CN115608376B - Palladium-iron nanomaterial based on saccharomycete residues as well as preparation method and application thereof - Google Patents

Palladium-iron nanomaterial based on saccharomycete residues as well as preparation method and application thereof Download PDF

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CN115608376B
CN115608376B CN202211260962.1A CN202211260962A CN115608376B CN 115608376 B CN115608376 B CN 115608376B CN 202211260962 A CN202211260962 A CN 202211260962A CN 115608376 B CN115608376 B CN 115608376B
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iron
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yeast
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谢建平
王国桢
刘宇星
崔浩
董海刚
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Central South University
Sino Platinum Metals Co Ltd
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Sino Platinum Metals Co Ltd
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Abstract

The invention relates to the technical field of metal nano materials, and provides a palladium-iron nano material based on saccharomycete residues, and a preparation method and application thereof. Mixing yeast residue and palladium-iron solution to obtain a palladium-iron adsorption bacterial residue material; and in a protective atmosphere, pyrolyzing the bacteria slag material absorbing palladium-iron and potassium hydroxide to obtain the palladium-iron nano material based on the yeast slag. Through adsorption-pyrolysis, the yeast residue forms a porous microbial carbon structure and supports FePd with a simple cubic structure 3 A nanocrystal. The surface elements of the material are uniformly distributed, can be quickly separated from the suspension with the help of the magnet, and can be quickly dispersed in the solution again after the magnet is removed for repeated use. Applied to reduction catalytic reaction of p-nitrophenol (p-NP), the apparent rate constant is 1.85 multiplied by 10 ‑1 In the reaction of 5 continuous cycles, the conversion rate reaches 96.6-98.9%.

Description

Palladium-iron nanomaterial based on saccharomycete residues as well as preparation method and application thereof
Technical Field
The invention relates to the technical field of metal nano materials, in particular to a palladium-iron nano material based on saccharomycete residues, and a preparation method and application thereof.
Background
The metal nanomaterials prepared from noble metals are very active in catalytic reduction reactions and have been widely used for cross-coupling reactions of carbon-carbon and carbon-heteroatom bonds and many directed, non-directed C-H activation reactions, with high conversion rates making them more efficient than other catalytic systems. The microorganism has a large number of oxygen-containing functional groups, can be tightly combined with noble metal ions without pretreatment, is stably and uniformly dispersed on the surface of the microorganism or the metal ions entering the interior of the microorganism through a transfer mechanism are reduced into metal nano particles through the microorganism and external gas, and then the carbon-loaded metal nano material is formed at a certain temperature.
The nano particles synthesized by utilizing microorganism adsorption-reduction of noble metal ions have small size and uniform dispersion, and meanwhile, the microbial thalli are natural carbon sources, nitrogen sources and the like, and the catalytic activity of the microbial carbon-loaded noble metal nano material is further improved through heteroatom doping generated by carbonized bacteria. However, the use of the conventional preparation of microbial carbon-supported noble metal nanomaterials is limited to a certain extent based on the high cost of noble metals and the complexity of separation, recovery, and reuse. In addition, compared with a single metal material, the synergistic effect of the bimetal enables the alloy nano material to show higher catalytic efficiency and more stable catalytic activity in catalytic reduction and catalytic oxidation. Liu et al reduced metal ions (Pd and Au) adsorbed on the surface of the cells by using electrochemically active bacteria Shewanella oneidensis MR-1, and alloyed the bimetal by hydrothermal reaction to synthesize Pd-Au alloy nanoparticles in situ. The electrochemically active bacteria are used as metal ion reducing agent, nanometer particle support carrier and heteroatom source to replace toxic surfactant, stabilizer and chemical reducing agent. The alloyed noble metal nano material reduces the preparation cost of the noble metal nano material and improves the catalytic performance. However, no research on magnetically separable alloying noble metal nano-materials based on microbial carbon carriers exists at present, so that the construction of a magnetically separable microbial carbon-supported noble metal nano-material is a current urgent problem to be solved.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a palladium-iron nanomaterial based on saccharomycete residues, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a palladium-iron nanomaterial based on yeast residues, which comprises the following steps:
(1) Mixing yeast residue and palladium-iron solution to obtain a palladium-iron adsorption bacterial residue material;
(2) And in a protective atmosphere, pyrolyzing the bacteria residue material absorbing palladium-iron and potassium hydroxide to obtain the palladium-iron nano material based on the yeast residue.
Preferably, the solvent of the palladium-iron solution is hydrochloric acid, and the concentration of the hydrochloric acid is 0.09-0.11M.
