CN114524470A - Nickel ferrite nano particle and green synthesis method and application thereof - Google Patents
Nickel ferrite nano particle and green synthesis method and application thereof Download PDFInfo
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Abstract
The invention provides nickel ferrite nano particles and a preparation method and application thereof for promoting hydrogen production, wherein eichhornia crassipes extract is used as a stabilizer and a regulator, mixed solution of nickel salt and ferric salt is added, after continuous stirring reaction, the mixture is heated and reacted in a water bath kettle at constant temperature to obtain viscous gel, and the viscous gel is dried; calcining, grinding, washing and drying the product to obtain the nickel ferrite nano particles. In the preparation process, no additional chemical reagent is added except the precursor nickel salt and iron salt, expensive instruments and equipment are not needed, the operation condition is mild, simple and feasible, economic and environment-friendly, and the further expansion of production and application is facilitated. The prepared nickel ferrite nano particles have stable performance, uniform particle size and good biocompatibility, and have the effects of promoting the synthesis of biological hydrogen and the utilization of reducing sugar in straw hydrolysate when being added into a dark fermentation hydrogen production system, so that the cumulative hydrogen yield, the glucose utilization rate and the xylose utilization rate obtained under the optimal addition concentration are respectively and obviously improved compared with the control treatment.
Description
Technical Field
The invention belongs to the technical field of synthesis regulation and control of nano materials and biohydrogen energy, and particularly relates to nickel ferrite nano particles, a green synthesis method thereof and application of the nickel ferrite nano particles in promoting hydrogen production.
Background
Nanotechnology is an important strategic emerging technology of human in the 21 st century, and the wide application of nano materials in various social fields promotes the great revolution of world industry. Most nanomaterials have been synthesized by physical methods or chemical methods so far, however, the physical methods have high energy and economic requirements in terms of production conditions, and require a stabilizer to disperse the produced nanoparticles. The chemical method can produce nano particles in a short time, but most of the nano particles use toxic and harmful chemical raw materials, and the biocompatibility is low, so that the application of the nano materials in the fields of biology and medicine is greatly limited. In recent years, with the ever-increasing application prospects of metal nanoparticles in the fields of biology, medicine and the like, the development of environment-friendly, green and safe synthetic methods and technologies has attracted extensive attention of researchers at home and abroad.
Plant tissues contain natural compounds such as polyphenols, flavonoids, alkaloids, terpenoids and the like, can be directly used as a regulator and a stabilizer for nanoparticle biosynthesis, do not need to add any additional surfactant or other chemical substances, and are currently important raw materials for green synthesis of nano materials. Eichhornia crassipes is a fast-growing and rapid-propagating aquatic plant, and the extract of the water hyacinth also contains various secondary metabolites such as phenols, sterols, flavonoids, terpenoids, anthraquinone compounds and the like, and can play a main role in the formation and the stabilization of nano particles. At present, certain researches report that the water hyacinth extracting solution can be used for green synthesis of some single metal nanoparticles, such as nano silver, nano platinum, nano iron, nano zinc oxide, nano ferroferric oxide, nano nickel oxide and the like. So far, reports of synthesizing bimetallic nanoparticles by taking eichhornia crassipes extract as a raw material are not seen.
Nickel ferrite (NiFe)2O4) The ferrite is a typical soft magnetic ferrite material and has the properties of high saturation magnetization, low coercive force, good thermal stability, chemical stability and the like. At present, researchers have prepared nano nickel ferrite with granular, rod-like, petal-like, spherical, cubic block-like structures by a hydrothermal method, a sol-gel method, a coprecipitation method, a heating reflux method and the like, and the nano nickel ferrite is applied to the aspects of catalysts, information storage, drug transmission, sewage treatment, gas sensitivity tests, lithium ion batteries, microwave elements, fuel cells and the like. However, no report has been found on the research of synthesizing nano nickel ferrite by using plant tissue extract.
