CN110172688B - Preparation method and application of derived functional pore wood for producing hydrogen by electrolyzing water - Google Patents
Preparation method and application of derived functional pore wood for producing hydrogen by electrolyzing water Download PDFInfo
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Abstract
A preparation method and application of derived functional pore wood for hydrogen production by water electrolysis relate to a preparation method and application of a wood functional pore composite material. The invention aims to solve the problems of complex process, poor combination of the transition metal phosphide and a wood substrate and unstable interface in the hydrogen production process by electrolysis of water in the conventional method. The method comprises the following steps: firstly, removing coarse fibers on the surface of the natural porous wood; II, loading Pd2+(ii) a III, load Pd0(ii) a Fourthly, loading nickel-phosphorus alloy; and fifthly, vacuum drying. The derived functional pore wood for hydrogen production by water electrolysis prepared by the invention is used for hydrogen production by water electrolysis. The derived functional pore wood prepared by the method has good stability under the alkaline condition, and the stability is more than 1000 mA-cm‑2The current hardly decayed at current density for up to 40 hours. The derived functional pore wood for hydrogen production by water electrolysis prepared by the invention is suitable for hydrogen production by water electrolysis.
Description
Technical Field
The invention relates to a preparation method and application of a wood functional pore composite material.
Background
Hydrogen energy is an ideal energy carrier, and the key to effective utilization of hydrogen energy is to develop a large-scale, cheap, clean and efficient hydrogen production technology. The hydrogen production by electrolyzing water is an important energy technology for realizing sustainable hydrogen. The device can be driven by electric energy converted from various renewable energy sources to realize clean, rapid and centralized production of high-purity hydrogen, so that the renewable energy sources with uneven time and space distribution are converted into stable chemical energy. The most important bottleneck for limiting the large-scale application of hydrogen production by water electrolysis is how to greatly reduce the electric energy consumption of the hydrogen production, so that the hydrogen production cost is greatly reduced. At present, although platinum (Pt) base has high activity and stability, it is limited by expensive cost and difficult to be applied in large scale. Transition Metal Phosphides (TMPs) having low cost and high activity are the subject of much attention of researchers in recent years. At present, porous materials such as foamed nickel, carbon paper and the like are mostly used as substrates for supporting TMPs. However, these substrates are susceptible to corrosion by strong acids and bases, and the active substances are easily detached from the substrate surface by the impact under a large current, and this instability of the hetero interface is disadvantageous for the large-scale production of hydrogen. Moreover, the existing technology for synthesizing TMPs is too complex, and the technology for quickly synthesizing TMPs with simple operation, low cost, high efficiency is urgently needed to be solved.
In addition, the growth process of the transition metal phosphide on porous substrates such as nickel foam and the like is complicated, and the interface of the transition metal phosphide is unstable in the process of electrolyzing water to produce hydrogen under large current.
Disclosure of Invention
The invention aims to solve the problems of complex process of transition metal phosphide prepared by the existing method, poor bonding of the transition metal phosphide and a wood substrate and unstable interface in the hydrogen production process by electrolysis, and provides a preparation method and application of a NiP/wood heterogeneous porous composite material.
A preparation method of derived functional pore wood for electrolyzing water to produce hydrogen is completed according to the following steps:
firstly, removing crude fibers on the surface of natural porous wood, then respectively ultrasonically cleaning in deionized water, absolute ethyl alcohol and acetone in sequence, and finally carrying out vacuum drying to obtain the natural porous wood with the crude fibers on the surface removed;
secondly, immersing the natural porous wood with the surface crude fibers removed into PdCl with the concentration of 0.1-0.3 g/L2Hydrochloric acid solution is added for 10min to 20min, and the solution is taken out and dried by hot air to obtain the loaded Pd2+The porous wood of (1);
thirdly, soaking the porous wood loaded with Pd ions into NaBH with the concentration of 4 g/L-6 g/L4Taking out the mixture from sodium hydroxide solution for 5-15 min and using hot airDrying to obtain the loaded Pd0The porous wood of (1);
fourthly, Pd is loaded0The porous wood is immersed into the plating solution for plating for 30min to 40min to obtain the porous wood loaded with the nickel-phosphorus alloy;
and fifthly, drying the porous wood loaded with the nickel-phosphorus alloy in vacuum to obtain the derived functional porous wood for hydrogen production by water electrolysis.