Preferably, the concentration of palladium ions in the palladium-iron solution in the step (1) is 90-110 mg/L, and the concentration of iron ions in the palladium-iron solution is 90-110 mg/L.
Preferably, in the step (1), the mass ratio of the yeast residue to the metal ions in the palladium-iron solution is 9-11: 1.
preferably, the rotation speed of the mixing in the step (1) is 130-170 rpm, the temperature of the mixing is 20-30 ℃, and the mixing time is 10-14 h.
Preferably, the mass ratio of the yeast residue in the step (1) to the potassium hydroxide in the step (2) is 9-11: 10 to 12.
Preferably, the heating rate of the pyrolysis in the step (2) is 4-6 ℃/min, the target temperature of the pyrolysis is 500-800 ℃, and the constant temperature time after the pyrolysis reaches the target temperature is 1.5-2.5 h.
The invention also provides the palladium-iron nano material based on the saccharomycete residues, which is obtained by the preparation method.
The invention also provides application of the palladium-iron nano material based on the yeast slag in reduction catalytic reaction of p-nitrophenol.
The beneficial effects of the invention are as follows:
(1) The invention provides a preparation method of a palladium-iron nano material based on saccharomycete residues, which comprises the steps of mixing saccharomycete residues with palladium-iron solution to obtain a palladium-iron adsorption microbial residue material; and in a protective atmosphere, pyrolyzing the bacteria slag material absorbing palladium-iron and potassium hydroxide to obtain the palladium-iron nano material based on the yeast slag. Through adsorption-pyrolysis, the yeast residue forms a porous microbial carbon structure and supports FePd with a simple cubic structure 3 A nanocrystal. The method provided by the invention has the advantages of simple preparation process and strong practicality and operability.
(2) The palladium-iron nano material based on the saccharomycete residues is of a multi-layer porous structure, nano particles are attached to the porous structure, the average size of the nano particles is 25.16nm, and C, N, O, P on the surface of the material, pd and Fe elements are uniformly distributed; the hysteresis loop of the material is thin and narrow, the soft magnetic ordering property of the sigmoid function shape is shown, the material is very sensitive to an external magnetic field, the material can be rapidly separated from suspension with the help of a magnet, and the characteristic of easy demagnetization can enable nano particles to be rapidly dispersed in a solution again for repeated recycling.
(3) The palladium-iron nano material based on the saccharomycete residues, provided by the invention, is applied to reduction catalytic reaction of p-nitrophenol, and has an apparent rate constant of 1.85 multiplied by 10 -1 And/s, which is superior to the related report of the existing noble metal catalyst in the same reaction system, the unique abundant porous structure of the microbial carbon enables the nanocrystalline to be sufficiently dispersed on the surface of the carrier, thereby becoming a good electron transmission carrier and accelerating the reaction. In addition, the palladium-iron nano material based on the saccharomycete residues has good recycling performance as a p-NP reduction catalyst, and the conversion rate reaches 96.6% -98.9% in the continuous 5-cycle reaction.
Drawings
FIG. 1 shows BC-FePd in example 1 3 Scanning electron microscope images of (a);
FIG. 2 is example 1BC-FePd in 3 Is a spectrum analysis chart of (1);
FIG. 3 shows BC-FePd in example 1 3 Transmission electron microscopy at 200 nm;
FIG. 4 shows BC-FePd in example 1 3 Transmission electron microscopy at 5 nm;
FIG. 5 shows BC-FePd in example 1 3 Is a dimensional profile of (a);
FIG. 6 shows BC-FePd at different pyrolysis temperatures in example 1 3 An XRD pattern of (b);
FIG. 7 is a schematic diagram of BC-FePd at different pyrolysis temperatures in example 1 3 Grain size and lattice parameter diagram of (a);
FIG. 8 is a chart of BC-FePd at different pyrolysis temperatures in example 1 3 A field-dependent magnetization curve graph of the material under a magnetic field of-20000 to 20000 Oe;
FIG. 9 is a chart of BC-FePd at different pyrolysis temperatures in example 1 3 A field dependent magnetization curve graph of the material under a magnetic field of-80 Oe;
FIG. 10 is a chart of BC-FePd at different pyrolysis temperatures in example 1 3 An apparent rate plot of catalytic reduction of p-NP;
FIG. 11 shows BC-FePd having a pyrolysis temperature of 700℃in example 1 3 UV-vis spectrogram after material;
FIG. 12 shows BC-FePd having a pyrolysis temperature of 700℃in example 1 3 Reusability map of catalytically reduced p-NPs.
