CN111690945A - Method for producing hydrogen by electrolyzing waste lignocellulose - Google Patents
Method for producing hydrogen by electrolyzing waste lignocellulose Download PDFInfo
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
The invention discloses a method for preparing hydrogen by electrolyzing waste lignocellulose, which comprises the steps of placing a pretreated substrate material into a mixed solution containing transition metal salt and a template agent, taking out after hydrothermal reaction, heating under inert gas after cleaning and drying, and carrying out phosphating reaction to obtain a catalyst; adding the waste lignocellulose raw material into a mixed solution containing an alkaline solution and polyhydric alcohol, and mixing to prepare an electrolyte; a two-electrode system is adopted, the activated catalyst is used as a working negative electrode and a working positive electrode, the working negative electrode and the working positive electrode are placed in electrolyte to form an electrolytic cell, and the light-driven electrolytic hydrogen production is realized by combining a photovoltaic module. The method provided by the invention can directly use the waste lignocellulose to produce hydrogen, not only can utilize and consume the waste lignocellulose, but also can reduce the energy consumption of hydrogen production by electrolyzing water, and can prepare clean energy hydrogen by using solar energy while reducing the waste and pollution caused by burning the lignocellulose, thereby improving the hydrogen production efficiency.
Description
Technical Field
The invention relates to the technical field of hydrogen production by biological raw materials, in particular to a method for producing hydrogen by electrolyzing waste lignocellulose.
Background
Fossil energy is the most main energy consumed globally at present, the percentage of fossil energy in the energy consumed globally in 2016 is as high as 85.5%, and the percentage of China is as high as 92%.
Along with the continuous exploitation of human beings, the exhaustion of fossil resources is inevitable, the shortage problem of the fossil resources is serious day by day, the price of petroleum is greatly floated, and the economic safety of China is seriously damaged. At the same time, the use of fossil energy produces large amounts of CO2And harmful gases, threatening the global ecology. Thus, the development of cleaner renewable energy sources is a development direction in the future.
Hydrogen is considered an ideal alternative to fossil fuels due to clean combustion, potential renewability, and high energy storage. At present, three main ways for industrial hydrogen production are steam methane reforming, coal gasification and water electrolysis. Among them, the steam methane reforming and coal gasification methods based on fossil fuels are low in cost, but both have pollution and CO2The problem of emission goes against the original purpose of hydrogen energy development; the hydrogen production by water electrolysis provides a clean and convenient method for efficiently producing high-purity hydrogen, but the energy consumption is high, the cost of the used noble metal catalyst is high, and meanwhile, a direct current power supply used by the traditional electrolysis is also from non-clean energy, namely fossil fuel, so that the development of hydrogen energy is hindered.
Lignocellulose (containing cellulose, hemicellulose and lignin) is the most abundant non-edible and renewable biomass resource in the nature, and has large storage capacity on the earth. However, lignocellulosic raw materials such as straw, weeds, wood chips, waste paper, etc. are not fully utilized, but are burned to cause waste of resources and serious air pollution.
The waste lignocellulose with low cost and wide sources is used for electrolytic hydrogen production, so that on one hand, the high-value utilization of the waste lignocellulose is realized, the resource waste is reduced, the environmental pollution is reduced, and the method has important significance in promoting the ecological utilization of renewable resources and relieving the shortage of fossil resources; on the other hand, the waste lignocellulose is used for hydrogen production by electrolysis, and the problem of high energy consumption in hydrogen production by water electrolysis is effectively solved.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for producing hydrogen by electrolyzing waste lignocellulose, wherein the waste lignocellulose is added into a reaction system for producing hydrogen by electrocatalysis, so that a large amount of agricultural wastes can be consumed, the pollution caused by the treatment of the agricultural wastes can be reduced, and the hydrogen production efficiency can be improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for producing hydrogen by utilizing waste lignocellulose through electrolysis comprises the following steps,
s1, placing the pretreated substrate material into a mixed solution containing transition metal salt and a template agent, taking out the substrate material after hydrothermal reaction, cleaning and drying the substrate material, heating the substrate material under the protection of inert gas, and carrying out a phosphating reaction under the action of a phosphating agent to obtain a catalyst, wherein the template agent is a mixture of urea and ammonium fluoride;
s2, crushing the waste lignocellulose raw material, drying, adding the crushed waste lignocellulose raw material into a mixed solution containing an alkaline solution and polyhydric alcohol, uniformly mixing, and heating and liquefying to obtain an electrolyte;
s3, activating the catalyst obtained in the step S1, then adopting a two-electrode system, taking the activated catalyst as a working negative and positive electrode, placing the working negative and positive electrode in the electrolyte obtained in the step S2 to form an electrolytic cell, and electrolytically producing hydrogen.