The derived functional pore wood for electrolyzing water to produce hydrogen is used for electrolyzing water to produce hydrogen.
The principle and the advantages of the invention are as follows:
according to the invention, nickel-phosphorus alloy is loaded on the pore channel structure of the natural porous wood through a chemical plating technology, and researches show that the hydrophilicity of the pores of the wood and the rough structure of the pore surface can anchor the nickel-phosphorus alloy efficiently; the natural hydrophilic and gas-permeable structure of the wood can reduce overpotential and rapid mass transfer in the HER process, and the broad-leaved poplar with the hierarchical porous structure can greatly improve the hydrogen production efficiency by water electrolysis; the derived functional pore wood prepared by the method has good stability under the alkaline condition, and the stability is more than 1000 mA-cm-2The current hardly decayed at current density for up to 40 hours. Therefore, the technology of the invention is hopeful to enable the natural porous wood to replace the substrates such as the foam nickel, the carbon paper and the like which are artificially synthesized at present to be used for hydrogen production by water electrolysis.
The derived functional pore wood for hydrogen production by water electrolysis prepared by the invention is suitable for hydrogen production by water electrolysis.
Drawings
FIG. 1 is an SEM image of a derivative functional pore wood prepared in the first example and used for hydrogen production by electrolysis of water, which is magnified by 500 times;
FIG. 2 is an SEM image of a derivative functional pore wood for hydrogen production by electrolysis of water, which is prepared in the first example, and is magnified by 5000 times;
FIG. 3 is an SEM image of a derivative functional pore wood prepared in example two and used for hydrogen production by electrolysis of water at a magnification of 500 times;
FIG. 4 is an SEM image of a derivative functional pore wood prepared in example two and used for hydrogen production by electrolysis of water, wherein the SEM image is magnified by 5000 times;
FIG. 5 is an SEM image of a derivative functional pore wood prepared in example III and used for hydrogen production by electrolysis of water at a magnification of 500 times;
FIG. 6 is an SEM image of a derivative functional pore wood prepared in example III and used for hydrogen production by electrolysis of water, wherein the SEM image is magnified by 5000 times;
FIG. 7 is an XRD (X-ray diffraction) diagram, wherein a is poplar, b is the derived functional pore wood for hydrogen production by electrolysis of water prepared in the first example, c is fraxinus mandshurica, d is the derived functional pore wood for hydrogen production by electrolysis of water prepared in the second example, e is larch, and f is the derived functional pore wood for hydrogen production by electrolysis of water prepared in the third example;
FIG. 8 is a high resolution TEM image of NiP on derivatized functional pore wood prepared in example one for hydrogen production from electrolyzed water;
FIG. 9 is a macroscopic view of a poplar cross-section;
FIG. 10 initial contact angle of poplar cross-section;
FIG. 11 is the contact angle after 10 s;
FIG. 12 is a schematic cross-sectional view of a cross-section of a natural porous wood;
FIG. 13 is a cross-sectional 3D topographical view of a natural porous wood;
fig. 14 is a hydrogen evolution polarization curve, in which a is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example one, b is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example two, and c is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example three;
fig. 15 is a Tafel slope curve, in which a is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example one, b is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example two, and c is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example three;
fig. 16 is an ac impedance spectrum in which a is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example one, b is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example two, and c is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example three;
FIG. 17 is an enlarged view of a portion of FIG. 16;
FIG. 18 is an i-t curve of a derived functional pore wood for hydrogen production from electrolyzed water prepared in example one;
fig. 19 is a scanning electron microscope image of the derived functional pore wood for hydrogen production from electrolyzed water prepared in example one after 44h of HER testing.