Detailed Description
The invention provides a preparation method of a palladium-iron nanomaterial based on yeast residues, which comprises the following steps:
(1) Mixing yeast residue and palladium-iron solution to obtain a palladium-iron adsorption bacterial residue material;
(2) And in a protective atmosphere, pyrolyzing the bacteria residue material absorbing palladium-iron and potassium hydroxide to obtain the palladium-iron nano material based on the yeast residue.
In the invention, saccharomycete fragments are sequentially centrifuged, washed, freeze-dried, crushed, ground, sieved and secondarily dried to obtain saccharomycete residues.
The rotational speed of the centrifugation is preferably 9000 to 11000rpm, more preferably 9500 to 10500rpm, and still more preferably 9800 to 10200rpm; the centrifugation time is preferably 8 to 12 minutes, more preferably 9 to 11 minutes, and still more preferably 9.5 to 10.5 minutes; the washed reagent is ultrapure water, and the washing is carried out until the upper layer is clarified; the temperature of the freeze drying is preferably-50 to-60 ℃, more preferably-52 to-58 ℃, and even more preferably-54 to-56 ℃; the time for the freeze-drying is preferably 6 to 10 hours, more preferably 7 to 9 hours, and still more preferably 7.5 to 8.5 hours; the mesh number during the sieving is preferably 150 to 250 mesh, more preferably 170 to 230 mesh, and still more preferably 200 mesh; the temperature of the secondary drying is preferably 20 to 30 ℃, more preferably 22 to 28 ℃, still more preferably 24 to 26 ℃, and the time of the secondary drying is preferably 4 to 8 hours, more preferably 5 to 7 hours, still more preferably 5.5 to 6.5 hours.
In the present invention, the solvent of the palladium-iron solution is hydrochloric acid, and the concentration of the hydrochloric acid is preferably 0.09 to 0.11M, more preferably 0.095 to 0.105M, and still more preferably 0.098 to 0.102M.
In the present invention, the concentration of palladium ions in the palladium-iron solution in the step (1) is preferably 90 to 110mg/L, more preferably 95 to 105mg/L, and still more preferably 98 to 102mg/L; the concentration of iron ions in the palladium-iron solution is preferably 90 to 110mg/L, more preferably 95 to 105mg/L, and even more preferably 98 to 102mg/L.
In the invention, in the palladium-iron solution, the palladium source is PdCl 2 ·2H 2 O, iron source is FeCl 3 ·6H 2 O。
In the invention, the mass ratio of the yeast residue in the step (1) to the metal ions in the palladium-iron solution is preferably 9-11: 1, more preferably 9.5 to 10.5:1, more preferably 9.8 to 10.2:1.
in the present invention, the rotational speed of the mixing in the step (1) is preferably 130 to 170rpm, more preferably 135 to 165rpm, still more preferably 145 to 155rpm; the temperature of the mixing is preferably 20 to 30 ℃, more preferably 22 to 28 ℃, and even more preferably 24 to 26 ℃; the mixing time is preferably 10 to 14 hours, more preferably 11 to 13 hours, and still more preferably 11.5 to 12.5 hours.
In the invention, after the mixing is finished, the bacteria residue material absorbing palladium-iron is sequentially subjected to suction filtration, freezing and drying.
In the present invention, the freezing temperature is preferably-15 to-25 ℃, more preferably-17 to-23 ℃, and even more preferably-19 to-21 ℃; the time for the freezing is preferably 10 to 14 hours, more preferably 11 to 13 hours, and still more preferably 11.5 to 12.5 hours.
In the present invention, the drying temperature is preferably-50 to-60 ℃, more preferably-52 to-58 ℃, and even more preferably-54 to-56 ℃; the drying time is preferably 6 to 10 hours, more preferably 7 to 9 hours, and even more preferably 7.5 to 8.5 hours; the vacuum degree of the drying is preferably 50Pa or less, more preferably 30Pa or less, and still more preferably 10Pa or less.
In the invention, after the drying of the bacteria residue material absorbing palladium-iron is finished, the bacteria residue material is mixed with potassium hydroxide for pyrolysis.
In the invention, the mass ratio of the yeast residue in the step (1) to the potassium hydroxide in the step (2) is preferably 9-11: 10 to 12, more preferably 9.5 to 10.5:10.5 to 11.5, more preferably 9.7 to 10.3:10.7 to 11.3.
In the invention, the bacteria residue material absorbing palladium-iron and potassium hydroxide are mixed and then placed in a muffle furnace for pyrolysis, wherein the heating rate of the pyrolysis is preferably 4-6 ℃/min, more preferably 4.5-5.5 ℃/min, and even more preferably 4.8-5.2 ℃/min; the target temperature of the pyrolysis is preferably 500 to 800 ℃, more preferably 600 to 700 ℃, and even more preferably 620 to 680 ℃; the constant temperature time after pyrolysis reaches the target temperature is preferably 1.5 to 2.5 hours, more preferably 1.7 to 2.3 hours, and still more preferably 1.9 to 2.1 hours.
