CN114524470B - Nickel ferrite nanoparticle and green synthesis method and application thereof - Google Patents
Nickel ferrite nanoparticle and green synthesis method and application thereof Download PDFInfo
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Abstract
The invention provides a nickel ferrite nanoparticle, a preparation method and hydrogen production promotion application thereof, wherein an eichhornia crassipes extracting solution is adopted as a stabilizer and a regulator, a mixed solution of nickel salt and ferric salt is added, and after continuous stirring reaction, the mixed solution is heated and reacted at constant temperature in a water bath kettle to obtain viscous gel, and the viscous gel is dried; and 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 ferric salt, and high instrument and equipment are not needed, so that the preparation method is mild in operation condition, simple and easy to implement, economical and environment-friendly, and convenient for further expanding production and application. The prepared nickel ferrite nano particles have stable performance, uniform particle size and good biocompatibility, and when being added into a dark fermentation hydrogen production system, the nickel ferrite nano particles have the effect of promoting 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.
Description
Technical Field
The invention belongs to the technical field of nano materials and biological hydrogen energy synthesis regulation and control, and particularly relates to nickel ferrite nano particles, a green synthesis method thereof and application of promoting hydrogen production.
Background
Nanotechnology is an important strategic emerging technology for humans in the 21 st century, and the wide application of nanomaterials in various fields of society has prompted a significant revolution in the world industry. To date, most nanomaterials have been synthesized by physical methods or chemical methods, however, physical methods have high energy and economic requirements on the preparation conditions, and require stabilizers to disperse the prepared nanoparticles. The chemical method can produce nano particles in a short time, but most of the chemical methods use toxic and harmful chemical raw materials, and have low biocompatibility, so that the application of the nano material in the biological and medical fields is greatly limited. In recent years, with the continuous and outstanding application prospects of metal nanoparticles in the fields of biology, medicine and the like, the development of an environment-friendly and green safe synthesis method and technology has attracted extensive attention from researchers at home and abroad.
The plant tissue contains natural compounds such as polyphenols, flavonoids, alkaloids, terpenes and the like, can be directly used as regulator and stabilizer for nanoparticle biosynthesis, does not need to add any additional surfactant or other chemical substances, and is an important raw material for green synthesis of nano materials. Eichhornia crassipes is an aquatic plant with rapid growth and propagation, and the extract also contains various secondary metabolites such as phenols, sterols, flavonoids, terpenes, anthraquinone compounds and the like, which can play a main role in the formation and stability of nano particles. At present, a certain research report that the eichhornia crassipes extract can be used for green synthesis of some single metal nano particles, such as nano silver, nano platinum, nano iron, nano zinc oxide, nano ferroferric oxide, nano nickel oxide and the like. To date, no report on synthesizing bimetallic nano-particles by taking eichhornia crassipes extract as a raw material is seen.
Nickel ferrite (NiFe) 2 O 4 ) Is a typical soft magnetic ferrite material, and has the properties of high saturation magnetization, low coercivity, good thermal stability, chemical stability and the like. At present, researchers have prepared nano nickel ferrite with structures such as particles, rods, petals, balls, cubes and the like by a hydrothermal method, a sol-gel method, a coprecipitation method, a heating reflux method and the like, and applied the nano nickel ferrite to the aspects of catalysts, information storage, drug transmission, sewage treatment, gas sensitivity test, lithium ion batteries, microwave elements, fuel cells and the like. However, related researches on synthesizing nano nickel ferrite by using plant tissue extract have not been reported yet.