In the above technical solution, the method for producing hydrogen by electrolysis of waste lignocellulose further comprises connecting the electrolytic cell in step S3 with a perovskite cell, and then placing the cell under sunlight to produce hydrogen by photolysis.
Further, in the above technical means, in step S2, the particle size of the crushed waste lignocellulosic raw material is less than 0.25 cm.
Further, in the above technical solution, in step S2, the drying temperature and the drying time of the waste lignocellulosic raw material are 75-90 ℃ and 8-15h, respectively.
Further, in the above technical solution, in step S2, the liquefaction temperature and time for the heating liquefaction are 250-350 ℃ and 3-8h, respectively.
Still further, in the above technical solution, in step S2, the alkaline solution is KOH or NaOH solution, and preferably KOH solution with a concentration of 1 mol/L.
Further, in the above technical solution, in step S1, the base material is one or more of carbon fiber paper, carbon fiber cloth, nickel foam and copper foam, and is preferably carbon fiber paper.
Further, in the above technical solution, in step S1, the template is a mixture of a molar ratio (1.5-2.0): 1 of urea and ammonium fluoride.
Further, in the above technical solution, in step S1, the transition metal salt is a nitrate or sulfate of Fe, Co or Ni, and preferably a molar ratio of (2.5-3.6): 1 cobalt nitrate and ferrous sulfate.
Further, in the above technical solution, in step S1, the phosphating agent is NaH2PO2·H2O。
Still further, in the above technical solution, in step S1, the reaction temperature and the reaction time of the hydrothermal reaction are 110-135 ℃ and 15-18h, preferably 120 ℃ and 16h, respectively.
Still further, in the above technical solution, in step S1, the reaction temperature and the reaction time of the phosphating reaction are 360-450 ℃ and 1.5-3h, preferably 400 ℃ and 2h, respectively.
Further, in the above-described aspect, in step S1, the pretreatment of the substrate is specifically a washing treatment with acetone, ethanol, secondary water, dilute nitric acid, and secondary water in this order.
Still further, in the above technical solution, in step S1, the cleaning and drying after the hydrothermal reaction of the matrix material is specifically performed by placing the matrix material in a vacuum drying oven and drying the matrix material at 55 to 75 ℃ for 2 to 4 hours.
Further, in the above technical solution, in step S3, the activation of the catalyst is specifically performed by placing the catalyst in a KOH solution of 1mol/L and scanning for activation.
Still further, in the above technical solution, in step S3, the sweep activation of the catalyst is cyclic voltammetry sweep with a sweep speed of 100mV S-1The number of scanning turns is 100 turns.
The invention also provides the application of the method in hydrogen production by electrolysis.
The invention has the advantages that:
the method provided by the invention can directly use the waste lignocellulose to produce hydrogen, not only can utilize and consume the waste lignocellulose, but also can reduce the energy consumption of hydrogen production by electrolyzing water, and can prepare clean energy hydrogen by using solar energy while reducing the waste and pollution caused by burning the lignocellulose, thereby improving the hydrogen production efficiency.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to specific examples.
The following examples are intended to illustrate the present invention, but not to limit the scope of the invention, which is defined by the claims.
Unless otherwise specified, the test reagents and materials used in the examples of the present invention are commercially available.
Unless otherwise specified, the technical means used in the examples of the present invention are conventional means well known to those skilled in the art.