In the invention, KOH high-temperature activation is favorable for forming a multi-layer porous structure inside the biochar, and when KOH exists, pyrolysis and activation simultaneously occur in the heating process, namely H is removed 2 O, release H 2 And CO, etc., the KOH dehydrates and etches carbon at high temperature to form carbon dioxide and carbon monoxide gas, and a hole structure is generated.
In the invention, natural cooling, cleaning, drying and grinding are sequentially carried out after pyrolysis is finished.
In the present invention, the target temperature for natural cooling is preferably 20 to 30 ℃, more preferably 22 to 28 ℃, and even more preferably 24 to 26 ℃.
In the present invention, the washing is a primary washing and a secondary washing which are sequentially performed; the one-time cleaning reagent is preferably deoxidized ultrapure water, and the number of times of one-time cleaning is preferably 2 times or more, more preferably 3 times or more, and still more preferably 4 times or more; the reagent for the secondary cleaning is hydrochloric acid, and the concentration of the hydrochloric acid is preferably 0.05-0.15M, more preferably 0.07-0.013M, and even more preferably 0.09-0.011M; the number of times of the secondary washing is preferably 2 times or more, more preferably 3 times or more, and still more preferably 4 times or more.
In the present invention, washing the synthesized sample with HCl can effectively remove potassium compounds, forming a carbon support structure with micropores and mesopores of large surface area.
In the present invention, the drying temperature is preferably 30 to 80 ℃, more preferably 40 to 60 ℃, still more preferably 45 to 55 ℃; the drying time is preferably 6 to 10 hours, more preferably 7 to 9 hours, and even more preferably 7.5 to 8.5 hours; the vacuum degree of the drying is preferably 50Pa or less, more preferably 30Pa or less, and still more preferably 10Pa or less.
The invention also provides the palladium-iron nano material based on the saccharomycete residues, which is obtained by the preparation method.
The invention also provides application of the palladium-iron nano material based on the yeast slag in reduction catalytic reaction of p-nitrophenol.
In the present invention, the yeast fragments are obtained from Hunan Fu Lager biotechnology Co., ltd.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Centrifuging yeast fragments at 10000rpm for 10minWashing with ultrapure water to clarify the upper layer, freeze-drying at-55deg.C for 8 hr, pulverizing, grinding, sieving with 200 mesh sieve, and secondary drying at 25deg.C for 6 hr to obtain yeast residue; pdCl is added to 2 ·2H 2 O and FeCl 3 ·6H 2 O is dissolved in 0.1M hydrochloric acid to obtain palladium-iron solution; 1g of fungus dreg is weighed and added into 500mL of palladium-iron solution, wherein Pd in the palladium-iron solution 2+ The mass concentration of (2) is 100mg/L, fe 3+ The mass concentration of (2) is 100mg/L; oscillating and absorbing for 12 hours at 25 ℃ at a rotating speed of 150rpm to obtain a palladium-iron-absorbed bacterial dreg material; filtering the material, and freezing at-20deg.C for 12 hr; drying for 8h under the condition that the vacuum degree is 10Pa and the temperature is-55 ℃; mixing with 1.1g KOH after finishing, placing in a muffle furnace, heating to 700 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2h; and naturally cooling to 25 ℃ after heat preservation is finished, taking out, washing with deoxidized ultrapure water for 2 times, washing with hydrochloric acid with the concentration of 0.1M for 3 times, drying for 8 hours under the condition that the vacuum degree is 8Pa and the temperature is 50 ℃, and grinding to obtain the palladium-iron nano material based on the saccharomycete residues.
