CN110272115A - Cu-Ce-Y spherical hollow space composite material and preparation method and application - Google Patents
Cu-Ce-Y spherical hollow space composite material and preparation method and application Download PDFInfo
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- CN110272115A CN110272115A CN201910702666.4A CN201910702666A CN110272115A CN 110272115 A CN110272115 A CN 110272115A CN 201910702666 A CN201910702666 A CN 201910702666A CN 110272115 A CN110272115 A CN 110272115A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
Abstract
The invention discloses a kind of Cu-Ce-Y spherical hollow space composite material and preparation method and applications, Cu-Ce-Y spherical hollow space composite material is by coating PVP on the outside of carbosphere template, a small amount of nanometer Y crystal seed is adhered to the outer surface of CSs@PVP, presoma CSs@PVP@Y is made, presoma CSs@PVP@Y is added in Y gel, spherical hollow space Y molecular sieve is obtained by crystallization, roasting, passes through rear infusion process Supported CuO and CeO by carrier of spherical hollow space Y molecular sieve2It obtains.By the way that cathode material for hydrogen evolution is made in Cu-Ce-Y spherical hollow space composite material drop coating on carbon paper.The present invention combines the characteristic advantage of soft or hard template to synthesize the Y molecular sieve with spherical hollow space structure, and is prepared for Cu-Ce-Y spherical hollow space composite material by rear infusion process, has and is applied to performance similar in noble metal liberation of hydrogen material in microorganism electrolysis cell.
Description
Technical field
The invention belongs to electro-catalysis technical fields, are related to the synthesis and application of a kind of electro-catalysis presoma, more particularly to
A kind of Cu-Ce-Y spherical hollow space composite material and preparation method and application.
Background technique
With traditional energy exhaustion and worsening ecological environment, the mankind will face pair of energy shortage and environmental pollution
Weight severe challenge.And relative to traditional energy, Hydrogen Energy energy density highest (H in various new energy2For 120MJ/kg, gasoline
For 44MJ/kg, CH4For 50MJ/kg, ethyl alcohol 26.8MJ/kg), and clean and environmental protection, it is a kind of important energy carrier.Hydrogen
There can be huge development potentiality in cleaning, sustainable energy technology field.
Microorganism electrolysis cell (microbial electrolysis cell MEC) be a kind of novel pollutant process and
The device of energy regenerating can recycle electric energy or Hydrogen Energy while handling organic wastewater, be one have preferably application before
The new technology of scape.MEC anode microorganism decomposition organic matter generates electronics and proton, and electronics reaches cathode, proton by external circuit
Cathodic region is reached by solution, outside plus under boost voltage, the two combines generation hydrogen.Hydrogen is produced using MEC biomass, maximum can
Obtain 300% ~ 400% energy yield.The evolving hydrogen reaction of MEC occurs in cathode chamber, the selection of cathode basic material and catalyst
Determine the height of evolving hydrogen reaction efficiency.Currently, Pt/C base catalyst is best catalyst (Molybdenum carbide-
carbon nanocomposites synthesized from a reactive template for
electrochemical hydrogen evolution[J]. Journal of Materials Chemistry A,
2014,2 (27): 10548-10556, Highly active and durable nanostructured molybdenum
carbide electrocatalysts for hydrogen production[J]. Energy & Environmental Science, 2013,6 (3): 943-951.), but higher cost is that it uses maximum limiting factor.Therefore, cheap gold
The exploitation of metal catalyst is most important for the sustainable development of MEC.
Y molecular sieve is a kind of porous crystalline material, has flourishing three-dimensional open-framework and higher specific surface area, bone
Frame silica alumina ratio, acidity, pore structure and ion-exchange performance are able to carry out modulation in a big way, and manufacturing cost is relatively
It is low, it has a clear superiority using it as MEC cathode carrier material.But the crystallite dimension of conventional Y molecular sieve is at 1 μm or more, and
The unit cell size of Y molecular sieve is mostly in 1~2.5 nm, this makes, and crystal pores road length, transgranular resistance be big, micropore diffusion low efficiency,
Cause inner hole that can not be fully utilized, reduces the effective rate of utilization of molecular sieve.
There is the spherical hollow space Y molecular sieve of cross-linked structure using the inside of soft or hard Template synthesis, it is special to have
Steric configuration and biggish specific surface area provide place for the selective catalysis of Y molecular sieve, meanwhile, this special cavity
Structure is conducive to promote effective dispersion of the metal component in carrier surface and duct, can also expose more active sites, be
The combination of MEC cathode Hydrogen Proton and electronics provides bigger reaction compartment.Secondly, its micro- mesoporous hierarchical porous structure for having, makes
It obtains the hydrogen molecule that cathode generates to be easier to desorb and spread, the liberation of hydrogen ability of cathode can be greatly improved.
King such as changes at (the preparation of nano NiO-Y composite cathode material and in microorganism electrolysis cell catalysis H2-producing capacity [J] combustion
Expect chemical journal, 2019,47 (6), 762-768.) addition carbosphere has synthesized nanometer Y points in no directed agents synthetic system
Son sieve, in its area load metal oxide (NiO) by way of incipient impregnation, has prepared NiO-Y nanometers of support type
Composite material, the sample of synthesis have high specific surface area and pore volume.The material is used for MEC cathode material, it is with higher
Hydrogen evolution activity, however, redox property is lower since its active component is single.