Detailed Description
The first embodiment is as follows: the embodiment is a preparation method of derived functional pore wood for hydrogen production by water electrolysis, which is completed according to the following steps:
firstly, removing crude fibers on the surface of natural porous wood, then respectively ultrasonically cleaning in deionized water, absolute ethyl alcohol and acetone in sequence, and finally carrying out vacuum drying to obtain the natural porous wood with the crude fibers on the surface removed;
secondly, immersing the natural porous wood with the surface crude fibers removed into PdCl with the concentration of 0.1-0.3 g/L2Hydrochloric acid solution is added for 10min to 20min, and the solution is taken out and dried by hot air to obtain the loaded Pd2+The porous wood of (1);
thirdly, soaking the porous wood loaded with Pd ions into NaBH with the concentration of 4 g/L-6 g/L4Taking out the solution of sodium hydroxide for 5-15 min, and drying the solution of sodium hydroxide by using hot air to obtain the loaded Pd0The porous wood of (1);
fourthly, Pd is loaded0The porous wood is immersed into the plating solution for plating for 30min to 40min to obtain the porous wood loaded with the nickel-phosphorus alloy;
and fifthly, drying the porous wood loaded with the nickel-phosphorus alloy in vacuum to obtain the derived functional porous wood for hydrogen production by water electrolysis.
The principle and advantages of the embodiment are as follows:
according to the embodiment, the nickel-phosphorus alloy is loaded on the pore channel structure of the natural porous wood through the chemical plating technology, and researches show that the hydrophilicity of the pores of the wood and the rough structure of the pore surface can anchor the nickel-phosphorus alloy efficiently; the natural hydrophilic and gas-permeable structure of the wood can reduce overpotential and rapid mass transfer in the HER process, and the broad-leaved poplar with the hierarchical porous structure can greatly improve the hydrogen production efficiency by water electrolysis; derived functional pore wood for electrolyzing water to produce hydrogen prepared by the embodimentHas good stability under alkaline condition, and is more than 1000mA cm-2The current hardly decayed at current density for up to 40 hours. Therefore, the technology of the embodiment is expected to enable the natural porous wood to replace the substrates such as the foam nickel, the carbon paper and the like which are artificially synthesized at present to be used for hydrogen production by water electrolysis.
The derived functional pore wood for hydrogen production by water electrolysis prepared by the embodiment is suitable for hydrogen production by water electrolysis.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the natural porous wood in the step one is poplar, fraxinus mandshurica or larch, and the size is 1.5cm multiplied by 1.0cm multiplied by 0.1 cm. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the first step, the natural porous wood is firstly polished for 10min to 20min by using 80-mesh sand paper, and then polished for 10min to 20min by using 240-mesh sand paper, so that the natural porous wood with the surface coarse fibers removed is obtained. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the ultrasonic cleaning time in the first step is 5min to 10min, and the ultrasonic cleaning power is 50W to 200W. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the temperature of the vacuum drying in the step one is 100-105 ℃, and the time of the vacuum drying is 5-8 h. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the PdCl with the concentration of 0.1-0.3 g/L in the step two2The preparation method of the hydrochloric acid solution comprises the following steps: 0.1g to 0.3g of PdCl2Dissolving the solution into 1L of hydrochloric acid with the mass fraction of 2 percent to obtain PdCl with the concentration of 0.1 to 0.3g/L2Hydrochloric acid solution. The other steps are the same as those in the first to fifth embodiments.
