Method for hydrogen production through photoelectric iron concerted catalysis of biomass reforming
Through photoelectric synergistic catalysis technology, non-precious metal iron catalysts are used to achieve biomass molecular fracture and proton reduction under visible light conditions, solving the problems of harsh reaction conditions and the use of precious metal catalysts in the existing technology, and achieving efficient and low-cost hydrogen production. It is both highly selective and environmentally friendly.
Patent Information
- Application Number
- CN202411321176.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-23
- Publication Date
- 2024-12-13
AI Technical Summary
The existing photocatalytic biomass hydrogen production technology has problems such as harsh reaction conditions, low use of precious metal catalysts, and low efficiency, especially the need to add a large amount of additives to the primary biomass, which leads to high costs and environmental pollution.
Using photoelectric synergistic catalysis method, the inexpensive and easy-to-get non-precious metal iron is used as a catalyst to transfer the charge from ligand to metal under visible light conditions through the formation of iron and biomass molecules, thereby realizing C-C bond rupture and proton reduction of biomass molecules. Complete efficient conversion of hydrogen.
No additives are required at room temperature and normal pressure, high hydrogen yield and high selectivity are achieved, cost and environmental pollution are reduced, and it is compatible with various biomass and their derivatives. The reaction conditions are mild and the catalytic system is highly compatible.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of biomass hydrogen production, and specifically relates to a method for producing hydrogen through photoelectric iron synergistic catalytic reforming of biomass. Background Art
[0002] Compared with traditional thermochemical catalytic methods, the photocatalytic conversion of biomass to produce H2 has milder reaction conditions (normal temperature and pressure) and requires lower energy consumption.
[0003] Professors Kawai and Sakata first proposed a method for producing hydrogen by photocatalytic biomass reforming (Kawai T, Sakata T. Conversion of carbohydrate into hydrogen fuel by a photocatalytic process. Nature, 1980, 286, 474-476.). This method uses RuO2 / TiO2 / Pt as photoactive materials and uses sugar compounds as electron sacrificial agents to produce hydrogen under the irradiation of a high-pressure mercury lamp (500 W, λ<320 nm). Since the reaction is carried out under ultraviolet conditions and 13 mg of substrate requires 150 mg of RuO2 / TiO2 / Pt photoactive material, it is not realistic to apply this method industrially. Professor Hsisheng Teng used graphene quantum dots loaded with precious metal platinum (Pt) as photoactive materials to produce hydrogen by oxidizing biomass to produce active oxygen species. The reaction only achieved an 18% yield in 6 days. In addition, when native biomass was used as the reaction substrate, the reaction required the addition of a large amount of strong base as an additive; therefore, this catalytic method not only used precious metal Pt as a co-catalyst, but also had a very low reaction efficiency (Van-Can, N., Nimbalkar, DB, Nam, LD, Lee, Y.-L. & Teng, H. Photocatalytic cellulose reforming for H2 and formate production by using graphene oxide-dot catalysts. ACS Catal., 2021, 11, 4955–4967.). Researcher Wang Feng and Professor Paolo Fornasiero jointly proposed a biomass H2 production method of "CC bond priority" cleavage. Ta-doped CeO2 was used to cleave the CC bonds of biopolyols and sugars and convert them into formic acid and formaldehyde. Then, Pt / P25 was used as a photocatalyst or Ru complex was used as a thermal catalyst to decompose formic acid and formaldehyde into H2. The hydrogen yields were theoretical values for hydrogen production from photocatalytic glucose reforming (C6H 12O6+6H2O→12H2+6CO2) (33% and 30% (Ren, P. et al. Stepwise photoassisted decomposition of carbohydrates to H2. Joule, 2023, 7, 333–349.). This method also inevitably uses the precious metal Pt as a co-catalyst, and the maximum hydrogen yield is only 33%.
[0004] In summary, the reaction conditions of the above existing methods are still relatively harsh. When using raw biomass as reactants, a large amount of additives need to be added, and expensive precious metals are used to prepare catalysts, which undoubtedly increases the cost of practical application. The essence of this type of catalyst is to directly oxidize biomass molecules through active oxygen species or holes. Since the oxidation process is not selective, the H2 yield and selectivity are low. Therefore, the development of a high-yield and high-selectivity biomass reforming hydrogen production method under mild conditions (normal temperature and pressure) using non-precious metals is an important problem that needs to be solved urgently. Summary of the invention
[0005] In order to overcome the shortcomings of the above-mentioned prior art, the purpose of the present invention is to provide a method for hydrogen production by biomass reforming by photoelectric-iron synergistic catalysis, which adopts a photoelectric combination method at room temperature and pressure without adding any additives, uses cheap and readily available non-precious metal iron as a catalyst, forms a complex with iron and biomass molecules, and a ligand-to-metal charge transfer process (LMCT) occurs under visible light conditions to achieve the sequential breaking of the C-C bonds of the biomass molecules to carbon dioxide and protons, and uses the electrochemical cathode to reduce protons to release hydrogen, thereby completing the efficient conversion of water reforming biomass to hydrogen.