In the field of the dark fermentation biological hydrogen production, metal Fe and Ni can be used as important binding elements of hydrogen-producing bacteria hydrogenase active centers so as to promote the production of hydrogen. In recent years, metal Fe, ni and oxide nano particles thereof are added into a dark fermentation hydrogen production system, and besides being used as a hydrogen enzyme active center binding element, the surface effect and the quantum size effect of the nano particles can also play a certain role in promoting the synthesis of biological hydrogen, so that the preparation of the nano particles and the application of the nano particles in the field of the dark fermentation hydrogen production are particularly attractive. The addition of single Fe, ni and oxide nanoparticles to a dark fermentation hydrogen production system has been reported to some extent, however, research on regulating and controlling pure culture hydrogen production bacteria in a nano nickel ferrite composite mode to dark fermentation biological hydrogen production has not been reported.
Disclosure of Invention
The invention aims to provide nickel ferrite nano particles and a green synthesis method thereof, which adopt eichhornia crassipes extract as a stabilizer and a regulator, and have the advantages of low cost, simple operation, environmental friendliness, safety and stability.
The invention also provides application of the nickel ferrite nano particles to a dark fermentation hydrogen production system.
The specific technical scheme of the invention is as follows:
the green synthesis method of the nickel ferrite nano particle comprises the following steps:
1) Adding the water hyacinth extract into the mixed solution of nickel salt and ferric salt at room temperature, continuously stirring for reaction, heating at constant temperature in a water bath kettle for reaction to obtain viscous gel, and drying;
2) And (3) calcining, grinding, washing and drying the product obtained in the step (1) to obtain the nickel ferrite nano particles.
The preparation method of the eichhornia crassipes extracting solution in the step 1) comprises the following steps:
taking 10g of fresh eichhornia crassipes, cleaning with tap water or distilled water successively, grinding into mud in a mortar, adding distilled water to wash the extract for 3 times, adding 50mL of distilled water, reserving precipitate each time, combining the precipitates for three times, heating and extracting in a water bath at 95-100 ℃ for 10min, cooling to room temperature, carrying out suction filtration, taking the supernatant, and fixing the volume to 50mL to obtain the eichhornia crassipes extract.
The fresh eichhornia crassipes is stems, leaves or stem and leaf mixtures of eichhornia crassipes.
By adopting the preparation method of the eichhornia crassipes extract, parameters such as raw material consumption, temperature and the like are controlled, so that cubic spherical nano particles with the size of 15-20 nm can be obtained.
In the step 1), ni in the mixed solution of the nickel salt and the ferric salt 2+ And Fe (Fe) 3+ The molar ratio is 1:2;
in the step 1), the final concentration of nickel salt in the mixed solution of the nickel salt and the ferric salt is 0.15mol/L, and the final concentration of ferric salt is 0.30mol/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 preparation method of the mixed solution of the nickel salt and the iron salt comprises the following steps: weighing nickel salt and ferric salt, and dissolving in 100mL of deionized water to make the final concentration of the nickel salt and the ferric salt be 0.15mol/L and 0.30mol/L respectively;
in the step 1), the volume ratio of the eichhornia crassipes extracting solution to the mixed solution of nickel salt and ferric salt is 1:2;
preferably, in the step 1), 50mL of eichhornia crassipes extract is added into 100mL of mixed solution of nickel salt and iron 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 kettle in the step 1) means that the water bath kettle is heated for 5 to 6 hours at a constant temperature, and the water bath kettle is stirred for 2 to 3 minutes every 1.5 hours until the 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 step 2) means: transferring the product into a porcelain crucible, and then placing the porcelain crucible into a muffle furnace for calcination at 600-700 ℃ for 6 hours;
the grinding in step 2) means: cooling the dried sample, grinding the cooled 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 absolute ethyl alcohol and deionized water for 3 times respectively;
the drying in step 2) means: and (5) placing the mixture in a constant temperature drying oven at 80 ℃ for drying for 6-8 hours until the weight is constant.
The nickel ferrite nanoparticle provided by the invention is a cubic spherical nanoparticle with the size of 15-20 nm and has a group of phenolic compounds in eichhornia crassipes extract, has good stability and biocompatibility, and is prepared by adopting the preparation method.