The yeast residue based palladium-iron nanomaterial prepared in this example (labeled BC-FePd) was observed using a scanning electron microscope (SEM, zeiss, sigma 300) equipped with an energy dispersive x-ray (EDS) analysis system 3 ) Form and composition of (C) to obtain BC-FePd 3 As shown in fig. 1; BC-FePd 3 As shown in fig. 2; observation of BC-FePd with a Transmission Electron microscope (TEM, JEM 2100F) 3 Microstructure, crystal morphology and dispersity of the obtained BC-FePd 3 Transmission electron microscopy at 200nm as shown in fig. 3; BC-FePd 3 Transmission electron microscopy at 5nm as shown in fig. 4; analyzing the crystal composition and the growth surface by photographing high-resolution contrast stripes of the material, and carrying out size and lattice spacing analysis on the Nano particles in FIG. 3 by combining Nano Measure 1.2 and Gatan DigitalMicrograph to obtain BC-FePd 3 As shown in fig. 5. As is evident from FIG. 1, BC-FePd 3 The porous structure is a multilayer porous structure, and nano particles are attached to the porous structure; as can be taken from fig. 5, the average size of the nanoparticles is 25.16nm;as can be seen from FIG. 4, lattice spacings of 0.222nm and 0.193nm correspond to FePd, respectively 3 The (111) and (200) growth surfaces of the card (JCPDS 65-3253) show that the pyrolysis process synthesizes FePd 3 A nanomaterial. As can be seen from FIG. 2, BC-FePd 3 The C, N, O, P and Pd and Fe elements on the surface are uniformly distributed.
The comparative example of this example was set, keeping other conditions unchanged, and the pyrolysis temperatures were replaced with 500 ℃, 600 ℃ and 800 ℃ respectively, to obtain a yeast residue-based palladium-iron nanomaterial at different pyrolysis temperatures.
Adopting X-ray diffraction (XRD, bruker D8 advance), taking Cu Ka as a radiation source, scanning at 5-90 degrees (scanning speed is 5 degrees/min), and researching BC-FePd obtained at different pyrolysis temperatures 3 The material has the advantages that the phase structure, phase components, grain size, grain orientation and the like of the material are adopted, the diffraction peak of crystals is fitted, the grain size is calculated by utilizing a Debye-Scherer formula, the crystal structure of the nanocomposite is analyzed by adopting Jade 6.5 software, and BC-FePd at different pyrolysis temperatures is obtained 3 As shown in figure 6; BC-FePd at different pyrolysis temperatures 3 As shown in fig. 7. As can be seen from FIG. 6, diffraction peaks at positions of 23.08 °, 32.86 °, 40.54 °, 47.16 °, 53.14 °, 58.68 °, 68.91 °, 73.75 °, 78.47 °, 83.12 °, and 87.72℃in 2. Theta. Correspond to FePd3 cards (JCPDS 65-3253) with high crystallinity, and represent FePd, respectively 3 The (100), (110), (111), (200), (210), (211), (220), (300), (310), (311) and (222) crystal planes of (C) indicate that FePd is formed 3 Nanocrystalline, which is a simple cubic structure. As can be obtained by combining fig. 6 and fig. 7, the material prepared at 500 ℃ has a wide diffraction peak and peak shape and accompanies some impurity phases, which indicates that the nanocrystalline prepared at the temperature has small size and poor crystallinity. As the pyrolysis temperature increases, the impurity phase disappears, the diffraction peak is gradually sharp, the intensity increases, and when the temperature reaches 700 ℃, the diffraction peak is narrow and strong, which indicates that the crystallinity of the material prepared at the pyrolysis temperature of 700 ℃ is highest. The diffraction peak of the crystal prepared at 800 ℃ is widened, the intensity is reduced, the peak position is shifted rightwards, and a small amount of impurity peak appears, which is probably caused by FePd due to the too high pyrolysis temperature 3 Grain portionDecomposing the mixture to generate an impurity phase; as the pyrolysis temperature increases, the average size of the grains increases from 12nm to 17nm, and when the pyrolysis temperature is 800 ℃, the grain size decreases to 13nm; the lattice parameter of the crystal grains is not greatly changed when the pyrolysis temperature is 500 ℃ to 700 ℃, and the lattice parameter is obviously reduced when the pyrolysis temperature is 800 ℃, which indicates that FePd prepared by the pyrolysis temperature 3 The internal components and the stress state of the crystal change.
