrared light of instrument record, i.e., For infrared spectroscopy.Solid photocatalysts are researched and analysed, frequently with the hydroxyl state of infrared spectrum analysis measurement sample surfaces.

Respectively to pure Cu₂Nitrating Cu made from O and embodiment 1-5₂O carries out ftir analysis, wherein The sample as made from embodiment 1-5 is denoted as NC0.8, NC1.6, NC2.8, NC3.2 and NC5.2 respectively, as a result as shown in Figure 3.

Fig. 3 is it is found that pure Cu₂There is characteristic absorption peak, nitrating Cu between 500-750cm-1 in O₂O respectively 3250~ 3500cm^-1, 1500-1750cm^-1, 1000-1250cm^-1, 750-1000cm^-1There is absorption peak；Wherein 3250-3500cm^-1It is special The stretching vibration peak that absorption peak is O-H key is levied, Cu can be construed to₂What the hydrone stretching vibration on O catalysis material surface generated； 1500-1750cm^-1Peak occur is to be hydrated the N-H key stretching vibration peak generated after hydrazine reaction；1000-1250cm^-1Absorption peak be Caused by N-Cu key stretching vibration；750-1000cm^-1Characteristic absorption peak can be construed to the stretching vibration peak between Cu-N-O production Raw.

Experimental example 4

X-ray diffraction (X-ray diffraction, XRD) analysis, is the X-ray diffraction effect based on Polycrystalline, right The existing forms of each component and phase structure carry out analysis method for measuring in sample, can measure the phase structure of material, point Analyse purity and the grain size etc. of sample.X-ray energy is higher, can expose to the atom in crystal, the elastic scattering of generation Diffraction occurs after interfering between wave again, the intensity and peak position of diffraction maximum and the atom composition and arrangement mode of sample have very Important Relations.Therefore by instrument record diffraction data, compared with standard diagram data, according to the diffraction maximum position of sample and Intensity may determine that the purity and grain size of sample.XRD characterization means have objectivity and higher confidence level, urge in solid Key player is acted as in terms of the characterization of agent, is one of most common method.

Respectively to pure Cu₂Nitrating Cu made from O and embodiment 1,2₂O carry out X-ray diffraction analysis, wherein by embodiment 1, Sample made from 2 is denoted as NC0.8, NC1.6 respectively, as a result as shown in Figure 4.

Fig. 4 is it is found that Cu₂The characteristic peak of O and standard pdf card are almost the same, and peak shape is sharp, Cu or CuO do not occur Diffraction maximum；And when N is doped to Cu₂After O semiconductor material, the strength reduction of diffraction maximum can be clearly observed, and There are widthization phenomenons, and then explain the incorporation of nitrogen, can reduce Cu₂The crystallization degree of O；In addition after nitrating, occur CuO's Diffraction maximum, one the possible reason is the Cu that surface is grown in drying process₂O is further oxided as CuO under drying temperature. By Cu is calculated₂The average grain diameter of O is 28nm, distortion coefficient of crystal lattice 0.1098；When drying temperature is 80 DEG C, nitrating is The average grain diameter of 0.8% sample is 15.7nm, distortion coefficient of crystal lattice 0.1951, the Cu that nitrating is 1.6%₂The average grain of O Diameter is 15.1nm, distortion coefficient of crystal lattice 0.2036.This is because N mixes Cu₂After O, the position of N substitution O causes Cu₂O lattice is abnormal Become and affect the crystallization behavior of material.