Copper oxide is a kind of diamagnetism p-type semiconductor, is represented as transition metal oxide, is had in liberation of hydrogen catalysis reaction
There is certain Hydrogen Evolution Performance, but the electric conductivity of copper oxide itself is poor, needs to carry out necessary improvement and be just able to satisfy as cathode
The needs of material.CuO-CeO2Composite material is a kind of new catalyst, and studies have shown that copper oxide and cerium oxide have to each other
Strong active force makes it have excellent catalytic activity, but since the active site of metal composite oxide exposure is few, unfavorable
In the progress of evolving hydrogen reaction.
Summary of the invention
In order to solve the problems, such as existing conventional Y molecular sieve and MEC development, the invention discloses a kind of Cu-Ce-Y
Spherical hollow space composite material and preparation method and application have synthesized spherical hollow space Y molecule in conjunction with the characteristic advantage of soft or hard template
Sieve, and is prepared for Cu-Ce-Y spherical hollow space composite material by rear infusion process, by by Cu-Ce-Y spherical hollow space composite material
Cathode material for hydrogen evolution is made in drop coating on carbon paper, has and is applied to property similar in noble metal liberation of hydrogen material in microorganism electrolysis cell
Energy.
The technical scheme of the present invention is realized as follows:
On the one hand, the invention discloses a kind of spherical hollow space Y molecular sieves to be made by the steps:
It (1) is Na according to molar ratio using deionized water, sodium hydroxide, sodium metaaluminate, white carbon black as raw material2O:Al2O3: SiO2:
H2O=(0.1 ~ 0.6): (1 ~ 4): (0.3 ~ 1.2): 100 mixing are successively stirred 15 ~ 28h at 20 ~ 30 DEG C, are stirred at 40 ~ 50 DEG C
20 ~ 28h, 10 ~ 14h is stirred at 55 ~ 65 DEG C, obtain Y gel；Then Y gel is put into reaction kettle and is sealed, it is quiet at 90 ± 5 DEG C
After state crystallization 4 ~ for 24 hours, by the product after crystallization through chilling, washing, filtering, 65 ~ 75 DEG C of 10 ~ 15 h of drying, a nanometer Y is obtained
Molecular sieve；
(2) into deionized water, successively carbosphere, PVP, ammonium hydroxide and dehydrated alcohol is added in interval, stirs to get A liquid；Wherein, PVP
Mass ratio with carbosphere is 1:(5 ~ 8)；Carbosphere and the mass ratio of deionized water are 1:(12 ~ 18), deionized water, ethyl alcohol and
The volume ratio of ammonium hydroxide is (32 ~ 38): (26 ~ 34): 1；Ammonium hydroxide and dehydrated alcohol can be improved the dispersibility of carbosphere；
(3) at room temperature, the spherical hollow space Y molecular sieve that step (1) obtains is added into deionized water, obtains white " milky " B liquid, is
Quickening dissolution process, can accelerate to dissolve by the way of ultrasonic vibration；
(4) B liquid is added dropwise in A liquid, at 65 ~ 75 DEG C stir 5 ~ 7h after, washing, then at 65 ~ 75 DEG C drying 10 ~
14h obtains the presoma CSs@PVP@Y of black；The volume ratio of A liquid and B liquid is (5 ~ 10): 1；B drop preferably exists after being added to A liquid
It is stirred in the case where sealing；
(5) the Y gel obtained presoma CSs@PVP@Y and step (1) is agitated, 90 ± 5 DEG C of static crystallizations, washing, drying,
Then grinding roasts 5 ~ 7h at 530 ~ 570 DEG C, obtain having internal crosslinking netted spherical Y molecular sieve；Preferably, Y is solidifying
The mass ratio of glue and presoma CSs@PVP@Y are (12 ~ 36): 1.
As a preferred implementation manner, in step (1), by raw material according to molar ratio be Na2O:Al2O3: SiO2: H2O=
(0.2 ~ 0.4): (1.5 ~ 3): (0.5 ~ 0.9): 100 mixing are successively stirred at 25 DEG C for 24 hours, stir for 24 hours, at 60 DEG C at 45 DEG C
12h is stirred, Y gel is obtained；Then by Y gel after 90 ± 5 DEG C of static crystallizations react 12h, by product through chilling, washing, mistake
Filter, 70 DEG C of 12 h of drying, obtain a nanometer Y molecular sieve.
Preferably, in step (2), carbosphere, PVP is added into deionized water and is stirred at room temperature 0.75 ~ 1.5h, then according to
Secondary addition ammonium hydroxide and ethyl alcohol continue to stir 6h at 65 ~ 75 DEG C, obtain A liquid；Wherein, the mass ratio 1:(6 of PVP and carbosphere ~
7), mass volume ratio 1:(14 ~ 16 of carbosphere and deionized water), the volume ratio of deionized water, ethyl alcohol and ammonium hydroxide be (33 ~
37): (28 ~ 32): 1.
Preferably, the mass ratio of nanometer Y molecular sieve and deionized water is 1:10 in step (3) of the present invention.
The raw material carbosphere for being used to prepare spherical hollow space Y molecular sieve of the present invention preferably uses glucose hydro-thermal carbonizatin method to synthesize,
Method disclosed in Li Saisai etc. " hydrothermal carbonization method prepares monodisperse carbosphere " is referred to be prepared.
After hydrothermal synthesis of carbon microballoon, PVP is coated on the outside of carbosphere template, is then adhered to a small amount of Y crystal seed
The outer surface of CSs@PVP is made presoma CSs@PVP@Y, presoma is added in Y gel, obtains ball by crystallization, roasting
Shape cavity Y molecular sieve, the average grain size of the spherical hollow space Y molecular sieve are 500 nm, have more small sky inside molecular sieve
Chamber is crosslinking shape between cavity, and pore size is mainly distributed on 3.8 nm or so and 8 ~ 10 nm or so, wherein 8 ~ 10 nm or so
Mesoporous gap mainly between cavity；The duct of 3.8 nm or so is mainly the gap between nanometer Y molecular sieve, supported catalyst
When agent, mesoporous presence is conducive to the high degree of dispersion and payload of metal component.