The application of the nickel ferrite nano particles provided by the invention is used for preparing hydrogen by dark fermentation organisms.
The specific method for preparing hydrogen by using the nickel ferrite nano particles in dark fermentation biology comprises the following steps:
adding the prepared nickel ferrite nano particles into a fermentation culture medium, uniformly mixing, sterilizing, cooling, inoculating Klebsiella sp.
Further, the nickel ferrite nano particles are added according to the final concentration of 10-50 mg/L.
The invention adds nickel ferrite nano particles into the straw hydrolysate fermentation hydrogen production system, has obvious effect of promoting biological hydrogen synthesis and reducing sugar utilization in hydrolysate, ensures that the cumulative hydrogen production obtained under the optimal addition concentration is 1.8 times of that of the control treatment, and has the cumulative hydrogen production improvement amplitude larger than that of single added Fe 3 O 4 The sum of the increase in NP and that of single addition of NiONP. The method for synthesizing the nickel ferrite nano particles is simple, mild in operation condition, low in cost, economical and environment-friendly, and the obtained nano particles are stable in performance, uniform in particle size, good in biocompatibility and remarkable in effect of promoting hydrogen production.
Compared with the prior art, the invention has the following advantages and effects:
1. in the preparation process of the green synthesized nickel ferrite nano particles, no additional chemical reagent is added except precursor nickel salt and ferric salt, and high instrument and equipment are not needed, so that the preparation process is mild in operation condition, simple and easy to implement, economical and environment-friendly, and convenient for further expansion of production and application;
2. the nickel ferrite nano particles prepared by the invention have stable performance, uniform particle size and good biocompatibility, and when being added into a dark fermentation hydrogen production system at a certain concentration, the nickel ferrite nano particles have the effect of promoting the synthesis of biological hydrogen and the utilization of reducing sugar in straw hydrolysate, so that the cumulative hydrogen production, 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 in example 1 of the present invention;
FIG. 2 is an infrared spectrum (FTIR) of the nickel ferrite nanoparticle 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 hysteresis loop (VSM) diagram of the nickel ferrite nanoparticle 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 of the nickel ferrite nanoparticle additive of the present invention;
FIG. 9 shows glucose and xylose utilization results with nickel ferrite nanoparticles added in accordance with the present invention;
FIG. 10 shows the cumulative hydrogen production results of the addition of different nanoparticles according to the present invention.
Detailed Description
The invention is further illustrated in the following drawings and specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
The green synthesis method of the nickel ferrite nano particle comprises the following steps:
1) Taking 10g of fresh eichhornia crassipes stems and leaves, cleaning the fresh eichhornia crassipes stems and leaves with tap water and distilled water sequentially, putting the fresh eichhornia crassipes stems and leaves into a mortar, grinding the mixture into mud, adding distilled water into the mud for 3 times, adding distilled water into the mixture to obtain 50mL of distilled water, combining the precipitates each time, three times, combining the precipitates, transferring the mixture into a beaker, further putting the beaker into a water bath with the temperature of 95-100 ℃ for heating and extracting for 10min, cooling the mixture to the room temperature, carrying out suction filtration, taking supernatant and carrying out constant volume to 50mL to obtain eichhornia crassipes extract;
2) Weighing nickel chloride and ferric nitrate, and dissolving in 100mL of deionized water to make the final concentration of the nickel chloride and the ferric nitrate be 0.15mol/L and 0.30mol/L respectively; adding 50mL of the water hyacinth extract prepared above into the salt solution at room temperature, and placing the salt solution on a magnetic stirrer for continuous stirring for 20min; heating the obtained mixed solution in a water bath kettle at a constant temperature of 60 ℃ for 6 hours, stirring every 1.5 hours, and stirring for 3 minutes each time until viscous gel is obtained; drying the obtained gel in a constant temperature drying oven at 100 ℃ for 18 hours;
3) Transferring the prepared dried product into a porcelain crucible, and calcining for 6 hours at 700 ℃ in a muffle furnace; grinding the obtained dried sample into fine powder by using a mortar, sieving with a 200-mesh sieve, respectively washing for 3 times by using absolute ethyl alcohol and deionized water, and drying in a constant-temperature drying oven at 80 ℃ for 8 hours to constant weight; thus obtaining the nickel ferrite nano particles.