Detailed description of the invention: the difference between this embodiment and one of the first to sixth embodiments is: the NaBH with the concentration of 4 g/L-6 g/L in the third step4The preparation method of the sodium hydroxide solution comprises the following steps: 4g to 6g of NaBH4Dissolving the NaBH into 1L of NaOH solution with the concentration of 2g/L to obtain NaBH with the concentration of 4g/L to 6g/L4Sodium hydroxide solution. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the plating solution in the fourth step is prepared from NiSO4·6H2O、NaH2PO2·H2O、C6H5Na3O7·2H2O、NH3·H2O and water; NiSO in the plating solution4·6H2The concentration of O is 15g/L to 25g/L, NaH2PO2·H2The concentration of O is 25 g/L-35 g/L, C6H5Na3O7·2H2The concentration of O is 70 g/L-80 g/L, NH3·H2The concentration of O is 50 g/L-65 g/L. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the temperature of the plating solution in the fourth step is 40-60 ℃; and the temperature of the vacuum drying in the step five is 100-105 ℃, and the time of the vacuum drying is 5-8 h. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the embodiment is that the derived functional pore wood for electrolyzing water to produce hydrogen is used for electrolyzing water to produce hydrogen. The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: a preparation method of derived functional pore wood for electrolyzing water to produce hydrogen is completed according to the following steps:
firstly, grinding the surface of natural porous wood for 15min by using 80-mesh abrasive paper, and then grinding the natural porous wood for 15min by using 240-mesh abrasive paper to obtain natural porous wood with surface coarse fibers removed; then respectively ultrasonically cleaning the wood in deionized water, absolute ethyl alcohol and acetone for 8min in sequence, wherein the ultrasonic power is 100W, and finally, drying the wood in vacuum at 102 ℃ for 6h to obtain the natural porous wood with the crude fibers removed;
the natural porous wood in the step one is poplar, and the size of the natural porous wood is 1.5cm multiplied by 1.0cm multiplied by 0.1 cm;
secondly, immersing the natural porous wood without the crude fibers into PdCl with the concentration of 0.2g/L2Taking out the solution of hydrochloric acid for 15min, and drying the solution of hydrochloric acid by using hot air to obtain the loaded Pd2+The porous wood of (1);
the PdCl with the concentration of 0.2g/L in the step two2The preparation method of the hydrochloric acid solution comprises the following steps: 0.2g of PdCl2Dissolving in 1L of 2% hydrochloric acid to obtain PdCl with concentration of 0.2g/L2A hydrochloric acid solution;
thirdly, soaking the porous wood loaded with Pd ions into NaBH with the concentration of 5g/L4Taking out the solution of sodium hydroxide for 10min, and drying the solution of sodium hydroxide by using hot air to obtain the loaded Pd0The porous wood of (1);
NaBH with the concentration of 5g/L in the third step4The preparation method of the sodium hydroxide solution comprises the following steps: mixing 5g NaBH4Dissolving in 1L NaOH solution with concentration of 2g/L to obtain NaBH with concentration of 5g/L4A sodium hydroxide solution;
fourthly, Pd is loaded0The porous wood is immersed into plating solution with the temperature of 50 ℃ for plating for 30min to obtain the porous wood loaded with the nickel-phosphorus alloy;
the plating solution in the fourth step is prepared from NiSO4·6H2O、NaH2PO2·H2O、C6H5Na3O7·2H2O、NH3·H2O and water; NiSO in the plating solution4·6H2The concentration of O is 21g/L, NaH2PO2·H2The concentration of O is 30g/L, C6H5Na3O7·2H2O concentration of 75g/L, NH3·H2The concentration of O is 58 g/L;
and fifthly, drying the porous wood loaded with the nickel-phosphorus alloy in vacuum at 102 ℃ for 6 hours to obtain the derived functional porous wood for hydrogen production by water electrolysis.
Example two: a preparation method of derived functional pore wood for electrolyzing water to produce hydrogen is completed according to the following steps:
firstly, grinding the surface of natural porous wood for 15min by using 80-mesh abrasive paper, and then grinding the natural porous wood for 15min by using 240-mesh abrasive paper to obtain natural porous wood with surface coarse fibers removed; then respectively ultrasonically cleaning the wood in deionized water, absolute ethyl alcohol and acetone for 8min in sequence, wherein the ultrasonic power is 100W, and finally, drying the wood in vacuum at 102 ℃ for 6h to obtain the natural porous wood with the crude fibers removed;