The present invention utilizes the special construction of spherical hollow space Y molecular sieve, then discloses one kind on spherical hollow space Y molecular sieve
Supported CuO-CeO2The novel C u-Ce-Y spherical hollow space composite material of active component, using rear Cu-Ce-Y ball prepared by infusion process
Shape cavity composite material exhibits go out remote super bare carbon paper (CP), the performance of the Pt/C cathode for the noble-metal-supported that matches in excellence or beauty.
The method of infusion process synthesis Cu-Ce-Y spherical hollow space composite material afterwards, is by spherical hollow space Y molecular sieve, Cu
(NO3)2·3H2O and Ce (NO3)3·6H2O is dissolved in deionized water, after 5 ~ 6h is stirred at room temperature, drying, then in 480 ~
5 ~ 7h is roasted at 560 DEG C obtains Cu-Ce-Y spherical hollow space composite material；Gained Cu-Ce-Y spherical hollow space composite material is by dividing
Dissipate carrier spherical hollow space Y molecular sieve and CuO-CeO2Active component composition, ball in the Cu-Ce-Y spherical hollow space composite material
The mass fraction of shape cavity Y molecular sieve is 75%, CuO-CeO2CeO in active component2Mass fraction be 28 ~ 52%.；Preferably,
CuO-CeO2CeO in active component2Mass fraction be 36%.
Cu-Ce-Y spherical hollow space composite material prepared by the present invention can be used as cathode material, be used to prepare microorganism electricity
The cathode electrode of Xie Chi, it is possible to further be used to handle waste water as cathode for hydrogen evolution electrode.
Specifically dispersing Cu-Ce-Y spherical hollow space composite material in dehydrated alcohol, drop coating is done in carbon paper surface
It is fixed after dry with Nafion solution, obtains the cathode material of microorganism electrolysis cell, it is preferable that use 0.02 wt%
The Cu-Ce-Y spherical hollow space composite material of carbon paper surface is fixed in Nafion solution, further, in the cathode material
The load capacity of Cu-Ce-Y spherical hollow space composite material is 0.5 ~ 1.5 mg/cm2。
The present invention combines the characteristic advantage of soft or hard template, first passes through the ageing of three steps and is aged to be formed using carbosphere as core again, PVP
For adhesive, nanometer Y molecular sieve is the core-shell structure of outer shell, is fired and has prepared internal crosslinking netted cavity structure
Spherical hollow space Y molecular sieve, be prepared for by rear infusion process by dispersible carrier spherical hollow space using spherical hollow space Y molecular sieve as carrier
Y molecular sieve and active component CuO-CeO2The Cu-Ce-Y spherical hollow space composite material of formation, so that metal component exposes more
Hydrogen evolution activity site, improve catalytic hydrogen evolution performance, by the way that Cu-Ce-Y spherical hollow space composite material drop coating is made on carbon paper
Cathode material for hydrogen evolution has and is applied to performance similar in noble metal liberation of hydrogen material in microorganism electrolysis cell.
Using spherical hollow space Y molecular sieve as CuO-CeO2Dispersible carrier so that metal component is well dispersed in spherical sky
The surface and duct of chamber molecular sieve expose more hydrogen evolution activity sites, thus during effectively reducing evolving hydrogen reaction
Activation energy promotes effective transmission of electronics, improves catalytic hydrogen evolution ability.Pass through linear scan and Tafel curve electro-chemical test
Evaluation has high electro-catalysis living using the microorganism electrolysis cell of cathode material made of Cu-Ce-Y spherical hollow space composite material
Property, within the continuous operation period, liberation of hydrogen current density, hydrogen output and hydrogen generation efficiency can mutually be equal to Pt/C cathode, and
It is much higher by CP cathode material, shows excellent catalytic hydrogen evolution performance.
The present invention uses cheap carbosphere as hard mould agent, and the advantage synthesizing spherical in conjunction with soft or hard template is empty
Chamber Y molecular sieve, and Cu-Ce-Y spherical hollow space composite material is synthesized by carrier of spherical hollow space Y molecular sieve, preparation method is simple
It is easy to operate and cheap, with the microorganism electrolysis cell cathode electrode of its preparation and include the noble metal electrode ratio including Pt/C
Compared with, significantly reduce cost, using load common metal electrode material be applied to microorganism electrolysis cell as liberation of hydrogen material, have
It hopes and noble metal is replaced to be applied to microorganism electrolysis cell as liberation of hydrogen material.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art
To obtain other drawings based on these drawings.
Fig. 1 is the XRD spectra of spherical hollow space Y molecular sieve in the embodiment of the present invention 1.
Fig. 2 is the SEM figure and spherical sky of nanometer Y molecular sieve in the embodiment of the present invention 1, carbosphere, spherical hollow space Y molecular sieve
The TEM of chamber Y molecular sieve schemes；Fig. 2 a is that the SEM of nanometer Y molecular sieve schemes, and Fig. 2 b is that the SEM of carbosphere schemes；Fig. 2 c is spherical hollow space Y
The SEM of molecular sieve schemes；2d is that the TEM of spherical hollow space Y molecular sieve schemes.