Characterization of green synthetic nickel ferrite nanoparticles prepared as described above:
the prepared nickel ferrite nano particles are characterized, the XRD pattern is shown in figure 1, diffraction peaks are relatively sharp, the sample has a relatively good spinel structure, 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 (111), (220), (311), (222), (400), (331), (422), (511), (440), (531), (620) and (533) crystal faces of the nickel ferrite, the sample completely accords with a standard card JCPDS (compact disc digital standard) NO.10-0325, and no other diffraction peaks exist, so that relatively pure nano nickel ferrite is prepared. FIG. 2 is an infrared spectrum of nano nickel ferrite at 603.02cm -1 、417.03cm -1 The absorption peak is strong, and the absorption peak corresponds to the stretching vibration of Fe-O, ni-O at 3442.26cm -1 、1633.24cm -1 There appears a strong surface free-OH absorption peak corresponding to H 2 Stretching and bending vibration of O molecules at 2713.35cm -1 Absorption peaks were also observed at this point, representing the-CH, C=O groups of the organic molecule, possiblyPhenolic compounds from eichhornia crassipes extract help to maintain nanoparticle stability. The SEM image of FIG. 3 reveals that the nickel ferrite nano particles have a cubic spherical structure from the surface morphology, 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 thereof shows that the average particle size of the nano particles is about 15-20 nm. Further testing magnetic performance of nano nickel ferrite, the hysteresis loop at room temperature is shown in figure 5, the green synthesized nickel ferrite nano particle has soft magnetic characteristic, and the saturation magnetization M s ＝31.30emu/g。
Example 2
The green synthesis method of the nickel ferrite nano particle comprises the following steps:
1) Taking 10g of fresh eichhornia crassipes leaves, cleaning the fresh eichhornia crassipes leaves with tap water and distilled water sequentially, grinding the fresh eichhornia crassipes leaves into mud in a mortar, adding distilled water to wash the extract for 3 times, adding 50mL of distilled water, reserving sediment each time, combining the sediment for three times, further placing the sediment in a water bath with the temperature of 95-100 ℃ to heat and extract for 10min, cooling the sediment to room temperature, carrying out suction filtration and fixing the volume to 50mL to obtain eichhornia crassipes extract;
2) Nickel acetate and ferric chloride are weighed and dissolved in 100mL of deionized water, so that the final concentration is 0.15mol/L and 0.30mol/L respectively; adding 50mL of the prepared eichhornia crassipes extract into the salt solution at room temperature, and placing the salt solution on a magnetic stirrer for continuous stirring for 20min; heating the obtained mixed solution in a water bath kettle at a constant temperature of 60 ℃ for 6 hours, and stirring for 3 minutes every 1.5 hours until viscous gel is obtained; further drying the obtained gel in a constant temperature drying oven at 100 ℃ for 17 hours;
3) Transferring the prepared dried product into a porcelain crucible, and calcining for 6 hours at 600 ℃ in a muffle furnace; grinding the obtained dried sample into fine powder by using a mortar, sieving with a 200-mesh sieve, respectively washing for 3 times by using absolute ethyl alcohol and deionized water, and drying in a constant-temperature drying oven at 80 ℃ until the weight is constant for 7 hours; the obtained nanoparticle is further subjected to XRD characterization, as shown in FIG. 6, the sample has a typical spinel structure, diffraction peaks at 18.4 degrees, 30.3 degrees, 35.7 degrees, 37.3 degrees, 43.4 degrees, 53.8 degrees, 57.4 degrees, 62.9 degrees, 71.5 degrees and 74.6 degrees respectively correspond to (111), (220), (311), (222), (400), (422), (511), (440), (620) and (533) crystal faces of nickel ferrite, and the diffraction peaks conform to the standard card JCPDS No.10-0325, but the typical (331) crystal faces of the nickel ferrite are not existed, and other diffraction peaks exist, so that the purity of the prepared nickel ferrite nanoparticle of the embodiment 1 with higher purity is not high enough, and the nickel ferrite nanoparticle is selected to be applied to dark fermentation biological hydrogen production.