Testing BC-FePd using vibrating sample magnetometer (VSM, PPMS-9) under temperature test conditions of + -2T range and 300K 3 Hysteresis loop and basic magnetic parameters of the material to obtain BC-FePd at different pyrolysis temperatures 3 A field dependent magnetization curve diagram of the material under the magnetic field of-20000 to 20000Oe is shown in fig. 8; BC-FePd at different pyrolysis temperatures 3 A field dependent magnetization curve of the material under a magnetic field of-80 to 80Oe is shown in fig. 9; BC-FePd 3 As shown in table 1. As can be seen from fig. 8 and 9, the hysteresis loop is thin and narrow, and all samples show soft magnetic ordering properties of sigmoid function shape, so that the samples are very sensitive to external magnetic field, can be rapidly separated from suspension with the help of magnet, and can be repeatedly used by dispersing nano particles in solution again rapidly due to the characteristic of easy demagnetization. As can be obtained by combining fig. 8, 9 and table 1, the magnitudes of the saturation magnetization Ms, the remanence Mr, and the coercive force Hc are closely related to the microstructure of the material, the internal stress, and the impurity content. As the pyrolysis temperature of the material increases, the Ms of the material increases uniformly from 26.26emu/g to 46.95emu/g; the pyrolysis temperature is increased from 500 ℃ to 700 ℃, the Mr of the sample is increased from 1.11emu/g to 3.30emu/g, and when the pyrolysis temperature is 800 ℃, the Mr is reduced to 3.00emu/g; as the pyrolysis temperature of the material increases, hc increases from 72Oe at 500℃ to 79Oe at 700℃, and then Hc decreases to 38Oe. FePd (FePd) 3 The degree of order of the structure is related to Hc, with the greater Hc, the higher the degree of order. The test results show that the samples prepared at a pyrolysis temperature of 600 ℃ are the highest in order, while the samples prepared at a pyrolysis temperature of 800 ℃ are the lowest in order. It is known that the pyrolysis temperature may be changed by changing the microstructure of the magnetic nanomaterial so that the magnetic nanomaterial exhibits different saturation magnetization, remanence, and coercivity at different pyrolysis temperatures.
TABLE 1 BC-FePd 3 Magnetic parameter meter for material
2mg of the yeast residue-based palladium-iron nanomaterial prepared in this example was weighed, 4mL of 1mM p-nitrophenol (p-NP) solution was added, and 1mL of 0.1M NaBH was added 4 The solution is used for measuring the ultraviolet visible absorption spectrum of a reaction product by using a UV-2600 ultraviolet spectrophotometer, and the catalytic reaction rate is calculated by adopting a quasi-first order kinetic equation, wherein the calculation formula is as follows: ln (C/C) 0 )＝ln(A/A 0 ) = -kt, where C is the concentration of p-NP at time t and k is the apparent rate constant. Obtaining the BC-FePd at the fitted different pyrolysis temperatures 3 An apparent rate plot of the catalytic reduction of p-NPs as shown in FIG. 10; BC-FePd with pyrolysis temperature of 700 DEG C 3 A UV-vis spectrum of the material, as shown in fig. 11; BC-FePd obtained in this example 3 Comparison with existing noble metal catalysts gave a comparison table of different catalyst systems, as shown in table 2. As can be derived from FIG. 10, BC-FePd 3 The pyrolysis temperature is 500 ℃, 600 ℃,700 ℃ and 800 ℃ respectively, and the k value of the catalytic p-NP reduction is 4.37 multiplied by 10 respectively -2 /s、4.46×10 -2 /s、1.85×10 -1 /s、8.30×10 -2 And/s, as the pyrolysis temperature is increased, the catalytic reaction rate of the material is faster, the catalytic activity is higher, and the catalytic performance of the material prepared at 800 ℃ is slightly reduced. As can be seen from the XRD data, the catalytic performance of the material is influenced by the crystallinity, and the catalytic activity and BC-FePd shown by the material in the p-NP catalytic reduction test 3 The change trend of the crystallinity is consistent. As can be seen from a combination of FIGS. 10, 11 and Table 2, the apparent rate constant of the samples prepared at 700℃was 1.85X 10 -1 And/s, is superior to the related report of the existing noble metal catalyst in the same reaction system. The special abundant porous structure of the microbial charcoalThe nano-crystal is dispersed on the surface of the carrier, so that the nano-crystal becomes a good electron transmission carrier, and the reaction is quickened. The pyrolysis temperature causes the internal components and stress of the material to change, the alloy effect generated by the bimetal and the interaction between metal and carbon to play an important role in enhancing the catalytic activity of the material by adjusting the electronic structure of the nano material.
Table 2 comparison of different catalyst systems
Literature 1 is Ilgin, p.; ozay, o.; ozay, h., A novel hydrogel containing thioether group as selective support material forpreparation ofgold nanoparticles: synthesis and catalytic applications applied Catalysis B-Environmental 2019,241,415-423.
Literature 2 is Thanh Binh, n.; huang, c.p.; doong, R. -a., enhanced catalytic reduction of nitrophenols by sodium borohydride over highly recyclable Au@graphic carbon nitride nanocomposites.applied Catalysis B-Environmental 2019,240,337-347.
Literature 3 is Fu, y; huang, t.; jia, b; zhu, j.; wang, X., reduction of nitrophenols to aminophenols under concerted catalysis by Au/g-C 3 N 4 contact system.Applied Catalysis B-Environmental 2017,202,430-437.