the natural porous wood in the step one is fraxinus mandshurica, and the size is 1.5cm multiplied by 1.0cm multiplied by 0.1 cm;
secondly, immersing the natural porous wood without the crude fibers into PdCl with the concentration of 0.2g/L2Taking out the solution of hydrochloric acid for 15min, and drying the solution of hydrochloric acid by using hot air to obtain the loaded Pd2+The porous wood of (1);
the PdCl with the concentration of 0.2g/L in the step two2The preparation method of the hydrochloric acid solution comprises the following steps: 0.2g of PdCl2Dissolving in 1L of 2% hydrochloric acid to obtain PdCl with concentration of 0.2g/L2A hydrochloric acid solution;
thirdly, soaking the porous wood loaded with Pd ions into NaBH with the concentration of 5g/L4Taking out the solution of sodium hydroxide for 10min, and drying the solution of sodium hydroxide by using hot air to obtain the loaded Pd0The porous wood of (1);
NaBH with the concentration of 5g/L in the third step4The preparation method of the sodium hydroxide solution comprises the following steps: mixing 5g NaBH4Dissolving in 1L NaOH solution with concentration of 2g/L to obtain NaBH with concentration of 5g/L4A sodium hydroxide solution;
fourthly, Pd is loaded0The porous wood is immersed into plating solution with the temperature of 50 ℃ for plating for 30min to obtain the porous wood loaded with the nickel-phosphorus alloy;
the plating solution in the fourth step is prepared from NiSO4·6H2O、NaH2PO2·H2O、C6H5Na3O7·2H2O、NH3·H2O and water; NiSO in the plating solution4·6H2The concentration of O is 21g/L, NaH2PO2·H2The concentration of O is 30g/L, C6H5Na3O7·2H2O concentration of 75g/L, NH3·H2The concentration of O is 58 g/L;
and fifthly, drying the porous wood loaded with the nickel-phosphorus alloy in vacuum at 102 ℃ for 6 hours to obtain the derived functional porous wood for hydrogen production by water electrolysis.
Example three: a preparation method of derived functional pore wood for electrolyzing water to produce hydrogen is completed according to the following steps:
firstly, grinding the surface of natural porous wood for 15min by using 80-mesh abrasive paper, and then grinding the natural porous wood for 15min by using 240-mesh abrasive paper to obtain natural porous wood with surface coarse fibers removed; then respectively ultrasonically cleaning the wood in deionized water, absolute ethyl alcohol and acetone for 8min in sequence, wherein the ultrasonic power is 100W, and finally, drying the wood in vacuum at 102 ℃ for 6h to obtain the natural porous wood with the crude fibers removed;
the natural porous wood in the step one is larch, and the size is 1.5cm multiplied by 1.0cm multiplied by 0.1 cm;
secondly, immersing the natural porous wood without the crude fibers into PdCl with the concentration of 0.2g/L2Taking out the solution of hydrochloric acid for 15min, and drying the solution of hydrochloric acid by using hot air to obtain the loaded Pd2+The porous wood of (1);
the PdCl with the concentration of 0.2g/L in the step two2The preparation method of the hydrochloric acid solution comprises the following steps: 0.2g of PdCl2Dissolving in 1L of 2% hydrochloric acid to obtain PdCl with concentration of 0.2g/L2A hydrochloric acid solution;
thirdly, soaking the porous wood loaded with Pd ions into NaBH with the concentration of 5g/L4Taking out the solution of sodium hydroxide for 10min, and drying the solution of sodium hydroxide by using hot air to obtain the loaded Pd0The porous wood of (1);
NaBH with the concentration of 5g/L in the third step4The preparation method of the sodium hydroxide solution comprises the following steps: mixing 5g NaBH4Dissolving in 1L NaOH solution with concentration of 2g/L to obtain solution with concentration of 2g/L5g/L NaBH4A sodium hydroxide solution;
fourthly, Pd is loaded0The porous wood is immersed into plating solution with the temperature of 50 ℃ for plating for 30min to obtain the porous wood loaded with the nickel-phosphorus alloy;
the plating solution in the fourth step is prepared from NiSO4·6H2O、NaH2PO2·H2O、C6H5Na3O7·2H2O、NH3·H2O and water; NiSO in the plating solution4·6H2The concentration of O is 21g/L, NaH2PO2·H2The concentration of O is 30g/L, C6H5Na3O7·2H2O concentration of 75g/L, NH3·H2The concentration of O is 58 g/L;
and fifthly, drying the porous wood loaded with the nickel-phosphorus alloy in vacuum at 102 ℃ for 6 hours to obtain the derived functional porous wood for hydrogen production by water electrolysis.