Example 3
The green synthesis method of the nickel ferrite nano particle comprises the following steps:
1) Taking 10g of fresh eichhornia crassipes stems, cleaning the fresh eichhornia crassipes stems with tap water and distilled water sequentially, putting the fresh eichhornia crassipes stems into a mortar, grinding the fresh eichhornia crassipes stems into mud, adding distilled water into the mud, washing the extract for 3 times, adding 50mL of distilled water, reserving sediment each time, combining the sediment for three times, further putting the sediment into a water bath with the temperature of 95-100 ℃ for heating and extracting for 10min, cooling the solution to the room temperature, carrying out suction filtration, and fixing the volume to 50mL to obtain eichhornia crassipes extract;
2) Nickel acetate and ferric chloride are weighed and dissolved in 100mL of deionized water, so that the final concentration is 0.15mol/L and 0.30mol/L respectively; adding 50mL of the prepared eichhornia crassipes extract into the salt solution at room temperature, and placing the salt solution on a magnetic stirrer for continuous stirring for 20min; heating the obtained mixed solution in a water bath kettle at a constant temperature of 60 ℃ for 6 hours, and stirring for 3 minutes every 1.5 hours until viscous gel is obtained; further drying the obtained gel in a constant temperature drying oven at 100 ℃ for 16 hours;
3) Transferring the prepared dried product into a porcelain crucible, and calcining for 6 hours at 600 ℃ in a muffle furnace; grinding the obtained dried sample into fine powder by using a mortar, sieving with a 200-mesh sieve, washing with absolute ethyl alcohol and deionized water for 3 times, and drying in a constant-temperature drying oven at 80 ℃ for 8 hours; the obtained nanoparticle is further subjected to XRD characterization, as shown in FIG. 7, the sample has a typical spinel structure, diffraction peaks at 18.4 degrees, 30.3 degrees, 35.7 degrees, 37.3 degrees, 43.4 degrees, 53.8 degrees, 57.4 degrees, 62.9 degrees, 71.5 degrees and 74.6 degrees respectively correspond to (111), (220), (311), (222), (400), (422), (511), (440), (620) and (533) crystal faces of nickel ferrite, and the diffraction peaks conform to the standard card JCPDS No.10-0325, but the typical (331) crystal faces of the nickel ferrite are not existed, and other diffraction peaks exist, so that the purity of the prepared nickel ferrite nanoparticle of the embodiment 1 with higher purity is not high enough, and the nickel ferrite nanoparticle is selected to be applied to dark fermentation biological hydrogen production.
Example 4
The application of the nickel ferrite nano-particles prepared in the embodiment 1 is used for preparing hydrogen by dark fermentation biology.