In the field of dark fermentation biological hydrogen production, metals Fe and Ni can be used as important binding elements of hydrogen-producing bacteria catalase active centers so as to promote the production of hydrogen. In recent years, metal Fe, Ni and oxide nanoparticles thereof are added to a dark fermentation hydrogen production system, and can be used as a catalase active center binding element, and the surface effect and the quantum size effect of the metal Fe, Ni and oxide nanoparticles can also play a certain role in promoting the synthesis of biological hydrogen, so that the preparation of the nanoparticles and the application of the nanoparticles in the field of dark fermentation hydrogen production are particularly attractive. The addition of single Fe, Ni and oxide nanoparticles thereof to a dark fermentation hydrogen production system has been reported to some extent, however, the research of adjusting and controlling pure culture hydrogen production bacteria in a nano nickel ferrite composite form to produce hydrogen by dark fermentation organisms has not been reported.
Disclosure of Invention
The invention aims to provide nickel ferrite nanoparticles and a green synthesis method thereof.
The invention also provides an application of the nickel ferrite nano particles in a dark fermentation hydrogen production system.
The specific technical scheme of the invention is as follows:
a green synthesis method of nickel ferrite nano particles comprises the following steps:
1) adding the water hyacinth extracting solution into a mixed solution of nickel salt and ferric salt at room temperature, continuously stirring for reaction, heating for reaction in a water bath kettle at constant temperature to obtain viscous gel, and drying;
2) calcining, grinding, washing and drying the product obtained in the step 1) to obtain the nickel ferrite nano particles.
The preparation method of the water hyacinth extracting solution in the step 1) comprises the following steps:
taking 10g of fresh water hyacinth, sequentially cleaning the fresh water hyacinth with tap water or distilled water, then placing the fresh water hyacinth in a mortar, grinding the mixture into mud, adding distilled water to wash the extract for 3 times, using 50mL of distilled water, keeping the precipitate every time, combining the precipitates for three times, placing the mixture in a water bath at 95-100 ℃ to heat and extract for 10min, cooling the mixture to room temperature, carrying out suction filtration, taking the supernatant, and fixing the volume to 50mL to obtain the water hyacinth extract.
The fresh Eichhornia crassipes is stems, leaves or stem and leaf mixture of Eichhornia crassipes.
By adopting the preparation method of the water hyacinth extracting solution, parameters such as the raw material dosage, the temperature and the like are controlled, and cubic spherical nanoparticles with the size of 15-20 nm can be obtained.
In the step 1), Ni is contained in the mixed solution of the nickel salt and the ferric salt2+And Fe3+The molar ratio is 1: 2;
in the step 1), in the mixed solution of the nickel salt and the ferric salt, the final concentration of the nickel salt is 0.15mol/L, and the final concentration of the ferric salt is 0.30 mol/L;
the nickel salt is nickel acetate or hydrated salt thereof, nickel chloride or hydrated salt thereof;
the ferric salt is ferric nitrate or hydrated salt thereof, ferric chloride or hydrated salt thereof;
preferably, in step 1), the method for preparing the mixed solution of the nickel salt and the iron salt comprises: weighing nickel salt and ferric salt, and dissolving in 100mL of deionized water to make the final concentrations respectively 0.15mol/L and 0.30 mol/L;
in the step 1), the volume ratio of the water hyacinth extracting solution to the mixed solution of the nickel salt and the ferric salt is 1: 2;
preferably, in the step 1), 50mL of the Eichhornia crassipes extractive solution is added into 100mL of the mixed solution of the nickel salt and the ferric salt at room temperature, and the mixture is placed on a magnetic stirrer to be continuously stirred for 15-20 min;
the constant-temperature heating reaction in the water bath in the step 1) is to heat the mixture in the water bath at the temperature of 60 ℃ for 5-6 hours at constant temperature, and stir the mixture for 2-3 min every 1.5 hours during the constant-temperature heating reaction until viscous gel is obtained.
The drying in the step 1) refers to drying in a constant-temperature drying oven at 100 ℃ for 16-18 h;
the calcination in the step 2) means: transferring the product into a ceramic crucible, and calcining for 6 hours in a muffle furnace at 600-700 ℃;
the grinding in the step 2) refers to: after cooling the dried sample, grinding the dried sample into fine powder by using a mortar, and sieving the fine powder by using a 200-mesh sieve;
the washing in step 2) means: washing with anhydrous alcohol and deionized water for 3 times;
the drying in the step 2) refers to: and (5) drying the mixture for 6-8 hours in a constant-temperature drying oven at the temperature of 80 ℃ until the weight is constant.