Example 1
The embodiment 1 of the invention provides a method for producing hydrogen by electrolyzing waste lignocellulose, which specifically comprises the following steps:
(1) 1.5mmol of cobalt nitrate (Co (NO) was weighed3)2·7H2O), 0.5mmol of ferrous sulfate (Fe (SO)4)2·7H2O) and 16mmol of urea (CO (NH)2)2) 10mmol of ammonium fluoride (NH)4F) Adding into a hydrothermal reaction kettle containing 35ml of deionized water, adding magnetons, and stirring on a magnetic stirrer for 15 min. After stirring, sequentially adding acetone, ethanol and secondary waterAnd soaking the carbon fiber paper (CF) subjected to the cleaning treatment by dilute nitric acid and secondary water in a reaction kettle for 15 min. And (3) putting the reaction kettle into an oven, setting the temperature at 120 ℃, adding the reaction kettle for 16h, washing the product with ethanol, and putting the product into the oven at 60 ℃ for vacuum drying for 3h to obtain the precursor of the transition metal phosphide.
(2) The precursor was mixed with 560mg of phosphating agent (NaH)2PO2·H2O) is placed at two ends of a porcelain boat and is placed into a tube furnace, and the porcelain boat is subjected to heat preservation and calcination for 120min at 400 ℃ under the protection of Ar environment, so that the precursor is subjected to phosphorization, and the multi-transition metal phosphide catalyst taking carbon fiber paper as a base material is obtained.
(3) Drying waste raw lignocellulose (waste paper) at 80 deg.C overnight, and pulverizing to particle size of less than 0.25 cm. 3g of waste paper is soaked in a 1mol/L KOH and crude glycerol solution and stirred for 3h at 250 ℃.
(4) The catalyst is used as an electrode and is placed in 1mol/L KOH, the reaction temperature is 25 ℃, and the reaction temperature is 100mV s-1And (5) carrying out cyclic voltammetry scanning at a scanning speed, and scanning for 100 circles to complete activation.
(5) And (3) adopting a two-electrode system, wherein the catalyst prepared in the step (2) is a working negative electrode and a working positive electrode, and the solution in the step (3) is used as an electrolyte. When the hydrogen evolution performance test is carried out, when j is 10mAcm-2The potential at the time of electrode versus the standard hydrogen electrode was 1.30Vvs RHE.
(6) And (5) connecting the electrolytic cell in the step (5) with the perovskite cell, and placing the cell under simulated sunlight to construct a full-green low-cost electrolytic hydrogen production system.
Example 2
The embodiment 2 of the invention provides a method for producing hydrogen by electrolyzing waste lignocellulose, which specifically comprises the following steps:
(1) 1.5mmol of cobalt nitrate (Co (NO) was weighed3)2·7H2O), 0.5mmol of ferrous sulfate (Fe (SO)4)2·7H2O) and 16mmol of urea (CO (NH)2)2) 10mmol of ammonium fluoride (NH)4F) Adding into a hydrothermal reaction kettle containing 35ml of deionized water, adding magnetons, and stirring on a magnetic stirrer for 15 min. After stirring, the carbon fiber is washed by acetone, ethanol, secondary water, dilute nitric acid and secondary water in sequenceThe paper (CF) was soaked in the autoclave for 15 min. And (3) putting the reaction kettle into an oven, setting the temperature at 120 ℃, adding the reaction kettle for 16h, washing the product with ethanol, and putting the product into the oven at 60 ℃ for vacuum drying for 3h to obtain the precursor of the transition metal phosphide.
(2) The precursor was mixed with 560mg of phosphating agent (NaH)2PO2·H2O) is placed at two ends of a porcelain boat and is placed into a tube furnace, and the porcelain boat is subjected to heat preservation and calcination for 120min at 400 ℃ under the protection of Ar environment, so that the precursor is subjected to phosphorization, and the multi-transition metal phosphide catalyst taking carbon fiber paper as a base material is obtained.
(3) Drying waste raw lignocellulose (waste paper) at 80 deg.C overnight, and pulverizing to particle size of less than 0.25 cm. 5g of waste paper is soaked in a 1mol/L KOH and crude glycerol solution and stirred for 3h at 250 ℃.
(4) The catalyst is used as an electrode and is placed in 1mol/L KOH, the reaction temperature is 25 ℃, and the reaction temperature is 100mV s-1And (5) carrying out cyclic voltammetry scanning at a scanning speed, and scanning for 100 circles to complete activation.