The specific application method comprises the following steps: the nickel ferrite nano particles synthesized by the stem and leaf of the eichhornia crassipes in the embodiment 1 are added into a fermentation medium for producing hydrogen by fermenting straw hydrolysate, so that the final concentration of the nickel ferrite nano particles is 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 KH 2 PO 4 0.5g，MgSO 4 ·7H 2 O0.5 g, sugar concentration 50g/L, pH8.0. Stirring and ultrasonic treatment are adopted to fully disperse nano particles in a fermentation culture medium, after sterilization and cooling, klebsiella sp seed solution is inoculated according to 10% of inoculum size, a sodium hydroxide solution method is periodically adopted to detect hydrogen production, the hydrogen production is accumulated day by day, the accumulated hydrogen production within 120 hours is converted, and the influence of nickel ferrite nano particle addition on the biological hydrogen synthesis of a straw hydrolysate fermentation hydrogen production system is analyzed, and the result is shown in figure 8. As can be seen from the curve change in the graph, in the range of the addition concentration of 10-50 mg/L, the accumulated hydrogen production of the strain fermentation for 120h is higher than that of the control treatment (0 mg/L), which shows that the nano particles have a wider hydrogen production promotion range and show good biocompatibility. Wherein, the accumulated hydrogen yield of 30mg/L nano nickel ferrite is highest, the accumulated hydrogen yield of 120h fermentation can reach 5956.3 +/-39.8 mL/L, which is 1.8 times of that of the control treatment (0 mg/L), which shows that the treatment can obviously promote Klebsiella sp.
The preparation of seed bacteria and straw hydrolysate of hydrogen-producing bacteria Klebsiella sp in this example is reported in the literature (research on transcriptional control mechanism of enhanced Klebsiella sp. Fermentation hydrogen production) on green synthesis of metal nanoparticles (Ding Pengfei, 2020).
The influence of the synthesized nickel ferrite nano particles on Klebsiella sp. The influence of glucose and xylose in straw hydrolysate is utilized:
the effect of nano nickel ferrite addition on the utilization rate of reducing sugar (glucose and xylose) in the straw hydrolysate was analyzed by periodically taking the fermentation broth, centrifuging, and detecting the concentration of glucose and xylose in the supernatant, and the result is shown in fig. 9. The results of FIG. 9 show that all treatments with nickel ferrite nanoparticles are beneficial to the utilization of reducing sugar in straw hydrolysate by hydrogen-producing bacteria, and the glucose and xylose utilization rate is improved compared with that of the control treatment (0 mg/L), especially the glucose and xylose utilization rate with the concentration of 30mg/L is highest (96.4% and 96.3%), and the glucose and xylose utilization rate is improved by 8.0% and 8.9% respectively compared with that of the control treatment (0 mg/L).
The nickel ferrite nano particles prepared by the invention influence the comparative analysis of dark fermentation hydrogen production:
ferroferric oxide nanoparticles (Fe) were added according to the method provided in example 4 3 O 4 NP), nickel oxide nanoparticles (NiONP), nickel ferrite nanoparticles (NiFe 2 O 4 NP) to a straw hydrolysate fermentation hydrogen production system and inoculation of a hydrogen producing bacterium Klebsiella sp, the three nanoparticles being in optimal concentration (Fe 3 O 4 NP 20mg/L、NiONP20mg/L、NiFe 2 O 4 NP 30 mg/L) was added, and the treatment without nanoparticles was used as a control treatment; the effect of different nanoparticle additions on the hydrogen production by fermentation of straw hydrolysate was analyzed by measuring the hydrogen volume and converting the cumulative hydrogen production by the method provided in example 2, and the results are shown in fig. 10. FIG. 10 shows that three nanoparticles are effective in promoting biohydrogen synthesis by hydrogen producing bacteria at optimal additive concentrations to yield significantly higher cumulative hydrogen production, particularly NiFe, than control treatments 2 O 4 The NP has the most obvious effect of promoting hydrogen production, which shows that the nano particles have the effect of promoting hydrogen production by coupling Fe and Ni, and the increasing range (80.0%) of the accumulated hydrogen production is larger than that of the single Fe 3 O 4 The sum of the increase of NP (20.0%) and that of single NiONP (46.4%) shows that NiFe prepared by the method 2 O 4 NP has the effect of promoting hydrogen production by coupling Fe and Ni, and the effect is better than that of singly adding Fe 3 O 4 NP or single additionNiONP.