Fig. 3 is the N of spherical hollow space Y molecular sieve in the embodiment of the present invention 12Adsorption-desorption curve and graph of pore diameter distribution；Fig. 3 a
For the N of spherical hollow space Y molecular sieve2Adsorption-desorption figure；Fig. 3 b is spherical hollow space Y molecular sieve graph of pore diameter distribution.
Fig. 4 is the XRD spectra of Cu-Ce-Y spherical hollow space composite material in application examples 1.
Fig. 5 is SEM and the EDX figure of Cu-Ce-Y spherical hollow space composite material in application examples 1.
Fig. 6 is the linear scan figure of tri- kinds of Cu-Ce-Y spherical hollow space composite material, CP and Pt/C electrodes in application examples 1.
Fig. 7 is that Cu-Ce-Y spherical hollow space composite material, the Ta Feier of tri- kinds of cathode electrodes of CP and Pt/C are oblique in application examples 1
Rate.
Fig. 8 is Cu-Ce-Y spherical hollow space composite material, the gas production in tri- kinds of MEC each periods of CP and Pt/C in application examples 1
With gas constitutional diagram.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
35mL deionized water is added in polytetrafluoroethylcontainer container, 3.16g glucose stirs 30min at room temperature, is put into reaction kettle
In, it is closed, it is placed in insulating box, is heated to 180 DEG C of static crystallization reaction 12h.Reaction kettle is taken out, is quickly cooled down in quenching slot
To room temperature, reaction product is taken out, is washed 3 times with deionized water and dehydrated alcohol respectively, filtered, it is dry in 70 DEG C in vacuum oven
Dry 12h, grinding obtain carbosphere powder.
By 30mL deionized water, 2.33g sodium hydroxide, 1.99g sodium metaaluminate, 2.33g white carbon black, 0.2g sodium chloride is added
It into polytetrafluoroethylcontainer container, is stirred at room temperature to gel state, is then successively stirred at 25 DEG C for 24 hours, stir at 45 DEG C
For 24 hours, 12h is stirred at 60 DEG C, obtain Y gel, be put into reaction kettle and seal, react 12 h in 90 DEG C of static crystallizations；Take out reaction
Kettle is rapidly cooled to room temperature in quenching slot, is taken out reaction product, is washed 3 times with deionized water and dehydrated alcohol respectively, is taken out
Filter, in 70 DEG C of 12 h of drying in vacuum oven, obtains a nanometer Y molecular sieve.
1.25g carbosphere is added in 18 mL deionized waters, 0.2 g PV is continuously added, stirs 1 h at room temperature,
Then 0.5 mL ammonium hydroxide and 15 mL ethyl alcohol are sequentially added, in 70 DEG C of stirring 6h, obtains A liquid.
At room temperature, 0.5g nanometers of Y molecular sieves are added in 5 mL deionized waters, ultrasonic vibration 0.5h, obtain white cream
Shape B liquid.
5mL B liquid is added drop-wise to dropwise in 34mL A liquid, is sealed, in 70 DEG C of stirring 6h, is then washed with dehydrated alcohol centrifugation
It washs 3 times, in 70 DEG C of 12 h of drying in vacuum oven, obtains black presoma CSs@PVP@Y.
0.75g CSs@PVP@Y and 15 mL Y gels are added in polytetrafluoroethylcontainer container, 1 h is stirred at room temperature, it is close
Envelope, is put into autoclave, is placed in insulating box, reacts 12h in 90 DEG C of static crystallizations.Reaction kettle is taken out, is taken out with distilled water
It is ground after being dried at filter washing 3 times, 70 DEG C, then roasts 6 h at 550 DEG C in Muffle furnace, obtained with crosslinking net cavity knot
The spherical Y molecular sieve of structure.
Fig. 1 gives the XRD spectra of spherical hollow space Y molecular sieve, from map it can be seen that 2θFor 5.12o, 10.06o,
There are sharp diffraction maximum, these diffraction in 11.8o, 15.6o, 18.6o, 20.3o, 23.4o, 27.0o, 31.3o and 34.0o etc.
Peak respectively corresponds (111), (220), (311), (331), (511), (440), (533), (642), (555) of NaY molecular sieve
(664) crystal face is waited with Lv Y in Generalized synthesis of core-shell structured nano-
The diffraction maximum one for the spherical hollow space Y molecular sieve reported in zeolite@ordered mesoporous silica composites
It causes.The spherical hollow space Y molecular sieve characteristic diffraction peak peak shape of synthesis is narrow, intensity is high, shows its crystallinity height.
Fig. 2 gives a nanometer Y molecular sieve, carbosphere, the SEM figure of spherical hollow space Y molecular sieve and spherical hollow space Y molecular sieve
TEM figure.Fig. 2 a is the SEM figure of nanometer Y molecular sieve, and as seen from the figure: nanometer Y molecular sieve even particle size distribution, size is small, grain
Diameter is about 50nm；Fig. 2 b is the SEM figure of carbosphere, it can be seen that the carbosphere dispersibility that hydro-thermal method is prepared is preferable, surface
It is smooth, and there is more regular spherical structure, average grain diameter 450nm.Fig. 2 c is the SEM figure of spherical hollow space Y molecular sieve, by scheming
It can be observed, the sample of synthesis has apparent chondritic and dispersibility is preferably, and average grain diameter is 500 nm.By 2d spherical hollow space
The TEM figure of Y molecular sieve is it can be seen that it is internal with numerous areolas and in cross-linked structure.May be due to carbosphere
The porous medicine ball being made of little particle, on spherical surface under the space confinement effect effect of micropore, silica-alumina gel is formed basic
Structural unit is grown along the gap of carbosphere, forms cross-linked structure, in high-temperature calcination process, carbosphere mould
Plate is removed, and forms numerous cavity structures.