(5) And (3) adopting a two-electrode system, wherein the catalyst prepared in the step (2) is a working negative electrode and a working positive electrode, and the solution in the step (3) is used as an electrolyte. When the hydrogen evolution performance test is carried out, when j is 10mAcm-2The potential at the time of electrode versus the standard hydrogen electrode was 1.34Vvs RHE.
(6) And (5) connecting the electrolytic cell in the step (5) with the perovskite cell, and placing the cell under simulated sunlight to construct a full-green low-cost electrolytic hydrogen production system.
Example 3
The embodiment 3 of the invention provides a method for producing hydrogen by electrolyzing waste lignocellulose, which specifically comprises the following steps:
(1) 1.5mmol of cobalt nitrate (Co (NO) was weighed3)2·7H2O), 0.5mmol of ferrous sulfate (Fe (SO)4)2·7H2O) and 16mmol of urea (CO (NH)2)2) 10mmol of ammonium fluoride (NH)4F) Adding into a hydrothermal reaction kettle containing 35ml of deionized water, adding magnetons, and stirring on a magnetic stirrer for 15 min. After stirring, soaking the carbon fiber paper (CF) which is washed by acetone, ethanol, secondary water, dilute nitric acid and secondary water in sequence in a reaction kettle for 15 min. Putting a reaction kettle intoAnd (3) drying in an oven, setting the temperature at 120 ℃, adding for 16h, washing the product with ethanol, and then putting the product into an oven at 60 ℃ for vacuum drying for 3h to obtain the precursor of the transition metal phosphide.
(2) The precursor was mixed with 560mg of phosphating agent (NaH)2PO2·H2O) is placed at two ends of a porcelain boat and is placed into a tube furnace, and the porcelain boat is subjected to heat preservation and calcination for 120min at 400 ℃ under the protection of Ar environment, so that the precursor is subjected to phosphorization, and the multi-transition metal phosphide catalyst taking carbon fiber paper as a base material is obtained.
(3) Drying waste raw lignocellulose (waste paper) at 80 deg.C overnight, and pulverizing to particle size of less than 0.25 cm. 3g of waste paper is soaked in 10mol/L KOH and crude glycerol solution and stirred for 3h at 250 ℃.
(4) The catalyst is used as an electrode and is placed in 1mol/L KOH, the reaction temperature is 25 ℃, and the reaction temperature is 100mV s-1And (5) carrying out cyclic voltammetry scanning at a scanning speed, and scanning for 100 circles to complete activation.
(5) And (3) adopting a two-electrode system, wherein the catalyst prepared in the step (2) is a working negative electrode and a working positive electrode, and the solution in the step (3) is used as an electrolyte. When the hydrogen evolution performance test is carried out, when j is 10mAcm-2The potential at the time of electrode versus the standard hydrogen electrode was 1.23Vvs RHE.
(6) And (5) connecting the electrolytic cell in the step (5) with the perovskite cell, and placing the cell under simulated sunlight to construct a full-green low-cost electrolytic hydrogen production system.
Example 4
The embodiment 4 of the invention provides a method for producing hydrogen by electrolyzing waste lignocellulose, which specifically comprises the following steps:
(1) 1.5mmol of cobalt nitrate (Co (NO) was weighed3)2·7H2O), 0.5mmol of ferrous sulfate (Fe (SO)4)2·7H2O) and 16mmol of urea (CO (NH)2)2) 10mmol of ammonium fluoride (NH)4F) Adding into a hydrothermal reaction kettle containing 35ml of deionized water, adding magnetons, and stirring on a magnetic stirrer for 15 min. After stirring, soaking the carbon fiber paper (CF) which is washed by acetone, ethanol, secondary water, dilute nitric acid and secondary water in sequence in a reaction kettle for 15 min. Putting the reaction kettle into an oven, setting the temperature at 120 ℃, adding the mixture for 16 hours, and obtaining the productWashing the material with ethanol, and then putting the washed material into a 60 ℃ oven for vacuum drying for 3h to obtain a precursor of the transition metal phosphide.
(2) The precursor was mixed with 560mg of phosphating agent (NaH)2PO2·H2O) is placed at two ends of a porcelain boat and is placed into a tube furnace, and the porcelain boat is subjected to heat preservation and calcination for 120min at 400 ℃ under the protection of Ar environment, so that the precursor is subjected to phosphorization, and the multi-transition metal phosphide catalyst taking carbon fiber paper as a base material is obtained.