Experimental example 5

The performance and granular size and shape characteristic of photochemical catalyst have important relationship, to nano-photocatalyst pattern The directly observation of (geometrical morphology, granularity and distribution of particle sizes) is extremely important.Scanning electron microscope (Scanning Electron Microscope, SEM) in terms of Analysis of Surface Topography, take on key player and more commonly used characterization One of means.In general, the magnification at high multiple photo of the microscopic appearance of sample surfaces needs the electronics by energy high concentration in sample Surface is scanned.After entering sample surfaces with the electronics of 0.5~30eV energy, will diffraction go out the two of many low energy Secondary electronics, the intensity of these secondary electrons and the shape characteristic of sample surfaces have much relations, and the acquisition of micrograph is exactly logical The intensity and different location of secondary electron, variation relation between the two is simulated by function in overwriting scanning area.By It is fairly simple in requirement of the scanning electron microscope to sample pre-treatments, generally for powder sample sample stage can be attached on conducting resinl On tested, and solid, bulk sample then can be tested directly.However photochemical catalyst belongs to semiconductor, conductive difference Characteristic, it is not clear enough to may cause image directly test, general Xu will by way of vacuum evaporation or ion sputtering Surface coats layer of Au film, to enhance its electric conductivity, is more clear the image of test.The preferable electric conductivity of sample can be with Inhibit being emerged for the accumulation of specimen surface charge, overheat or hot spot, increase the yield of secondary electron, improve the signal-to-noise ratio of image, Clearly SEM is obtained to scheme.In addition after basic electronics is converted to secondary electron, scattered electron and X-ray after also generating simultaneously.Afterwards The intensity of scattered electron is related with the composition element atomic number of sample, and the X-ray released by analysis, can be had Close the information of element atomic number.Therefore SEM usually has EDX power spectrum attachment, can tentatively carry out surface by gamma-spectrometric data Analysis determines element composition and the distribution of sample surfaces.

To nitrating Cu made from embodiment 2₂O is denoted as NC1.6, has gone Flied emission electron-microscope scanning, as a result such as Fig. 5,6,7.

It is a little to be irregular spherical by the SEM figure of sample it can be seen that octahedral structure is presented in sample particle mostly, partial size It is distributed in 50~700nm, and the partial size of most particles is in 400nm or less.The constituent content such as following table of sample surfaces is measured by EDX 3-1, the results showed that sample surfaces are made of element O, Cu in test zone, and mass fraction accounts for 19.7%, Cu for O and accounts for 80.3%, Atomicity accounting accounts for 49.35%, Cu for O and accounts for 50.65%.This ratio is higher than Cu₂The element ratio of O and Cu in O, explanation The O of sample surfaces is in addition to deriving from Cu₂O, it is also possible to from the molecular oxygen and hydroxyl oxygen of sample surfaces absorption.

1 EDX of table measures sample surfaces constituent content

Experimental example 6

X-ray photoelectron spectroscopy (XPS) is a kind of surface analysis technique of high sensitivity, investigation depth is generally 4~ The surface information of 15nm is the effective means of the physical property such as element composition and the chemical form on study sample surface.The test base of XPS In photo-ionisation action principle, one timing of incident X-ray energy in testing can be in the hope of by the kinetic energy of measurement work function and electronics The combination energy of electronics out generallys use the X-ray of higher-energy as excitaton source, while inspiring valence electron in atom valence orbit With the inner orbital electrons on fermi level.Because the photoelectronic energy generated in excitation process only with the type of element and institute The atomic orbital of excitation is related, according to photoelectronic combination can qualitative analysis compound element species, according to Pu Feng Intensity can carry out semi-quantitative analysis, but be only a kind of relative amount of surface composition, quantitative in catalysis material analysis Analysis is only used as a kind of reference.The electron binding energy of another aspect fermi level in different chemical environments there are fine difference, Referred to as chemical shift.In general, chemical valence state becomes negative valency after element obtains extra electron, then element binding energy is just It can reduce；Conversely, after element loses electronics, valence state becomes just, in conjunction with can also will increase.General apparent charge changes 2~3 Unit, chemical shift are 2~4eV, and oxidizability changes 1 unit, causes the chemical shift of about 1eV.Utilize this combination energy Fine difference analyzes element existence form in the sample and chemical valence, this is the important component of XPS analysis.

To nitrating Cu made from embodiment 2₂O has carried out x-ray photoelectron spectroscopy test, and Fig. 8 is the xps energy spectrum of sample.

Fig. 8 is it is found that sample surfaces are primarily present this five kinds of elements of Cu, O, N, C, S.Bond material prepares raw material and above-mentioned point Analysis, it can be determined that Cu and O element derives from Cu₂O and CuO；N element is mainly derived from urea；C element is in addition to additional standard solid Outside carbon source, it is also possible to derive from urea；S element should be then by raw material CuSO₄It introduces.