Literature 4 is Fu, j.; wang, s.; zhu, j.; wang, k; gao, m; wang, x.; xu, q., au-Ag bimetallic nanoparticles decorated multi-amino cyclophosphazene hybrid microspheres as enhanced activity catalysts for the reduction of4-nitrophenol.
Literature 5 is Mao, h; ji, c; liu, m; cao, z.; sun, d.; xing, Z.; chen, x; zhang, y; song, X. -M. -Enhanced catalytic activity of Ag nanoparticles supported on polyacrylamide/polypyrrole/graphene oxide nanosheets forthe reduction of-nitrophenol. Applied Surface Science 2018,434,522-533.
Document 6 is Xu, y; shi, x; hua, r.; zhang, r.; yao, y; zhao, b.; liu, t.; zheng, j.; lu, g., remarkably catalytic activity in reduction of4-nitrophenol and methylene blue by Fe 3 O 4 @COF supported noble metal nanoparticles.Applied Catalysis B-Environmental 2020,260.
Document 7 is Chan, h.f.; shi, c.c.; wu, z.x.; sun, s.h.; zhang, s.k.; yu, z.h.; he, m.h.; chen, g.x.; wan, x.f.; tie, j.f., superhydrophilic three-dimensional porous spent coffee ground reduced palladium nanoparticles for efficient catalytic reduction. Journal of Colloid and Interface Science 2022,608,1414-1421.
Literature 8 is Yan, z.l.; fu, L.J.; zuo, x.c.; yang, H.M., green assembly of stable and uniform silver nanoparticles on 2D silica nanosheets for catalytic reduction of4-nitrophenol.applied Catalysis B-Environmental 2018,226,23-30.
Document 9 is Xu, h; xiao, y; xu, m; cui, h.; tan, l.; feng, n.; liu, x; qiu, g.; dong, h.; xie, J., microbial synthesis of Pd-Pt alloy nanoparticles using Shewanella oneidensis MR-1with enhanced catalytic activity fornitrophenol and azo dyes reduction.Nanotechnology 2019,30 (6).
In addition to simple synthetic strategies and excellent catalytic activity, catalyst reusability is also critical for practical use. The BC-FePd was tested in this study by successive catalytic reaction cycles 3 Is not limited, and the reuse performance of the same is improved. After completion of the above reaction, the material was separated from the reaction solution by an external magnet, and 4mL of 1mM p-NP solution and 1mL of 0.1M NaBH were added again 4 Continuously reacting the solution for 5 cycles to obtain BC-FePd 3 A reusability map of the catalytic reduction p-NPs as shown in FIG. 12; as can be seen from FIG. 12, the conversion rate reached 96.6% -98.9% in the continuous 5-cycle reaction, indicating BC-FePd 3 As pThe NP reduction catalyst has good recycling properties.
Example 2
Centrifuging the saccharomycete fragment at 9000rpm for 12min, washing with water until the saccharomycete fragment is clarified, freeze-drying at-58 ℃ for 7h, crushing and grinding, sieving with a 150-mesh sieve, and secondary drying at 27 ℃ for 5h to obtain saccharomycete residues; pdCl is added to 2 ·2H 2 O and FeCl 3 ·6H 2 O is dissolved in 0.105M hydrochloric acid to obtain palladium-iron solution; 1.1g of fungus dreg is weighed and added into 500mL of palladium-iron solution, wherein Pd in the palladium-iron solution 2+ The mass concentration of (2) is 105mg/L, fe 3+ The mass concentration of (2) is 106mg/L; oscillating and absorbing for 13h at 27 ℃ at 160rpm to obtain a palladium-iron-absorbed bacterial dreg material; filtering the material, freezing at-22deg.C for 11 hr, and drying at-57 deg.C under vacuum degree of 9Pa for 7.5 hr; mixing with 1.2g KOH after finishing, placing in a muffle furnace, heating to 800 ℃ at a heating rate of 6 ℃/min, and preserving heat for 2.3h; and naturally cooling to 27 ℃ after heat preservation is finished, taking out, cleaning for 3 times by using deoxidized ultrapure water, cleaning for 2 times by using hydrochloric acid with the concentration of 0.15M, drying for 7 hours under the condition that the vacuum degree is 10Pa and the temperature is 55 ℃, and grinding to obtain the palladium-iron nano material based on the saccharomycete residues.
The sample obtained in this example was tested for catalytic performance and cycle performance by the same test method as in example 1 to obtain a palladium-iron nanomaterial based on yeast residue having an apparent rate constant of 8.51X10 in this example -2 S; in the reaction of 5 continuous cycles, the conversion rate reaches 96.3% -98.7%.