(3) Drying the waste raw lignocellulose (straw) at 80 ℃ overnight, and crushing the waste raw lignocellulose (straw) to the particle size of less than 0.25 cm. Soaking 3g of straws in 1mol/L KOH and crude glycerol solution, and stirring for 3h at 250 ℃.
(4) The catalyst is used as an electrode and is placed in 1mol/L KOH, the reaction temperature is 25 ℃, and the reaction temperature is 100mV s-1And (5) carrying out cyclic voltammetry scanning at a scanning speed, and scanning for 100 circles to complete activation.
(5) And (3) adopting a two-electrode system, wherein the catalyst prepared in the step (2) is a working negative electrode and a working positive electrode, and the solution in the step (3) is used as an electrolyte. When the hydrogen evolution performance test is carried out, when j is 10mAcm-2The potential at the time of electrode versus the standard hydrogen electrode was 1.35Vvs RHE.
(6) And (5) connecting the electrolytic cell in the step (5) with the perovskite cell, and placing the cell under simulated sunlight to construct a full-green low-cost electrolytic hydrogen production system.
Example 5
The embodiment 5 of the invention provides a method for producing hydrogen by electrolyzing waste lignocellulose, which specifically comprises the following steps:
(1) 1.5mmol of cobalt nitrate (Co (NO) was weighed3)2·7H2O), 0.5mmol of ferrous sulfate (Fe (SO)4)2·7H2O) and 16mmol of urea (CO (NH)2)2) 10mmol of ammonium fluoride (NH)4F) Adding into a hydrothermal reaction kettle containing 35ml of deionized water, adding magnetons, and stirring on a magnetic stirrer for 15 min. After stirring, soaking the foamed nickel which is washed by acetone, ethanol, secondary water, dilute nitric acid and secondary water in the reaction kettle for 15 min. Putting the reaction kettle into an oven, setting the temperature at 120 ℃, adding the reaction kettle for 16h, washing the product with ethanol, putting the product into an oven at 60 ℃, and drying the product for 3h in vacuum to obtain the productTo a transition metal phosphide precursor.
(2) The precursor was mixed with 500mg of a phosphating agent (NaH)2PO2·H2O) is placed at two ends of a porcelain boat and is placed into a tube furnace, and the porcelain boat is subjected to heat preservation and calcination for 120min at 440 ℃ under the protection of Ar environment, so that the precursor is subjected to phosphorization, and the multi-transition metal phosphide catalyst taking carbon fiber paper as a base material is obtained.
(3) Drying waste raw lignocellulose (weed) at 80 deg.C overnight, and pulverizing to particle size of less than 0.25 cm. 3g of waste paper is soaked in 1mol/L NaOH and crude glycerol solution and stirred for 3h at 250 ℃.
(4) The catalyst is used as an electrode and is placed in 1mol/L KOH, the reaction temperature is 25 ℃, and the reaction temperature is 100mV s-1And (5) carrying out cyclic voltammetry scanning at a scanning speed, and scanning for 100 circles to complete activation.
(5) And (3) adopting a two-electrode system, wherein the catalyst prepared in the step (2) is a working negative electrode and a working positive electrode, and the solution in the step (3) is used as an electrolyte. When the hydrogen evolution performance test is carried out, when j is 10mAcm-2The potential at the time of electrode versus the standard hydrogen electrode was 1.32Vvs RHE.
(6) And (5) connecting the electrolytic cell in the step (5) with the perovskite cell, and placing the cell under simulated sunlight to construct a full-green low-cost electrolytic hydrogen production system.
Example 6
The embodiment 6 of the invention provides a method for producing hydrogen by electrolyzing waste lignocellulose, which specifically comprises the following steps:
(1) 2.0mmol of cobalt nitrate (Co (NO) was weighed3)2·7H2O) and 18mmol of urea (CO (NH)2)2) 10mmol of ammonium fluoride (NH)4F) Adding into a hydrothermal reaction kettle containing 35ml of deionized water, adding magnetons, and stirring on a magnetic stirrer for 15 min. And after stirring, soaking the carbon fiber cloth which is sequentially washed by acetone, ethanol, secondary water, dilute nitric acid and secondary water in the reaction kettle for 15 min. And (3) putting the reaction kettle into an oven, setting the temperature to be 135 ℃, adding the reaction kettle for 15h, washing the product with ethanol, and putting the product into the oven at 60 ℃ for vacuum drying for 3h to obtain the precursor of the transition metal phosphide.