Experimental example 7

It is arranged pure Cu₂Nitrating Cu made from O group, embodiment 1-5₂O group, totally 6 sample sets, in 50ml methyl orange solution Light source is done with tungsten halogen lamp in (40mg/L) and is photocatalytic degradation experiment 3h, its percent of decolourization and TOC is measured by sampling every half hour Removal rate.Wherein, the sample as made from embodiment 1-5 is denoted as NC0.8, NC1.6, NC2.8, NC3.2 and NC5.2 respectively, as a result As shown in Figure 3,4.Use power for 500W, wavelength is the tungsten halogen lamp of 400~700nm as visible light source.When experiment, with first Base orange is added in interlayer cylindrical glass reactor, is passed through in laminated glass in light reaction procedure cold as target degradation product Condensate, so that the temperature of reaction solution keeps homeostasis.Specific steps are as follows: the certain density methyl orange solution of 50mL is placed in reactor In, 0.04g catalyst sample is added, magnetic agitation constitutes suspension system, opens light source after being protected from light stirring 1h, reacts every certain Time sampling takes filtrate after being filtered with 0.45 micron membrane filter.

As can be seen that the N of NC1.6 adulterates Cu from Fig. 9 and Figure 10₂O photocatalysis effect is best, its percent of decolourization when 90min It has had reached 90.3%, 3h rear decoloring rate and has reached 94.8%；The catalyst percent of decolourization of NC3.2 and NC5.2, it is urged when 90min Changing effect is 82.5.NC1.6 be also to the removal rate of TOC it is best, 2h removal rate be 75.9%, NC3.2 to TOC removal rate also compared with It is high.Comprehensive percent of decolourization and the curve map analysis of TOC removal rate, itrogen content of getter with nitrogen doped are higher or lower than 1.6, and catalytic effect is all declined. Cu₂Suitable foreign ion is mixed in O catalysis material can be improved the separating effect of photo-generated carrier, to reduce Cu2O material The photo-generate electron-hole recombination rate for expecting surface improves its photocatalysis effect, and excessively impurity ion is in suitable feelings Also it can become the complex centre of photo-generate electron-hole under condition, once Cu₂The recombination rate of O material surface increases, and carrier is to interface Transmit process will be obstructed, inhibit Cu instead₂The photocatalysis performance of O.

Experimental example 8

It is arranged nitrating Cu made from embodiment 2₂O group catalysis material by 0.206,0.416,0.804,1.608,3.198, The concentration of 6.406g/L is added in 50ml methyl orange solution (40mg/L), is done light source with tungsten halogen lamp and is carried out photocatalytic degradation experiment Its percent of decolourization and TOC removal rate is measured by sampling every 30min in 3h.As a result such as Figure 11 and Figure 12.

From in Figure 11 and Figure 12 as can be seen that 90min before 0.416g/L dosage under decolorizing effect it is best, Zhi Houshi The percent of decolourization of 0.804g/L is best, but difference is little compared with the percent of decolourization of 0.416g/L.As can be seen from the figure TOC removal effect Fruit 0.416g/L and 0.804g/L is not much different, and TOC removal rate is more slightly higher under 0.416g/L dosage.And 0.206g/L is added It measures percent of decolourization and TOC removal rate is all worst.When catalyst amounts are less, the photon energy that light source generates cannot abundant quilt It utilizes, reaction speed is slower, and photocatalysis effect is significantly lower than other when dosage is 0.206g/L.After increasing dosage, with N Adulterate Cu₂The degradation rate of the increase methyl orange of O catalyst reduces.This phenomenon explains N doping Cu₂The excessive throwing of O catalysis material Add, it is excessively high to will lead to molecules in solution density, generates overlapping, serious light scattering phenomenon can be also generated, to reduce effective light By force.In degradation process, the N in middle layer solution and bottom solution adulterates Cu₂O catalysis material cannot effectively utilize visible light, make It is ineffective to obtain catalytic process.Therefore final choice 0.416g/L is optimum dosage.

Experimental example 9

Be respectively 10 to concentration, 20,30,40,50mg/L methyl orange solution carries out in the case where not changing other conditions Photocatalytic degradation experiment.As a result such as Figure 13 and Figure 14.