The nickel ferrite nanoparticles provided by the invention are cubic spherical nanoparticles with the size of 15-20 nm, have groups derived from phenolic compounds in eichhornia crassipes extract, have good stability and biocompatibility, and are prepared by adopting the preparation method.
The invention provides an application of nickel ferrite nano particles for biological hydrogen production by dark fermentation.
The specific method for using the nickel ferrite nano particles in the dark fermentation biological hydrogen production provided by the invention comprises the following steps:
adding the prepared nickel ferrite nano particles into a fermentation culture medium, uniformly mixing, sterilizing and cooling, inoculating Klebsiella sp seed liquid, periodically detecting the hydrogen production by adopting a sodium hydroxide solution discharging method, accumulating day by day, and converting the accumulated hydrogen production within 120 h.
Further, the nickel ferrite nano particles are added according to the final concentration of 10-50 mg/L.
The invention adds the nickel ferrite nano particles into the straw hydrolysate fermentation hydrogen production system, has obvious effect of promoting the synthesis of the biological hydrogen and the utilization of the reducing sugar in the hydrolysate, and ensures the obtained reduction sugar under the optimal adding concentrationThe accumulated hydrogen production is 1.8 times of that of the control treatment, and the increase of the accumulated hydrogen production is larger than that of the single addition of Fe3O4The sum of the increase of NP and the increase of NiONP added alone. The nickel ferrite nano particle provided by the invention has the advantages of simple synthesis method, mild operation conditions, low cost, economy and environmental protection, and the obtained nano particle has stable performance, uniform particle size, good biocompatibility and remarkable hydrogen production promoting effect.
Compared with the prior art, the invention has the following advantages and effects:
1. the preparation process of the green synthetic nickel ferrite nano particles does not need to add extra chemical reagents except the precursor nickel salt and iron salt, does not need expensive instruments and equipment, has mild operation conditions, is simple and easy to implement, is economic and environment-friendly, and is convenient for further expanding production and application;
2. the nickel ferrite nano particles prepared by the method have stable performance, uniform particle size and good biocompatibility, and can be added into a dark fermentation hydrogen production system at a certain concentration to promote the synthesis of biological hydrogen and the utilization of reducing sugar in straw hydrolysate, so that the cumulative hydrogen yield, the glucose utilization rate and the xylose utilization rate obtained under the optimal addition concentration are respectively and obviously improved compared with the control treatment.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of nickel ferrite nanoparticles prepared according to example 1 of the present invention;
FIG. 2 is a graph of the infrared spectrum (FTIR) of nickel ferrite nanoparticles prepared in example 1 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of nickel ferrite nanoparticles prepared in example 1 of the present invention;
FIG. 4 is a Transmission Electron Microscope (TEM) image of nickel ferrite nanoparticles prepared in example 1 of the present invention;
FIG. 5 is a diagram of a magnetic hysteresis loop (VSM) of nickel ferrite nanoparticles prepared in example 1 of the present invention;
FIG. 6 is an X-ray diffraction (XRD) pattern of nickel ferrite nanoparticles prepared in example 2 of the present invention;
FIG. 7 is an X-ray diffraction (XRD) pattern of nickel ferrite nanoparticles prepared in example 3 of the present invention;
FIG. 8 is a graph showing the cumulative hydrogen production by adding nickel ferrite nanoparticles according to the present invention;
FIG. 9 shows the results of glucose and xylose utilization with nickel ferrite nanoparticles according to the present invention;
FIG. 10 is a graph showing the cumulative hydrogen production results of the present invention with different nanoparticles added.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
A green synthesis method of nickel ferrite nano particles comprises the following steps:
1) taking 10g of fresh eichhornia crassipes stems and leaves, cleaning the stems and leaves with tap water and distilled water in sequence, putting the stems and leaves in a mortar, grinding the stems and leaves into mud, adding distilled water to wash the extract for 3 times, using 50mL of distilled water, combining the precipitates every time, precipitating for three times, combining the precipitates, transferring the combined precipitates into a beaker, further putting the beaker in a water bath at 95-100 ℃, heating and extracting the mixture for 10min, cooling the beaker to room temperature, performing suction filtration, taking supernate, and fixing the volume to 50mL to obtain an eichhornia crassipes extracting solution;
2) weighing nickel chloride and ferric nitrate, and dissolving in 100mL of deionized water to make the final concentrations respectively 0.15mol/L and 0.30 mol/L; adding 50mL of the prepared water hyacinth extracting solution into the salt solution at room temperature, and continuously stirring for 20min on a magnetic stirrer; heating the obtained mixed solution in a 60 deg.C water bath at constant temperature for 6h, stirring once every 1.5h, and stirring for 3min each time to obtain viscous gel; drying the obtained gel in a drying oven at constant temperature of 100 ℃ for 18 h;
3) transferring the prepared dried substance into a ceramic crucible, and calcining for 6 hours in a muffle furnace at 700 ℃; grinding the obtained dried sample into fine powder by using a mortar, sieving the fine powder by using a 200-mesh sieve, washing the fine powder for 3 times by using absolute ethyl alcohol and deionized water respectively, and drying the washed fine powder for 8 hours in a constant-temperature drying oven at the temperature of 80 ℃ until the weight is constant; thus obtaining the nickel ferrite nano particles.