Example 3
Centrifuging the saccharomycete fragment at 11000rpm for 8min, washing with water until the saccharomycete fragment is clarified, freeze-drying at-52 ℃ for 9h, crushing and grinding, sieving with a 250-mesh sieve, and secondary drying at 24 ℃ for 6.5h to obtain saccharomycete residues; pdCl is added to 2 ·2H 2 O and FeCl 3 ·6H 2 O is dissolved in 0.095M hydrochloric acid to obtain palladium-iron solution; 0.9g of fungus dreg is weighed and added into 500mL of palladium-iron solution, wherein Pd in the palladium-iron solution 2+ The mass concentration of (2) is 96mg/L, fe 3+ The mass concentration of (2) is 94mg/L; oscillating and absorbing for 13h at 23 ℃ at a rotating speed of 140rpm to obtain a palladium-iron absorbed bacterial dreg material; filtering the material, freezing at-18deg.C for 13h, and drying at-53deg.C under vacuum degree of 8Pa for 8.5h; mixing with 1.1g KOH after finishing, placing in a muffle furnace, heating to 600 ℃ at a heating rate of4 ℃/min, and preserving heat for 1.8h; and naturally cooling to 24 ℃ after heat preservation is finished, taking out, cleaning for 4 times by using deoxidized ultrapure water, cleaning for 2 times by using hydrochloric acid with the concentration of 0.08M, drying for 9 hours under the condition that the vacuum degree is 9Pa and the temperature is 45 ℃, and grinding to obtain the palladium-iron nano material based on the saccharomycete residues.
The sample obtained in this example was tested for catalytic performance and cycle performance by the same test method as in example 1 to obtain a palladium-iron nanomaterial based on yeast residue having an apparent rate constant of 4.60×10 in this example -2 S; in the reaction of 5 continuous cycles, the conversion rate reaches 95.7% -98.1%.
According to the embodiment, the palladium-iron nano material based on the yeast slag is in a multi-layer porous structure, nano particles are attached to the porous structure, the average size of the nano particles is 25.16nm, and C, N, O, pd and Fe elements on the surface of the material are uniformly distributed; the hysteresis loop of the material is thin and narrow, the soft magnetic ordering property of the sigmoid function shape is shown, the material is very sensitive to an external magnetic field, the material can be rapidly separated from a suspension liquid with the help of a magnet, and the characteristic of easy demagnetization can enable nano particles to be rapidly dispersed in the solution again for repeated recycling; after being applied to reduction catalytic reaction of p-nitrophenol, the apparent rate constant is 1.85 multiplied by 10 -1 And/s, is superior to the related report of the existing noble metal catalyst in the same reaction system. In addition, the palladium-iron nano material based on the saccharomycete residues has good recycling performance as a p-NP reduction catalyst, and the conversion rate reaches 96.6% -98.9% in the continuous 5-cycle reaction.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1. The preparation method of the palladium-iron nano material based on the yeast slag is characterized by comprising the following steps of:
(1) Mixing yeast residue and palladium-iron solution to obtain a palladium-iron adsorption bacterial residue material;
(2) Pyrolyzing a bacteria residue material absorbing palladium-iron and potassium hydroxide in a protective atmosphere to obtain the palladium-iron nano material based on the yeast residue;
the mass ratio of the saccharomycete residue to metal ions in the palladium-iron solution in the step (1) is 9-11: 1, a step of;
the mass ratio of the yeast residue in the step (1) to the potassium hydroxide in the step (2) is 9-11: 10 to 12.
2. The method according to claim 1, wherein the solvent of the palladium-iron solution is hydrochloric acid, and the concentration of the hydrochloric acid is 0.09-0.11M.
3. The preparation method according to claim 2, wherein the concentration of palladium ions in the palladium-iron solution in the step (1) is 90 to 110mg/L, and the concentration of iron ions in the palladium-iron solution is 90 to 110mg/L.
4. A method according to any one of claims 1 to 3, wherein the rotational speed of the mixing in step (1) is 130 to 170rpm, the temperature of the mixing is 20 to 30 ℃, and the time of the mixing is 10 to 14 hours.
5. The method according to claim 4, wherein the heating rate of the pyrolysis in the step (2) is 4-6 ℃/min, the target temperature of the pyrolysis is 500-800 ℃, and the constant temperature time after the pyrolysis reaches the target temperature is 1.5-2.5 h.
6. The palladium-iron nanomaterial based on yeast residue obtained by the preparation method of any one of claims 1 to 5.
7. The use of the yeast residue based palladium-iron nanomaterial in a catalytic reduction reaction of p-nitrophenol.
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