(2) The precursor was mixed with 560mg of phosphating agent (NaH)2PO2·H2O) is placed at two ends of a porcelain boat and is placed into a tube furnace, and the porcelain boat is subjected to heat preservation and calcination for 120min at 400 ℃ under the protection of Ar environment, so that the precursor is subjected to phosphorization, and the multi-transition metal phosphide catalyst taking carbon fiber paper as a base material is obtained.
(3) Drying waste raw lignocellulose (waste paper) at 80 deg.C overnight, and pulverizing to particle size of less than 0.25 cm. 3g of waste paper is soaked in a 1mol/L KOH and crude glycerol solution and stirred for 3h at 300 ℃.
(4) The catalyst is used as an electrode and is placed in 1mol/L KOH, the reaction temperature is 25 ℃, and the reaction temperature is 100mV s-1And (5) carrying out cyclic voltammetry scanning at a scanning speed, and scanning for 100 circles to complete activation.
(5) And (3) adopting a two-electrode system, wherein the catalyst prepared in the step (2) is a working negative electrode and a working positive electrode, and the solution in the step (3) is used as an electrolyte. When the hydrogen evolution performance test is carried out, when j is 10mAcm-2The potential at the time of electrode versus the standard hydrogen electrode was 1.20Vvs RHE.
(6) And (5) connecting the electrolytic cell in the step (5) with the perovskite cell, and placing the cell under simulated sunlight to construct a full-green low-cost electrolytic hydrogen production system.
Example 7
The embodiment 7 of the invention provides a method for producing hydrogen by electrolyzing waste lignocellulose, which specifically comprises the following steps:
(1) 1.5mmol of cobalt nitrate (Co (NO) was weighed3)2·7H2O), 0.5mmol of ferrous sulfate (Fe (SO)4)2·7H2O) and 16mmol of urea (CO (NH)2)2) 10mmol of ammonium fluoride (NH)4F) Adding into a hydrothermal reaction kettle containing 35ml of deionized water, adding magnetons, and stirring on a magnetic stirrer for 15 min. After stirring, soaking the carbon fiber paper (CF) which is washed by acetone, ethanol, secondary water, dilute nitric acid and secondary water in sequence in a reaction kettle for 15 min. And (3) putting the reaction kettle into an oven, setting the temperature at 120 ℃, adding the reaction kettle for 16h, washing the product with ethanol, and putting the product into the oven at 60 ℃ for vacuum drying for 3h to obtain the precursor of the transition metal phosphide.
(2) The precursor was mixed with 560mg of phosphating agent (NaH)2PO2·H2O) are arranged at the two ends of the porcelain boat,and (3) putting the precursor into a tube furnace, and carrying out heat preservation and calcination for 120min at 400 ℃ under the protection of Ar environment to phosphorize the precursor, thereby obtaining the multi-transition metal phosphide catalyst taking carbon fiber paper as a base material.
(3) Drying waste raw lignocellulose (waste paper) at 80 deg.C overnight, and pulverizing to particle size of less than 0.25 cm. 3g of waste paper is soaked in a 1mol/L KOH and crude glycerol solution and stirred for 3h at 350 ℃.
(4) The catalyst is used as an electrode and is placed in 1mol/L KOH, the reaction temperature is 25 ℃, and the reaction temperature is 100mV s-1And (5) carrying out cyclic voltammetry scanning at a scanning speed, and scanning for 100 circles to complete activation.
(5) And (3) adopting a two-electrode system, wherein the catalyst prepared in the step (2) is a working negative electrode and a working positive electrode, and the solution in the step (3) is used as an electrolyte. When the hydrogen evolution performance test is carried out, when j is 10mAcm-2The potential at the time of electrode versus the standard hydrogen electrode was 1.19Vvs RHE.
(6) And (5) connecting the electrolytic cell in the step (5) with the perovskite cell, and placing the cell under simulated sunlight to construct a full-green low-cost electrolytic hydrogen production system.