FIG. 1 is an SEM image of a derivative functional pore wood prepared in the first example and used for hydrogen production by electrolysis of water, which is magnified by 500 times;
FIG. 2 is an SEM image of a derivative functional pore wood for hydrogen production by electrolysis of water, which is prepared in the first example, and is magnified by 5000 times;
FIG. 3 is an SEM image of a derivative functional pore wood prepared in example two and used for hydrogen production by electrolysis of water at a magnification of 500 times;
FIG. 4 is an SEM image of a derivative functional pore wood prepared in example two and used for hydrogen production by electrolysis of water, wherein the SEM image is magnified by 5000 times;
FIG. 5 is an SEM image of a derivative functional pore wood prepared in example III and used for hydrogen production by electrolysis of water at a magnification of 500 times;
FIG. 6 is an SEM image of a derivative functional pore wood prepared in example III and used for hydrogen production by electrolysis of water, wherein the SEM image is magnified by 5000 times;
as can be seen from the analysis of fig. 1 to 6, the NiP alloy is uniformly and densely deposited on the pore walls of the natural porous wood, and fluctuates with the structure of the wood; after the NiP alloy is loaded, the constructed derived functional pore wood for electrolyzing water to produce hydrogen still has the porous characteristic of wood. Due to the different pore channels of the three kinds of wood, the surface microscopic morphology of the three kinds of wood has obvious structural difference.
FIG. 7 is an XRD (X-ray diffraction) diagram, wherein a is poplar, b is the derived functional pore wood for hydrogen production by electrolysis of water prepared in the first example, c is fraxinus mandshurica, d is the derived functional pore wood for hydrogen production by electrolysis of water prepared in the second example, e is larch, and f is the derived functional pore wood for hydrogen production by electrolysis of water prepared in the third example;
as can be seen from fig. 7, the crystallization peaks of cellulose appeared at 2 θ ═ 16.2 ° and 22.3 ° in poplar, ash and larch, and after the electroless plating treatment, the cellulose peaks of them were significantly reduced, but the peak of Ni (111) appeared at 2 θ ═ 45.2 ° and the peak had "steamed bread"; it was preliminarily confirmed that the NiP alloy had an amorphous structure.
FIG. 8 is a high resolution TEM image of NiP on derivatized functional pore wood prepared in example one for hydrogen production from electrolyzed water;
as can be seen from FIG. 8, the NiP alloy is composed of amorphous NiPxAlloy and crystalline metallic nickel with face-centered cubic structure, the defect structure formed can obviously improve the performance of HER.
FIG. 9 is a macroscopic view of a poplar cross-section;
the distribution of the early and late woods is clearly observed in fig. 9.
The contact angle test shows (fig. 10) that the initial contact angle of the porous wood is 95 degrees, and after 10s (fig. 11), the contact angle value is reduced to 23 degrees, and good hydrophilic performance is shown.
FIG. 10 initial contact angle of poplar cross-section;
FIG. 11 is the contact angle after 10 s;
fig. 12 is a schematic cross-sectional view of a cross-section of a natural porous wood, wherein the surface structure is relatively rough, and the 3D topography further indicates that the surface has a "mountain" and "valley" structure (fig. 13). The rough structure and the hydrophilicity of the wood can lay a good foundation for the stable combination of the metal and the porous wood.