Characterization of the prepared green synthetic nickel ferrite nanoparticles:
the prepared nickel ferrite nano particle is characterized, an XRD pattern is shown in figure 1, diffraction peaks are sharp, and the sample has a better spinel structure, the diffraction peaks at 18.4 degrees, 30.3 degrees, 35.7 degrees, 37.3 degrees, 43.4 degrees, 47.5 degrees, 53.8 degrees, 57.4 degrees, 62.9 degrees, 66.2 degrees, 71.5 degrees and 74.6 degrees respectively correspond to crystal faces (111), (220), (311), (222), (400), (331), (422), (511), (440), (531), (620) and (533) of the nickel ferrite, and completely accord with the crystal faces of JCPDS NO.10-0325 of a standard card, and no other diffraction peaks exist, so that the purer nano nickel ferrite is prepared. FIG. 2 is the infrared spectrum of nano nickel ferrite at 603.02cm-1、417.03cm-1The absorption peak is strong and corresponds to the stretching vibration of Fe-O, Ni-O and is 3442.26cm-1、1633.24cm-1A stronger surface free-OH absorption peak is appeared, corresponding to H2Stretching and bending vibration of O molecule at 2713.35cm-1An absorption peak was also observed, representing the-CH, C ═ O group of the organic molecule, possibly from phenolic compounds of the eichhornia crassipes extract, helping to maintain the stability of the nanoparticles. The SEM image of FIG. 3 reveals that the nickel ferrite nano-particles are in a cubic sphere structure from the surface appearance, and certain agglomeration exists among the particles. The TEM image of FIG. 4 reveals the cubic structure of nano nickel ferrite, and analysis of the crystal particle size of the nano nickel ferrite shows that the average particle size of the nano particles is about 15-20 nm. The magnetic performance of the nano nickel ferrite is further tested, the hysteresis loop at room temperature is shown in figure 5, the green synthesized nickel ferrite nano particle has the soft magnetic characteristic, and the saturation magnetization M of the green synthesized nickel ferrite nano particles＝31.30emu/g。
Example 2
A green synthesis method of nickel ferrite nano particles comprises the following steps:
1) taking 10g of fresh eichhornia crassipes leaves, sequentially cleaning the fresh eichhornia crassipes leaves by using tap water and distilled water, placing the fresh eichhornia crassipes leaves in a mortar, grinding the mixture into mud, adding distilled water to wash the extract for 3 times, sharing 50mL of distilled water, keeping the precipitate every time, combining the precipitates for three times, further placing the mixture in a water bath with the temperature of 95-100 ℃, heating and extracting the mixture for 10min, cooling the mixture to room temperature, carrying out suction filtration, and fixing the volume to 50mL to obtain an eichhornia crassipes extract;
2) weighing nickel acetate and ferric chloride, and dissolving in 100mL of deionized water to make the final concentrations respectively 0.15mol/L and 0.30 mol/L; at room temperature, adding 50mL of Eichhornia crassipes (L.) Gaertn extract into the above salt solution, and continuously stirring for 20min on a magnetic stirrer; heating the obtained mixed solution in a 60 deg.C water bath at constant temperature for 6h, and stirring for 3min every 1.5h to obtain viscous gel; further placing the obtained gel in a drying oven at constant temperature of 100 ℃ for drying for 17 h;