Fig. 3 is the N of spherical hollow space Y molecular sieve2Adsorption-desorption curve and graph of pore diameter distribution.By Fig. 3 a N2Adsorption-desorption is bent
Line chart can be seen that N2The shape of adsorption-desorption isothermal shows as IV type.IV type thermoisopleth is that mesoporous solid most generally occurs
Absorption behavior.In N2When relative pressure is smaller, N2Adsorbance increase with the raising of relative pressure.?P/P 0 Greater than 0.5
When adsorption curve obviously upwarp, there is biggish hysteresis loop.This shows capillary condensation phenomenon occurred, illustrates to contain in molecular sieve
There is mesopore orbit structure.By the graph of pore diameter distribution in Fig. 3 b it is observed that the pore size of spherical hollow space Y molecular sieve is main
Mesoporous by mesoporous and 8 ~ 10 nm that are distributed in 3.8 nm or so or so forms.In conjunction with Fig. 3 b spherical hollow space Y molecular sieve
Tem analysis is distributed in the gap between the mesoporous mainly cavity of 8 ~ 10 nm or so, this also demonstrates the formation of cavity structure.Point
Cloth is in the gap that the duct of 3.8 nm or so is mainly between nano molecular sieve.
Embodiment 2
Carbosphere powder is prepared according to 1 method of embodiment.
By 30mL deionized water, 1.33g sodium hydroxide, 1.42g sodium metaaluminate, 1.55g white carbon black, 0.2g sodium chloride is added
It into polytetrafluoroethylcontainer container, is stirred at room temperature to gel state, is then successively stirred at 25 DEG C for 24 hours, stir at 45 DEG C
For 24 hours, 12h is stirred at 60 DEG C, obtain Y gel, be put into reaction kettle and seal, react 12 h in 90 DEG C of static crystallizations；Take out reaction
Kettle is rapidly cooled to room temperature in quenching slot, is taken out reaction product, is washed 3 times with deionized water and dehydrated alcohol respectively, is taken out
Filter, in 70 DEG C of 12 h of drying in vacuum oven, obtains a nanometer Y molecular sieve.
1g carbosphere is added in 16.5 mL deionized waters, 0.2 g PVP is continuously added, stirs 1 h at room temperature,
Then 0.5 mL ammonium hydroxide and 14 mL ethyl alcohol are sequentially added, in 70 DEG C of stirring 6h, obtains A liquid.
At room temperature, 0.4g nanometers of Y molecular sieves are added in 5 mL deionized waters, ultrasonic vibration 0.5h, obtain white cream
Shape B liquid.
5mL B liquid is added drop-wise to dropwise in 31mL A liquid, is sealed, in 70 DEG C of stirring 6h, is then washed with dehydrated alcohol centrifugation
It washs 3 times, in 70 DEG C of 12 h of drying in vacuum oven, obtains black presoma CSs@PVP@Y.
0.5g CSs@PVP@Y and 15 mL Y gels are added in polytetrafluoroethylcontainer container, 1 h is stirred at room temperature, it is close
Envelope, is put into autoclave, is placed in insulating box, reacts 10 h in 90 DEG C of static crystallizations.Reaction kettle is taken out, is taken out with distilled water
It is ground after being dried at filter washing 3 times, 70 DEG C, roasts 6 h at 550 DEG C in Muffle furnace, obtain with crosslinking net cavity structure
Spherical Y molecular sieve.
Embodiment 3
Carbosphere powder is prepared according to 1 method of embodiment.
By 30mL deionized water, 2.66g sodium hydroxide, 2.84g sodium metaaluminate, 2.80g white carbon black, 0.2g sodium chloride is added
It into polytetrafluoroethylcontainer container, is stirred at room temperature to gel state, is then successively stirred at 25 DEG C for 24 hours, stir at 45 DEG C
For 24 hours, 12h is stirred at 60 DEG C, obtain Y gel, be put into reaction kettle and seal, react 12 h in 90 DEG C of static crystallizations；Take out reaction
Kettle is rapidly cooled to room temperature in quenching slot, is taken out reaction product, is washed 3 times with deionized water and dehydrated alcohol respectively, is taken out
Filter, in 70 DEG C of 12 h of drying in vacuum oven, obtains a nanometer Y molecular sieve.
1. 5g carbospheres are added in 18.5 mL deionized waters, 0.2 g PV is continuously added, stirs 1 at room temperature
Then h sequentially adds 0.5 mL ammonium hydroxide and 17 mL ethyl alcohol, in 70 DEG C of stirring 6h, obtain A liquid.
At room temperature, 0.6g nanometers of Y molecular sieves are added in 5 mL deionized waters, ultrasonic vibration 0.5h, obtain white cream
Shape B liquid.
5mL B liquid is added drop-wise to dropwise in 36mL A liquid, is sealed, in 70 DEG C of stirring 6h, is then washed with dehydrated alcohol centrifugation
It washs 3 times, in 70 DEG C of 12 h of drying in vacuum oven, obtains black presoma CSs@PVP@Y.
1.5g CSs@PVP@Y and 15 mL Y gels are added in polytetrafluoroethylcontainer container, 1 h is stirred at room temperature, it is close
Envelope, is put into autoclave, is placed in insulating box, reacts 13h in 90 DEG C of static crystallizations.Reaction kettle is taken out, is taken out with distilled water
It is ground after being dried at filter washing 3 times, 70 DEG C, roasts 6 h at 550 DEG C in Muffle furnace, obtain with crosslinking net cavity structure
Spherical Y molecular sieve.