It can be seen from the figure that methyl orange solution percent of decolourization and TOC removal rate that initial concentration is 40mg/L are better than other Concentration, percent of decolourization tends towards stability with TOC removal rate when 2h, and respectively reaches 91.7%, and 66.3%.With the increasing of initial concentration Add, percent of decolourization is significantly raised, maximum value occurs when reaching 40mg/L, continues growing initial concentration, percent of decolourization is declined again. TOC removal rate is to increase sharply after 20mg/L TOC removal rate reduces in concentration, in 40mg/L with the raising of initial concentration Downward trend is presented again after there is maximum value.When methyl orange solution concentration is lower, the reaction molecular in solution is difficult to spread Cu is adulterated to N₂The surface of O catalysis material reacts, and when concentration continues to be increased in OK range, N adulterates Cu₂O material Catalytic effect is best, and with initial concentration increases again, and methyl orange solution darkens after reaction molecular excess, solution it is saturating Photosensitiveness is deteriorated, and N adulterates Cu₂The photon numbers that O catalysis material can utilize reduce, and percent of decolourization also declines therewith.In summary it analyzes, The optimal initial concentration for determining methyl orange solution is 40mg/L.

Experimental example 10

Catalyst circulation is used 7 times.By the material after using by filtering with microporous membrane recycle, and with dehydrated alcohol, Deionized water is washed for several times, and natural drying in drier is put into, and is carried out repeating experiment, is obtained Figure 15.

It can be seen from the figure that being declined to the percent of decolourization of methyl orange, after materials'use 7 times by original 94.7% drops to 73.9%, and TOC removal rate also drops to 58.5% by original 75.6%, and catalyst still maintains certain light Catalytic activity.Catalyst inactivation has several reasons, and the intermediate product or final product that photocatalysis generates are deposited on catalyst surface, or The absorption property of intermediate product causes competitive Adsorption better than reactant, reduces concentration of substrate, consumes living radical, or even Catalyst particles are after prolonged use in suspension, and crystallite particles polymerization causes catalyst size to become larger, specific surface The reasons such as product reduction, which all will lead to, leads to catalyst activity reduction or inactivation.

Experimental example 11

N adulterates Cu₂O, which passes through false First order dynamic model to the Photocatalytic Degradation Process of different initial concentration methyl oranges, to carry out Description.As a result as shown in figure 16.The apparent reaction rate constant and linear phase under different initial concentrations are obtained using linear fit Relationship number such as table 2.

The false first order kinetics parameter of the different initial concentrations of table 2

It can be seen from the figure that N adulterates Cu₂Degradation of the O catalysis material to the Methyl Orange in Wastewater of different initial concentrations Good (the R of linear relationship between Cheng Zhong, ln (C0/Ct) and reaction time t²0.95 or more).As shown in Table 2, work as methyl orange When initial concentration increases to 40mg/L by 10mg/L, the observed rate constant of reaction has with the increase of methyl orange initial concentration Increased, apparent reaction rate constant is but declined slightly when continuing to increase to 50mg/L.Because the catalysis on catalyst material is living Property centre concentration it is lower when, reactant molecule catalyst surface adsorb not yet reach saturation state, therefore reaction rate with react Object initial concentration is positively correlated.When concentration increases, dyestuff reaches saturation in the absorption of catalyst surface, so that reaction rate is normal Number reduces.

The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (5)

1. a kind of preparation method of N doping cuprous oxide catalysis material, which comprises the following steps:

S1. to CuSO₄·5H₂CO (NH is added in O solution₂)₂, it is uniformly mixed；

S2. it obtains that NaOH is added in mixed liquor into step S1, stirs, until becoming blackish green precipitating；

S3. N is added into blackish green precipitating obtained in step S2₂H₄·H₂O, stirring until become rufous suspension completely；

S4. suspension obtained in step S3 is filtered, then precipitating is washed；

S5. precipitating obtained in step S4 is dried, grinding obtains finished product.

2. the preparation method of N doping cuprous oxide catalysis material according to claim 1, it is characterised in that: described CuSO₄·5H₂O、CO(NH₂)₂, NaOH and N₂H₄·H₂The molar ratio of O is 4.5-5.5:0.002-0.028:8-12:3-8.

3. the preparation method of N doping cuprous oxide catalysis material according to claim 2, it is characterised in that: described CuSO₄·5H₂O、CO(NH₂)₂, NaOH and N₂H₄·H₂The molar ratio of O is 5.0:0.016:10:5.

4. the preparation method of N doping cuprous oxide catalysis material according to claim 1, it is characterised in that: the S5 Drying process is to be dried under nitrogen protection in step.

5. the N doping cuprous oxide catalysis material prepared by any one of claim 1-4 the method.