The method provided by the embodiment of the invention can directly use the waste lignocellulose to prepare hydrogen, not only can utilize and consume the waste lignocellulose, but also can reduce the energy consumption of hydrogen preparation by water electrolysis, and can prepare clean energy hydrogen by using solar energy while reducing the waste and pollution caused by lignocellulose incineration, thereby improving the hydrogen preparation efficiency.
The above embodiments are merely illustrative of the present invention, and not restrictive, and many modifications and changes may be made by those skilled in the art without departing from the spirit of the invention, and it is intended that all such modifications and changes as fall within the true spirit of the invention and the scope of the claims be determined by those skilled in the art.
Claims (10)
1. A method for producing hydrogen by utilizing waste lignocellulose through electrolysis is characterized by comprising the following steps,
s1, placing the pretreated substrate material into a mixed solution containing transition metal salt and a template agent, taking out the substrate material after hydrothermal reaction, cleaning and drying the substrate material, heating the substrate material under the protection of inert gas, and carrying out a phosphating reaction under the action of a phosphating agent to obtain a catalyst, wherein the template agent is a mixture of urea and ammonium fluoride;
s2, crushing the waste lignocellulose raw material, drying, adding the crushed waste lignocellulose raw material into a mixed solution containing an alkaline solution and polyhydric alcohol, uniformly mixing, and heating and liquefying to obtain an electrolyte;
s3, activating the catalyst obtained in the step S1, then adopting a two-electrode system, taking the activated catalyst as a working negative and positive electrode, placing the working negative and positive electrode in the electrolyte obtained in the step S2 to form an electrolytic cell, and electrolytically producing hydrogen.
2. The method according to claim 1, further comprising exposing the cell of step S3 to sunlight to photolytically produce hydrogen after connecting the cell to a perovskite cell.
3. The method according to claim 1 or 2, wherein, in step S2,
the particle size of the crushed waste lignocellulose raw material is less than 0.25 cm;
and/or the drying temperature and the drying time of the waste lignocellulose raw material are respectively 75-90 ℃ and 8-15 h;
and/or the liquefaction temperature and time of the heating liquefaction are respectively 250-350 ℃ and 3-8 h.
4. The method according to any one of claims 1 to 3, wherein in step S2, the alkaline solution is KOH or NaOH solution, preferably KOH solution with a concentration of 1 mol/L.
5. The method according to claim 1 or 2, wherein, in step S1,
the matrix material is one or more of carbon fiber paper, carbon fiber cloth, foam nickel and foam copper, and preferably carbon fiber paper;
and/or, the template is a mixture of the following components in a molar ratio (1.5-2.0): 1, a mixture of urea and ammonium fluoride;
and/or the transition metal salt is nitrate or sulfate of Fe, Co or Ni, and preferably the molar ratio is (2.5-3.6): 1, a mixture of cobalt nitrate and ferrous sulfate;
and/or the phosphating agent is NaH2PO2·H2O。
6. The method according to any one of claims 1 to 5, wherein, in step S1,
the reaction temperature and the reaction time of the hydrothermal reaction are respectively 110-135 ℃ and 15-18h, preferably 120 ℃ and 16 h;
and/or the reaction temperature and the reaction time of the phosphating reaction are respectively 360 ℃ and 450 ℃ and 1.5-3h, and preferably 400 ℃ and 2 h.
7. The method according to any one of claims 1 to 6, wherein, in step S1,
the pretreatment of the matrix material is specifically that acetone, ethanol, secondary water, dilute nitric acid and secondary water are sequentially used for cleaning treatment;
and/or cleaning and drying the matrix material after the hydrothermal reaction, namely drying the matrix material in a vacuum drying oven at 55-75 ℃ for 2-4 h.
8. The method according to claim 1 or 2, wherein in step S3, the catalyst is activated by scanning the catalyst in 1mol/L KOH solution.
9. The method of claim 8, wherein in step S3, the sweep activation of the catalyst is cyclic voltammetry sweep at a sweep rate of 100mV S-1The number of scanning turns is 100 turns.
10. Use of the method of any one of claims 1 to 9 for the electrolytic production of hydrogen.
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| CN201910197029.6A CN111690945B (en) | 2019-03-15 | 2019-03-15 | Method for producing hydrogen by electrolyzing waste lignocellulose |
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