Embodiment 4
Carbosphere powder is prepared according to 1 method of embodiment.
By 30mL deionized water, 1.66g sodium hydroxide, 1.84g sodium metaaluminate, 1.80g white carbon black, 0.2g sodium chloride is added
It into polytetrafluoroethylcontainer container, is stirred at room temperature to gel state, is then successively stirred at 25 DEG C for 24 hours, stir at 45 DEG C
For 24 hours, 12h is stirred at 60 DEG C, obtain Y gel, be put into reaction kettle and seal, react 12 h in 90 DEG C of static crystallizations；Take out reaction
Kettle is rapidly cooled to room temperature in quenching slot, is taken out reaction product, is washed 3 times with deionized water and dehydrated alcohol respectively, is taken out
Filter, in 70 DEG C of 12 h of drying in vacuum oven, obtains a nanometer Y molecular sieve.
1.15g carbosphere is added in 17 mL deionized waters, 0.2 g PV is continuously added, stirs 1 h at room temperature,
Then 0.5 mL ammonium hydroxide and 16.5 mL ethyl alcohol are sequentially added, in 70 DEG C of stirring 6h, obtains A liquid.
At room temperature, 0.45g nanometers of Y molecular sieves are added in 5 mL deionized waters, ultrasonic vibration 0.5h, obtain white cream
Shape B liquid.
5mL B liquid is added drop-wise to dropwise in 33.5mL A liquid, seals, in 70 DEG C of stirring 6h, is then centrifuged with dehydrated alcohol
Washing 3 times, in 70 DEG C of 12 h of drying in vacuum oven, obtains black presoma CSs@PVP@Y.
0.7g CSs@PVP@Y and 15 mL Y gels are added in polytetrafluoroethylcontainer container, 1 h is stirred at room temperature, it is close
Envelope, is put into autoclave, is placed in insulating box, reacts 7h in 90 DEG C of static crystallizations.Reaction kettle is taken out, is filtered with distilled water
It is ground after being dried at washing 3 times, 70 DEG C, roasts 6 h at 550 DEG C in Muffle furnace, obtain that there is crosslinking net cavity structure
Spherical Y molecular sieve.
Application examples 1
Carbon paper is cut into 2cm × 2cm size, successively uses 0.5mol/L H2SO4Solution and 0 .5mol/L NaOH solution are respectively soaked
2h is steeped, to remove the impurity of carbon paper surface.Then it with distilled water immersion 5h, after the bronsted lowry acids and bases bronsted lowry for removing carbon paper surface, dries spare.
Spherical hollow space Y molecular sieve, the 0.2424g Cu that 0.5 g embodiment 1 obtains are sequentially added in 2.5ml deionized water
(NO3)2·3H2O and 0.1142g Ce (NO3)3·6H2O, is stirred at room temperature 5h, and gained slurries are dried at 70 DEG C until dry
It is dry.Then 5 h are roasted at 500 DEG C to get Cu-Ce-Y spherical hollow space composite material.
4mg Cu-Ce-Y spherical hollow space composite material is added in 0 .5mL dehydrated alcohol, is ultrasonically treated 0 .5h to be formed
Uniform suspension draws suspension with liquid-transfering gun, and uniform drop coating is on the above-mentioned carbon paper two sides handled well.After natural drying,
Carbon paper surface 10 μ L of drop coating, 0 .02wt% Nafion solution again, dries at room temperature, it is compound that Cu-Ce-Y spherical hollow space is prepared
Material load amount is 1mg/cm2Cathode electrode.
The XRD spectra of the Cu-Ce-Y spherical hollow space composite material shown by Fig. 4 is it can be seen that Cu-Ce-Y spherical hollow space is answered
There is the characteristic peak of CuO in 35.5o and 38.7o in condensation material, and 28.5o and 47.5 ° CeO occurs2Characteristic diffraction peak.Into one
Step analysis XRD diagram, Cu-Ce-Y spherical hollow space composite material is 2θPosition be 5.12o, 11.8o, 15.6o, 18.6o, 20.3o,
23.4o, 27.0o, 31.3o etc. still remain the characteristic diffraction peak of Y, the active component CuO-CeO that infusion process loads after explanation2
There is no the structures for destroying spherical hollow space Y molecular sieve.But peak intensity weakens, and crystallinity decreases.
Fig. 5 is that the SEM and EDX of Cu-Ce-Y spherical hollow space composite material scheme.Cu-Ce-Y is spherical it can be seen from SEM figure
The pattern of cavity composite material be still in it is spherical, it can be seen that it is internal to have cavity structure from broken particle.Pass through analysis
The EDX of Cu-Ce-Y spherical hollow space composite material schemes, it can be seen that has copper and Ce elements in sample.
At room temperature, it is analyzed using 660 electrochemical workstation of CHI of Shanghai Chen Hua instrument company, to be coated with Cu-Ce-Y ball
The carbon paper of shape cavity composite material makees cathode, and platinized platinum is auxiliary electrode (to electrode), and Ag/AgCl is three electricity that reference electrode is constituted
Polar body system is tested.
The scanning range -1.5 of LSV linear scan~0.5V, 10 mV/s of sweep speed；The scanning range-of Tafel curve
0.9~-0.3V sweeps 10 mV/s of the rate of hastening.
It is respectively comparison with bare carbon paper CP, Pt/C and Cu-Ce-Y spherical hollow space cathode of composite material electrode, in identical item
Its chemical property is tested under part.