3) transferring the prepared dried substance into a ceramic crucible, and calcining for 6 hours in a muffle furnace at 600 ℃; grinding the obtained dried sample into fine powder by using a mortar, sieving the fine powder by using a 200-mesh sieve, washing the fine powder for 3 times by using absolute ethyl alcohol and deionized water respectively, and drying the washed fine powder in a constant-temperature drying oven at the temperature of 80 ℃ until the weight is constant for 7 hours; the obtained nanoparticles are further characterized by XRD, as shown in FIG. 6, the sample has a typical spinel structure, and the diffraction peaks at 18.4 °, 30.3 °, 35.7 °, 37.3 °, 43.4 °, 53.8 °, 57.4 °, 62.9 °, 71.5 °, and 74.6 ° respectively correspond to the (111), (220), (311), (222), (400), (422), (511), (440), (620), and (533) crystal faces of nickel ferrite, and are consistent with the JCPDS NO.10-0325 standard card, but the typical (331) and (531) crystal faces of the nano nickel ferrite do not exist, and other diffraction peaks exist, which indicates that the purity of the prepared nano nickel ferrite is not high enough, and therefore the nickel ferrite nanoparticles prepared in example 1 with higher purity are selected to be applied to the biological hydrogen production by dark fermentation.
Example 3
A green synthesis method of nickel ferrite nano particles comprises the following steps:
1) taking 10g of fresh eichhornia crassipes stems, sequentially cleaning the fresh eichhornia crassipes stems by using tap water and distilled water, placing the fresh eichhornia crassipes stems in a mortar, grinding the mixture into mud, adding distilled water to wash the extract for 3 times, using 50mL of distilled water, keeping the precipitate every time, combining the precipitates for three times, further placing the mixture in a water bath with the temperature of 95-100 ℃ to heat and extract for 10min, cooling the mixture to room temperature, carrying out suction filtration, and fixing the volume to 50mL to obtain an eichhornia crassipes extract;
2) weighing nickel acetate and ferric chloride, and dissolving in 100mL of deionized water to make the final concentrations respectively 0.15mol/L and 0.30 mol/L; at room temperature, adding 50mL of Eichhornia crassipes (L.) Gaertn extract into the above salt solution, and continuously stirring for 20min on a magnetic stirrer; heating the obtained mixed solution in a 60 deg.C water bath at constant temperature for 6h, and stirring every 1.5h for 3min to obtain viscous gel; further drying the obtained gel in a drying oven at constant temperature of 100 ℃ for 16 h;
3) transferring the prepared dried substance into a ceramic crucible, and calcining for 6 hours in a muffle furnace at 600 ℃; grinding the obtained dried sample into fine powder by using a mortar, sieving the fine powder by using a 200-mesh sieve, washing the fine powder for 3 times by using absolute ethyl alcohol and deionized water, and drying the washed fine powder in a constant-temperature drying oven at the temperature of 80 ℃ until the weight is constant for 8 hours; the obtained nanoparticles are further characterized by XRD, as shown in FIG. 7, the sample has a typical spinel structure, and the diffraction peaks at 18.4 °, 30.3 °, 35.7 °, 37.3 °, 43.4 °, 53.8 °, 57.4 °, 62.9 °, 71.5 °, and 74.6 ° respectively correspond to the (111), (220), (311), (222), (400), (422), (511), (440), (620), and (533) crystal faces of nickel ferrite, and are consistent with the JCPDS NO.10-0325 standard card, but the typical (331) and (531) crystal faces of the nano nickel ferrite do not exist, and other diffraction peaks exist, which indicates that the purity of the prepared nano nickel ferrite is not high enough, and therefore the nickel ferrite nanoparticles prepared in example 1 with higher purity are selected to be applied to the biological hydrogen production by dark fermentation.
Example 4
The application of the nickel ferrite nano particles prepared in the example 1 is used for biological hydrogen production through dark fermentation.