Example 5
Application of the nickel ferrite nanoparticle prepared in example 1 in hydrogen production by fermentation of straw hydrolysate by enterobacter cloacae.
The nickel ferrite nano particles synthesized by the stem and leaf of Eichhornia crassipes in example 1 are added to a hydrogen production medium of a fermentation straw hydrolysate of Enterobacter cloacae in the treatment mode of example 4, and the formula of the medium is the same as that of example 4, and the detection and conversion of hydrogen production by fermentation and hydrogen production are carried out by adopting the method consistent with that of example 4. The result shows that the nickel ferrite nano particles added with the concentration of 10-50 mg/L can promote the increase of the hydrogen production of enterobacter cloacae, so that the accumulated hydrogen production of the fermentation for 120 hours is higher than that of the control treatment (0 mg/L), and the accumulated hydrogen production obtained when the nano nickel ferrite with the concentration of 20mg/L is added is highest and reaches 5057.8 +/-110.9 mL/L, which is 45.9 percent higher than that of the control treatment. The application effects of the embodiment and the embodiment 4 show that the nickel ferrite nano particles prepared by the invention have obvious hydrogen production promoting effect on pure culture hydrogen-producing bacteria, and show good biocompatibility.
The Enterobacter cloacae producing hydrogen in the embodiment is a hydrogen producing strain reported in the literature (Qu Xiaowei, etc. 2018) on the influence of segmented pH value regulation on the hydrogen production of hydrolyzed sugar solution of cotton stalk fermented by the Enterobacter cloacae WL 1318.
Claims (9)
1. A method for preparing nickel ferrite nano-particles, which is characterized by comprising the following steps:
1) Adding the water hyacinth extract into the mixed solution of nickel salt and ferric salt at room temperature, continuously stirring for reaction, heating at constant temperature in a water bath kettle for reaction to obtain viscous gel, and drying;
2) Calcining, grinding, washing and drying the product of the step 1) to obtain nickel ferrite nano particles;
the preparation method of the eichhornia crassipes extracting solution in the step 1) comprises the following steps:
taking 10g of fresh eichhornia crassipes, cleaning with tap water or distilled water successively, grinding into mud in a mortar, adding distilled water to wash the extract for 3 times, adding 50mL of distilled water, reserving precipitate each time, combining the precipitates for three times, heating and extracting in a water bath at 95-100 ℃ for 10min, cooling to room temperature, carrying out suction filtration, taking the supernatant, and fixing the volume to 50mL to obtain the eichhornia crassipes extract;
the nickel ferrite nano particles are in a cubic sphere shape with the size of 15-20 nm.
2. The method according to claim 1, wherein in step 1), ni is contained in the mixed solution of the nickel salt and the iron salt 2+ And Fe (Fe) 3+ The molar ratio is 1:2.
3. The preparation 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 are 0.15mol/L and 0.30mol/L respectively.
4. The preparation method according to claim 1, wherein in the step 1), the volume ratio of the eichhornia crassipes extracting solution to the mixed solution of nickel salt and iron salt is 1:2.
5. the preparation method according to claim 1, wherein the constant temperature heating reaction in the water bath in the step 1) means constant temperature heating in the water bath at 60 ℃ for 5-6 hours, and stirring for 2-3 minutes every 1.5 hours until the viscous gel is obtained.
6. The method according to claim 1, wherein the calcination in step 2) means: transferring the product into a porcelain crucible, and calcining for 6 hours at 600-700 ℃ in a muffle furnace.
7. A nickel ferrite nanoparticle prepared by the method of any one of claims 1-6.
8. Use of the nickel ferrite nanoparticle prepared by the preparation method of any one of claims 1-6 for the production of hydrogen by dark fermentation organisms.
9. The application according to claim 8, characterized in that the application specific method is:
adding nickel ferrite nano particles into a fermentation culture medium, uniformly mixing, sterilizing, cooling, inoculating Klebsiella sp.
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