Linear scan test point can be carried out using electrochemistry of the three-electrode system to Cu-Ce-Y spherical hollow space composite material
Analysis, chooses bare carbon paper (CP) and Pt/C electrode carries out the test of the performance comparison under the same terms.Fig. 6 is Cu-Ce-Y spherical empty
The linear scan figure of chamber composite material, CP and Pt/C electrode.As can be seen from the figure: under the voltage of -1.5V, Cu-Ce-Y ball
The current density of shape cavity cathode of composite material is 36.77 A/m2, it is much higher than CP cathode, is essentially close to Pt/C electrode, explanation
Cu-Ce-Y spherical hollow space composite electrode liberation of hydrogen catalytic capability with higher.
Tafel slope is the important parameter for reacting electrocatalytic hydrogen evolution kinetics.Pass through the linear zone to polarization curve
It is fitted and is balanced potential and exchange current density, the complexity of an electrode reaction can be measured.Wherein, balance electricity
The smaller reaction of gesture is more easy to happen, and the bigger reaction of exchange current density is more easy to happen, and evolving hydrogen reaction rate is also faster.
Fig. 7 is the Tafel slope of tri- kinds of Cu-Ce-Y spherical hollow space composite material, CP and Pt/C cathode electrodes.From figure
As can be seen that the Tafel slope of Cu-Ce-Y spherical hollow space composite material is 41.54mV/dec, the Ta Feier of Pt/C electrode is oblique
Rate is 39.66 mV/dec, and the Tafel slope of the two is close, and is far below CP electrode (91.11 mV/dec), shows Cu-
Ce-Y spherical hollow space composite material is close with the catalytic activity for hydrogen evolution of Pt/C electrode, consistent with linear scan result.
In order to further verify the analysis of LSV and Tafel electrochemical property test as a result, Cu-Ce-Y spherical hollow space is compound
Material is as cathode for hydrogen evolution and runs MEC device, for handling coking wastewater and being catalyzed production hydrogen.The MEC device uses 100mL
Single chamber reactor, 20 milliliters of activation bacterium sludge and 80 milliliters of nutrient solutions will wherein be added.Wherein it is useless to be derived from coking for activated sludge
Water treatment plant.Nutrient solution is micro for 7 phosphate buffer and calcic, magnesium and manganese etc. by matrix (1 g/L glucose), pH value
The nutrient solution that the liquid microelement of element is constituted, the carbon felt for the electricity production bacterium tamed using attachment are reference electricity as anode, Ag/AgCl
Pole, Cu-Ce-Y spherical hollow space composite material, CP and Pt/C electrode are that cathode carries out producing hydrogen test.Applied voltage be 0.7 V,
MEC is run under conditions of 35 DEG C, is monitored using multimeter and produces hydrogen electric current, records a gas production every 0.5 h.Collected using draining
The gas that gas method collection device generates, using the composition of gas chromatograph detection gas.
Fig. 8 be Cu-Ce-Y spherical hollow space composite material, tri- kinds of cathode materials of Pt/C and CP MEC each period production gas
Amount and gas constitutional diagram.Within each cycle of operation the gas production of Cu-Ce-Y spherical hollow space cathode of composite material MEC be 14.4 ±
The gas production of 0.72 mL, Pt/C cathode material MEC are 16.6 ± 0.83 mL, and the gas production of the two is close, and are much higher than CP
The gas production (5.9 ± 0.295 mL) of cathode material MEC.Further gas component is analyzed, discovery Cu-Ce-Y is spherical empty
Chamber composite electrode produces H in gas total amount2Content accounts for H in 73.71%, Pt/C2Content accounts for 83%, and the two all shows high hydrogen
Selectivity.In addition, the methane selectively of methane selectively (10.84%) and Pt/C of Cu-Ce-Y spherical hollow space composite material
(9.24%) it is close, and lower.Generate CH4The reason of be cathode material after MEC stable a period of time, with battalion
The consumption of substrate in nutrient solution, the proton and electron number shifted in solution are reduced, and current density starts to reduce, and methanogen accounts for master
It leads, to consume H2And CO2Gas generates CH4, so that CH4Content rises.The above result shows that compound with Cu-Ce-Y spherical hollow space
Material has high electro catalytic activity as microorganism electrolysis cell (MEC) cathode.
Embodiment 5
Spherical hollow space Y molecular sieve, the 0.2714g Cu that 0.5 g embodiment 1 obtains are sequentially added in 2.5ml deionized water
(NO3)2·3H2O and 0.0883g Ce (NO3)3·6H2O, is stirred at room temperature 5h, and gained slurries are dried at 70 DEG C until dry
It is dry.Then 5 h are roasted at 500 DEG C to get Cu-Ce-Y spherical hollow space composite material.
Embodiment 6
Spherical hollow space Y molecular sieve, the 0.1828g Cu that 0.5 g embodiment 1 obtains are sequentially added in 2.5ml deionized water
(NO3)2·3H2O and 0.1617g Ce (NO3)3·6H2O, is stirred at room temperature 5h, and gained slurries are dried at 70 DEG C until dry
It is dry.Then 5 h are roasted at 500 DEG C to get Cu-Ce-Y spherical hollow space composite material.
Embodiment 7
Spherical hollow space Y molecular sieve, the 0.2130g Cu that 0.5 g embodiment 1 obtains are sequentially added in 2.5ml deionized water
(NO3)2·3H2O and 0.1389g Ce (NO3)3·6H2O, is stirred at room temperature 5h, and gained slurries are dried at 70 DEG C until dry
It is dry.Then 5 h are roasted at 500 DEG C to get Cu-Ce-Y spherical hollow space composite material.