The specific application method comprises the following steps: the nickel ferrite nanoparticles synthesized by the stem and leaves of eichhornia crassipes of example 1 are added into a fermentation medium for hydrogen production by fermenting straw hydrolysate in Klebsiella sp so that the final concentrations are 0, 10, 20, 30, 40 and 50mg/L respectively, and the formula of the fermentation medium is as follows: 1000mL of straw hydrolysate, 5g of beef extract, 10g of peptone, 5g of NaCl and KH2PO40.5g，MgSO4·7H2O0.5 g, sugar concentration 50g/L, pH8.0. Fully dispersing the nanoparticles in a fermentation culture medium by adopting a stirring and ultrasonic treatment mode, inoculating Klebsiella sp seed liquid according to the inoculation amount of 10% after sterilization and cooling, detecting the hydrogen production by periodically adopting a sodium hydroxide solution discharging method, accumulating day by day, converting the accumulated hydrogen production within 120h, and analyzingThe influence of the nickel ferrite nano-particle addition on the biological hydrogen synthesis of the straw hydrolysate fermentation hydrogen production system is shown in figure 8. As can be seen from the curve change in the figure, the cumulative hydrogen production amount of the strain fermented for 120h is higher than that of the strain fermented for the control treatment (0mg/L) within the addition concentration range of 10-50 mg/L, which indicates that the nano particles have a wider hydrogen production promoting range and represent good biocompatibility. The accumulated hydrogen yield of the straw hydrolysate can reach 5956.3 +/-39.8 mL/L which is 1.8 times of that of the contrast treatment (0mg/L), and the treatment can obviously promote the Klebsiella sp fermentation to produce hydrogen.
The preparation of hydrogen-producing bacteria Klebsiella sp. seed bacteria and the preparation of straw hydrolysate in this example are reported in the literature, "research on transcription regulation mechanism of green synthesis of metal nanoparticles and enhanced Klebsiella sp.
The nickel ferrite nano-particles synthesized by the method have the following influence on the utilization of glucose and xylose in the straw hydrolysate in Klebsiella sp:
by referring to the method provided in example 4, nickel ferrite nanoparticles are added to the straw hydrolysate fermentation hydrogen production medium and inoculated with hydrogen production bacteria Klebsiella sp, the fermentation broth is periodically taken out and centrifuged, the concentrations of glucose and xylose in the supernatant are detected, and the influence of the addition of the nickel ferrite nanoparticles on the utilization rate of reducing sugars (glucose and xylose) in the straw hydrolysate is analyzed, and the result is shown in fig. 9. The results in FIG. 9 show that all treatments with nickel ferrite nanoparticles are beneficial to hydrogen-producing bacteria to utilize reducing sugar in the straw hydrolysate, and the glucose and xylose utilization rates are improved compared with those of the control treatment (0mg/L), especially the glucose and xylose utilization rates with the addition concentration of 30mg/L are the highest (96.4% and 96.3%) and are respectively improved by 8.0% and 8.9% compared with those of the control treatment (0 mg/L).
The contrast analysis of the influence of the nickel ferrite nano particles on the dark fermentation hydrogen production:
ferroferric oxide nanoparticles (Fe) were added according to the method provided in example 43O4NP), nickel oxide nanoparticles (NiONP), nickel ferrite nanoparticles (NiFe)2O4NP) to straw hydrolysate fermentation hydrogen production systemInoculating hydrogen-producing bacteria Klebsiella sp, and selecting the three nanoparticles according to the optimal concentration (Fe)3O4NP 20mg/L、NiONP20mg/L、NiFe2O4NP 30mg/L), using the treatment without adding nano particles as the control treatment; the method provided by the embodiment 2 is referred to detect the volume of hydrogen and convert the accumulated hydrogen yield, the influence of different nano particle addition on the fermentation hydrogen production of the straw hydrolysate is analyzed, and the result is shown in figure 10. The results in FIG. 10 show that the three nanoparticles can effectively promote the synthesis of hydrogen-producing bacteria biological hydrogen under the optimal addition concentration, and the cumulative hydrogen yield is obviously improved compared with the control treatment, especially NiFe2O4The NP has the most obvious effect of promoting hydrogen production, which shows that the nano particle has the effect of promoting hydrogen production by coupling Fe and Ni, and the increase range (80.0%) of the accumulated hydrogen production is larger than that of the single addition of Fe3O4The sum of the increase of NP (20.0%) and the increase of NiONP (46.4%) added singly shows that the NiFe prepared by the invention2O4NP plays a hydrogen production promoting effect of coupling Fe and Ni, and the effect is superior to that of single addition of Fe3O4NP or NiONP alone.