FIG. 12 is a schematic cross-sectional view of a cross-section of a natural porous wood;
FIG. 13 is a cross-sectional 3D topographical view of a natural porous wood;
example one test of hydrogen production performance of electrolyzed water of derived functional pore wood prepared for hydrogen production by electrolyzed water was as follows:
the experiment utilizes a CHI 750E electrochemical workstation to perform characterization under a three-electrode system (a working electrode: the derived functional pore wood for electrolyzing water to produce hydrogen, which is prepared in the first embodiment, the size of the working electrode is 10mm multiplied by 1mm, a reference electrode: a saturated Ag/AgCl electrode, an auxiliary electrode: a carbon rod electrode), the test temperature of all samples is room temperature, hydrogen is introduced before the test, the hydrogen in the solution is saturated, and the Cyclic Voltammetry (CV), the Linear Scanning Voltammetry (LSV) and the alternating current impedance spectrogram (EIS) of the derived functional pore wood for electrolyzing water to produce hydrogen, which is prepared in the first embodiment, are tested in 1.0mol/L KOH. CV curve: setting a testing method as cyclic voltammetry, adjusting the voltage range to-0.9V to-1.2V, and performing working electrode activation treatment until the electrode activation curve is stable; LSV curve: setting the test method as a linear scanning method, setting the scanning speed to be 5mV/s, adjusting the voltage range to be-0.9V-1.6V, testing to obtain a polarization curve of the working electrode, and analyzing the curve to obtain the wave-starting potential, Tafel slope, overpotential and the like of the material; EIS spectrogram: testing the electrode by AC impedance method, setting open-circuit voltage as voltage and frequency as 105Hz～10-2Hz, the alternating voltage is 5mV, and an alternating impedance spectrogram is obtained; and (3) cyclic stability: the test was carried out using a time-current curve, with a current density set at 250mA cm-2The corresponding constant working voltage keeps the electrode in a continuous hydrogen production state for 44h (in a time-current curve test, in order to prevent the damage of a large current to an electrochemical workstation instrument, the size of a test piece is adjusted to be 0.5cm multiplied by 0.5cm, and the current density is 1000 mA-cm-2The dimensions of the corresponding test pieces were 1cm × 1cm, and the above properties were shown in FIGS. 14 to 19.
The hydrogen production performance by electrolyzed water of the derived functional pore wood for hydrogen production by electrolyzed water prepared in example two and example three was tested in the same manner, as shown in fig. 14 to 16.
Fig. 14 is a hydrogen evolution polarization curve, in which a is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example one, b is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example two, and c is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example three;
fig. 15 is a Tafel slope curve, in which a is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example one, b is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example two, and c is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example three;
fig. 16 is an ac impedance spectrum in which a is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example one, b is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example two, and c is the derived functional pore wood for hydrogen production by electrolysis of water prepared in example three;
FIG. 17 is an enlarged view of a portion of FIG. 16;
FIG. 18 is an i-t curve of a derived functional pore wood for hydrogen production from electrolyzed water prepared in example one;
fig. 19 is a scanning electron microscope image of the derived functional pore wood for hydrogen production from electrolyzed water prepared in example one after 44h of HER testing.
As shown in FIG. 14, the derived functional pore wood for hydrogen production by electrolysis of water prepared in the first example reached a current density of 10mA cm-2Only 83mV over potential is needed, and 150mV and 105mV over potential are needed for reaching the same current density of the derived functional pore wood for hydrogen production by water electrolysis prepared in the example two and the derived functional pore wood for hydrogen production by water electrolysis prepared in the example three respectively. This shows that the HER performance of the derived functional pore wood for hydrogen production by electrolysis of water prepared in example one is superior to that of the derived functional pore wood for hydrogen production by electrolysis of water prepared in example two and that of the derived functional pore wood for hydrogen production by electrolysis of water prepared in example three. Further, the dynamic performance of the test piece was evaluated by Tafel slopes, and as can be seen from fig. 15, the Tafel slopes of the derived functional pore wood for hydrogen production by electrolysis of water prepared in example one, the derived functional pore wood for hydrogen production by electrolysis of water prepared in example two, and the derived functional pore wood for hydrogen production by electrolysis of water prepared in example three were 73.2mV dec-1、114.5mV dec-1And 81.2mV dec-1It is shown that the derived functional pore wood for hydrogen production by electrolysis of water prepared in example one exhibits rapid kinetic properties. Meanwhile, the alternating-current impedance spectrum also shows that the NiP/poplar electrode has good charge transfer performance (figure 16). Example one the superior HER performance of the derived functional pore wood prepared for hydrogen production by electrolysis of water is in force of the hierarchical porous structure of the porous poplar substrate. Time (t) -current (i) was used to evaluate the cycling stability of the material, and it can be seen from fig. 18 that the derived functional pore wood for hydrogen production by electrolysis of water prepared in example one could reach 1000mA cm at current density-2There was no significant decay for as long as 44h, and after a long period of HER testing, scanning electron microscopy showed little change in the morphology of the NiP alloy and wood porous substrate (fig. 19). The ultra-strong circulation stability of the wood porous material has important significance in the actual large-scale production of hydrogen.