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
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the Y molecular sieve with spherical hollow space structure, which is characterized in that be to be achieved by the steps of
:
It (1) is Na according to molar ratio using deionized water, sodium hydroxide, sodium metaaluminate, white carbon black as raw material2O:Al2O3: SiO2:
H2O=(0.1 ~ 0.6): (1 ~ 4): (0.3 ~ 1.2): 100 mixing are successively stirred 15 ~ 28h at 20 ~ 30 DEG C, are stirred at 40 ~ 50 DEG C
20 ~ 28h, 10 ~ 14h is stirred at 55 ~ 65 DEG C, obtain Y gel；Then by Y gel after 90 ± 5 DEG C of static crystallizations react 8 ~ 20h,
By product through chilling, washing, filtering, 65 ~ 75 DEG C of 10 ~ 15 h of drying, a nanometer Y molecular sieve is obtained；
(2) into deionized water, successively carbosphere, PVP, ammonium hydroxide and dehydrated alcohol is added in interval, stirs to get A liquid；Wherein, PVP
Mass ratio with carbosphere is 1:(5 ~ 8)；Carbosphere and the mass ratio of deionized water are 1:(12 ~ 18), deionized water, ethyl alcohol
Volume ratio with ammonium hydroxide is (32 ~ 38): (26 ~ 34): 1；
(3) the nanometer Y molecular sieve that step (1) obtains is added into deionized water, obtains white " milky " B liquid；
(4) B liquid is added dropwise in A liquid, after stirring 5 ~ 7h at 65 ~ 75 DEG C, then washing dries 10 at 65 ~ 75 DEG C
~ 14h obtains the presoma CSs@PVP@Y of black；The volume ratio of A liquid and B liquid is (5 ~ 10): 1；
(5) the Y gel obtained presoma CSs@PVP@Y and step (1) is agitated, 90 ± 5 DEG C of static crystallizations, washing, drying,
Then grinding roasts 5 ~ 7h at 530 ~ 570 DEG C, obtain the internal spherical Y molecular sieve with crosslinking net cavity structure.
2. the preparation method of the Y molecular sieve with spherical hollow space structure as described in claim 1, it is characterised in that: step (1)
In, by raw material according to molar ratio be Na2O:Al2O3: SiO2: H2O=(0.2 ~ 0.4): (1.5 ~ 3): (0.5 ~ 0.9): 100 mixing, according to
It is secondary stirred at 25 DEG C for 24 hours, stir at 45 DEG C for 24 hours, at 60 DEG C stir 12h, obtain Y gel；Then by Y gel at 90 ± 5 DEG C
After static crystallization reacts 12h, by product through chilling, washing, filtering, 70 DEG C of 12 h of drying, a nanometer Y molecular sieve is obtained.
3. the preparation method of the Y molecular sieve with spherical hollow space structure as described in claim 1, it is characterised in that: step (2)
In, carbosphere, PVP is added into deionized water, 0.75 ~ 1.5h is stirred at room temperature, sequentially adds ammonium hydroxide and ethyl alcohol, 65 ~
6h is stirred at 75 DEG C, obtains A liquid；Wherein, the mass ratio of PVP and carbosphere is 1:(6 ~ 7), the quality of carbosphere and deionized water
Than for 1:(14 ~ 16), the volume ratio of deionized water, ethyl alcohol and ammonium hydroxide is (33 ~ 37): (28 ~ 32): 1.
4. the preparation method of the Y molecular sieve with spherical hollow space structure as described in claim 1, it is characterised in that: step (3)
In, the mass ratio of nanometer Y molecular sieve and deionized water is 1:(7 ~ 13).
5. the preparation method of the Y molecular sieve with spherical hollow space structure as described in claim 1, it is characterised in that: step (5)
In, the mass ratio of Y gel and presoma CSs@PVP@Y are (12 ~ 36): 1.
6. a kind of preparation method of Cu-Ce-Y spherical hollow space composite material, it is characterised in that: by spherical hollow space Y molecular sieve, Cu
(NO3)2·3H2O and Ce (NO3)3·6H2O is dissolved in deionized water, after 4 ~ 6h is stirred at room temperature, drying, then in 480 ~
5 ~ 7h is roasted at 560 DEG C obtains Cu-Ce-Y spherical hollow space composite material；Gained Cu-Ce-Y spherical hollow space composite material is by ball
Shape cavity Y molecular sieve and CuO-CeO2Active component composition, Y molecular sieve in the Cu-Ce-Y spherical hollow space composite material
Mass fraction is 75%, CuO-CeO2CeO in active component2Mass fraction be 28 ~ 52%.
7. a kind of Cu-Ce-Y that the preparation method with Cu-Ce-Y spherical hollow space composite material described in claim 6 obtains is spherical empty
Chamber composite material.
8. a kind of application of Cu-Ce-Y spherical hollow space composite material on the cathode material for preparing microorganism electrolysis cell.
9. a kind of cathode material of microorganism electrolysis cell, it is characterised in that: be to disperse Cu-Ce-Y spherical hollow space composite material in
In dehydrated alcohol, drop coating is fixed with Nafion solution after dry in carbon paper surface, obtains the cathode material of microorganism electrolysis cell
Material.
10. the cathode material of microorganism electrolysis cell as claimed in claim 9, it is characterised in that: Cu- in the cathode material
The load capacity of Ce-Y spherical hollow space composite material is 0.5 ~ 1.5 mg/cm2。
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