Example 5
The nickel ferrite nano particles prepared in the embodiment 1 are applied to hydrogen production by fermenting straw hydrolysate with enterobacter cloacae.
The nickel ferrite nanoparticles synthesized from the eichhornia crassipes stems and leaves in example 1 were added to a hydrogen production medium prepared from enterobacter cloacae fermented straw hydrolysate according to the treatment method of example 4, the formula of the medium was the same as that in example 4, and the fermented hydrogen production and the amount of hydrogen produced were detected and converted by the method consistent with example 4. The result shows that the addition of 10-50 mg/L nickel ferrite nanoparticles can promote the increase of the hydrogen production of the enterobacter cloacae, so that the cumulative hydrogen production of the enterobacter cloacae after fermentation for 120 hours is higher than that of the control treatment (0mg/L), and the cumulative hydrogen production obtained when 20mg/L nano nickel ferrite is added is the highest and reaches 5057.8 +/-110.9 mL/L, which is increased by 45.9 percent compared with that of the control treatment. The application effects of the embodiment and the embodiment 4 both show that the nickel ferrite nano-particles prepared by the invention have obvious hydrogen production promoting effect on pure culture hydrogen-producing bacteria, and reflect good biocompatibility.
The enterobacter cloacae for hydrogen production in the embodiment is a hydrogen-producing strain reported in the literature "influence of segmented pH value control on hydrogen production of hydrolysis sugar solution of cotton stalk fermented by enterobacter cloacae WL1318 (dawn et al, 2018).
Claims (10)
1. A preparation method of nickel ferrite nano particles is characterized by comprising the following steps:
1) adding the water hyacinth extracting solution into a mixed solution of nickel salt and ferric salt at room temperature, continuously stirring for reaction, heating for reaction in a water bath kettle at constant temperature to obtain viscous gel, and drying;
2) calcining, grinding, washing and drying the product obtained in the step 1) to obtain the nickel ferrite nano particles.
2. The method according to claim 1, wherein the method for preparing the water hyacinth extract in step 1) comprises:
taking 10g of fresh water hyacinth, sequentially cleaning the fresh water hyacinth with tap water or distilled water, then placing the fresh water hyacinth in a mortar, grinding the mixture into mud, adding distilled water to wash the extract for 3 times, using 50mL of distilled water, keeping the precipitate every time, combining the precipitates for three times, placing the mixture in a water bath at 95-100 ℃ to heat and extract for 10min, cooling the mixture to room temperature, carrying out suction filtration, taking the supernatant, and fixing the volume to 50mL to obtain the water hyacinth extract.
3. The method according to claim 1, wherein in step 1), Ni is contained in the mixed solution of the nickel salt and the iron salt2+And Fe3+The molar ratio is 1: 2.
4. The method according to claim 1, wherein in the step 1), the final concentration of the nickel salt and the final concentration of the iron salt in the mixed solution of the nickel salt and the iron salt are 0.15mol/L and 0.30mol/L, respectively.
5. The preparation method according to claim 1, wherein in the step 1), the volume ratio of the water hyacinth extract to the mixed solution of the nickel salt and the iron salt is 1: 2.
6. the preparation method according to claim 1, wherein the constant-temperature heating reaction in the water bath in the step 1) is that the constant-temperature heating reaction is carried out in the water bath at 60 ℃ for 5-6 hours, and the stirring is carried out for 2-3 min every 1.5 hours until viscous gel is obtained.
7. The method according to claim 1, wherein the calcining in step 2) is: the product is transferred to a porcelain crucible and then is calcined in a muffle furnace at 600-700 ℃ for 6 h.
8. A nickel ferrite nanoparticle prepared by the preparation method according to any one of claims 1 to 7.
9. Use of nickel ferrite nanoparticles prepared by the preparation method according to any one of claims 1 to 7 for the biological production of hydrogen by dark fermentation.
10. The application of claim 9, wherein the application specific method is:
adding nickel ferrite nano particles into a fermentation culture medium, uniformly mixing, sterilizing and cooling, inoculating Klebsiella sp seed liquid, and periodically detecting the hydrogen yield by adopting a sodium hydroxide solution discharging method.
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