Claims (8)
1. A preparation method of derived functional pore wood for hydrogen production by water electrolysis is characterized in that the preparation method of derived functional pore wood for hydrogen production by water electrolysis is completed according to the following steps:
firstly, removing crude fibers on the surface of natural porous wood, then respectively ultrasonically cleaning in deionized water, absolute ethyl alcohol and acetone in sequence, and finally carrying out vacuum drying to obtain the natural porous wood with the crude fibers on the surface removed;
the natural porous wood in the step one is poplar, fraxinus mandshurica or larch, and the size is 1.5cm multiplied by 1.0cm multiplied by 0.1 cm;
secondly, immersing the natural porous wood with the surface crude fibers removed into PdCl with the concentration of 0.1-0.3 g/L2Hydrochloric acid solution is added for 10min to 20min, and the solution is taken out and dried by hot air to obtain the loaded Pd2+The porous wood of (1);
thirdly, soaking the porous wood loaded with Pd ions into NaBH with the concentration of 4 g/L-6 g/L4Taking out the solution of sodium hydroxide for 5-15 min, and drying the solution of sodium hydroxide by using hot air to obtain the loaded Pd0The porous wood of (1);
fourthly, Pd is loaded0The porous wood is immersed into the plating solution for plating for 30min to 40min to obtain the porous wood loaded with the nickel-phosphorus alloy;
the plating solution in the fourth step is prepared from NiSO4·6H2O、NaH2PO2·H2O、C6H5Na3O7·2H2O、NH3·H2O and water; NiSO in the plating solution4·6H2The concentration of O is 15g/L to 25g/L, NaH2PO2·H2The concentration of O is 25 g/L-35 g/L, C6H5Na3O7·2H2The concentration of O is 70 g/L-80 g/L, NH3·H2The concentration of O is 50 g/L-65 g/L;
and fifthly, drying the porous wood loaded with the nickel-phosphorus alloy in vacuum to obtain the derived functional porous wood for hydrogen production by water electrolysis.
2. The method for preparing the derived functional porous wood for hydrogen production by electrolysis of water according to claim 1, wherein in the step one, the natural porous wood is firstly polished for 10min to 20min by using 80-mesh sand paper, and then polished for 10min to 20min by using 240-mesh sand paper, so as to obtain the natural porous wood with the surface coarse fibers removed.
3. The method for preparing the derived functional pore wood for electrolyzing water to produce hydrogen according to claim 1, wherein the ultrasonic cleaning time in the step one is 5-10 min, and the ultrasonic cleaning power is 50-200W.
4. The method for preparing the derived functional porous wood for hydrogen production by electrolysis of water according to claim 1, wherein the temperature of vacuum drying in the step one is 100 ℃ to 105 ℃, and the time of vacuum drying is 5h to 8 h.
5. The method for preparing derived functional pore wood for hydrogen production by electrolysis of water as claimed in claim 1, wherein the concentration in step two is 0.1 g/L-0.3 g/HPdCl of L2The preparation method of the hydrochloric acid solution comprises the following steps: 0.1g to 0.3g of PdCl2Dissolving the solution into 1L of hydrochloric acid with the mass fraction of 2 percent to obtain PdCl with the concentration of 0.1 to 0.3g/L2Hydrochloric acid solution.
6. The method for preparing derived functional pore wood for electrolyzing water to produce hydrogen according to claim 1, wherein the concentration of NaBH in step three is 4-6 g/L4The preparation method of the sodium hydroxide solution comprises the following steps: 4g to 6g of NaBH4Dissolving the NaBH into 1L of NaOH solution with the concentration of 2g/L to obtain NaBH with the concentration of 4g/L to 6g/L4Sodium hydroxide solution.
7. The method for preparing the derived functional porous wood for hydrogen production by electrolyzing water as claimed in claim 1, wherein the temperature of the plating solution in the fourth step is 40-60 ℃; and the temperature of the vacuum drying in the step five is 100-105 ℃, and the time of the vacuum drying is 5-8 h.
8. The use of the derived functional pore wood for hydrogen production by electrolysis of water, prepared by the preparation method as claimed in claim 1, wherein the derived functional pore wood for hydrogen production by electrolysis of water is used for hydrogen production by electrolysis of water.
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