[0006] In order to achieve the above object, the technical solution adopted by the present invention is:
[0007] A method for producing hydrogen by photoelectric iron synergistic catalytic reforming of biomass comprises the following steps:
[0008] The biomass and its derivatives are placed in an aqueous solution, and an iron salt catalyst and an inorganic salt electrolyte are added, wherein 6-180 mL of aqueous solution, 0.00808-0.4 g of iron salt catalyst, and 0.1-3 g of inorganic salt electrolyte are added for every 1 g of biomass and its derivatives, and bubbling deoxygenation is performed; a graphite electrode is used as an anode, and a Ni, Cu, Mg or graphite electrode is used as a cathode, 1-50 mA current is passed for electrolysis, and a light reaction is carried out at 20-40°C, the light intensity is: 3-20 W, and the light wavelength is: 400-480 nm.
[0009] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2.
[0010] The biomass and its derivatives are glucose, xylose, arabinose, rhamnose, erythrose, glyceraldehyde, glycoaldehyde, cellobiose, xylan, cellulose, fructose, sorbitol, glycerol, and wheat straw, corn straw, rice straw or reed stalk.
[0011] The iron salt catalyst is FeCl2·4H2O, FeCl3·6H2O, Fe2(SO4)3, Fe(NO3)3·9H2O, Fe(acac)3 or Fe(OTf)3.
[0012] The inorganic salt electrolyte is NaCl, NaNO3, Na2SO4, Na2CO3, LiCl, LiNO3 or LiClO4.
[0013] Table 1 Summary of methods and conditions for photocatalytic biomass reforming to produce hydrogen
[0014]
[0015] Referring to Table 1, compared with the prior art, the beneficial effects of the present invention are as follows:
[0016] 1. The reaction conditions are milder. The present invention achieves a higher hydrogen yield without using ultraviolet light and a lower power light source.
[0017] 2. The catalyst is cheap, readily available and non-toxic. The co-catalysts used in the prior art heterogeneous photocatalytic biomass hydrogen production reaction are mostly precious metal catalysts, and the cadmium in cadmium sulfide (CdS) is toxic and seriously pollutes the environment; the iron catalyst used in the present invention is cheap, readily available and non-polluting to the environment.
[0018] 3. Reduced use of additives. In the prior art, except for water-soluble compounds such as glucose as substrates, other poorly soluble substrates require the use of a certain amount of additives to promote biomass conversion, which invisibly increases the conversion cost and limits its industrial application. The present invention can achieve efficient conversion of biomass and its derivatives without any additives, and does not require the participation of a large amount of organic solvents, thereby reducing costs and environmental pollution.
[0019] 4. Highest hydrogen yield. In addition to the two literatures mentioned in the background technology that reported H2 yields of 18% and 33% (calculated relative to the theoretical value of hydrogen production from photocatalytic glucose reforming), most literature only gives the unit of mmolg - 1 h -1 The data do not give percentage yields.
[0020] In summary, the present invention adopts a photoelectric combination method under normal temperature and pressure without adding additives, uses cheap and easily available non-precious metal iron as a catalyst, forms a complex with iron and biomass molecules, and a ligand-to-metal charge transfer process (LMCT) occurs under visible light conditions to achieve the sequential breaking of the CC bonds of biomass molecules to carbon dioxide and protons, and uses electrochemical cathode reduction of protons to release hydrogen, completing the efficient conversion of water reforming biomass to produce hydrogen. Compared with the prior art, the original ecological biomass hydrogen production yield of the present invention is high; the present invention is a water-phase reaction system, which does not require the participation of a large amount of organic solvents, reducing costs and environmental pollution; compared with other catalytic systems, the catalytic system of the present invention has strong compatibility (compatible with various biomass and its derivatives), mild reaction conditions (visible light, normal temperature, normal pressure), high H2 selectivity, and low cost (non-precious metal, no additives required). DETAILED DESCRIPTION
[0021] The present invention is described in detail below with reference to the embodiments.
[0022] Example 1, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0023] Biomass and its derivative glucose are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 6 mL of aqueous solution, 0.00808 g of FeCl3·6H2O, and 0.1 g of NaCl are added to every 1 g of glucose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 1 mA current is passed through for electrolysis, and a light reaction is carried out at 20°C, the light intensity is 3 W, and the light wavelength is 400 nm.
[0024] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 68% (calculated based on the C atoms in the feed amount).
[0025] Example 2, a method for producing hydrogen by photoelectric iron synergistic catalytic reforming of biomass, comprising the following steps:
[0026] Biomass and its derivative glucose are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 12mL of aqueous solution, 0.016g of FeCl3·6H2O, and 0.2g of NaCl are added to every 1g of glucose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 5mA current is passed through for electrolysis, and a light reaction is carried out at 20°C, the light intensity is: 10W, and the light wavelength is: 410nm.
[0027] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 77% (calculated based on the C atoms in the feed amount).
[0028] Embodiment 3, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0029] Biomass and its derivative glucose are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 30 mL of aqueous solution, 0.048 g of FeCl3·6H2O, and 0.6 g of NaCl are added to every 1 g of glucose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 10 mA current is passed through for electrolysis, and a light reaction is carried out at 20°C, the light intensity is: 20 W, and the light wavelength is: 440 nm.
[0030] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 89% (calculated based on the C atoms in the feed amount).
[0031] Example 4, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0032] The biomass and its derivative glucose are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 60 mL of aqueous solution, 0.081 g of FeCl3·6H2O, and 3 g of NaCl are added to every 1 g of glucose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 50 mA current is passed through for electrolysis, and a light reaction is carried out at 20°C, the light intensity is: 20 W, and the light wavelength is: 480 nm.
[0033] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 90% (calculated based on the C atoms in the feed amount).
[0034] Example 5, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0035] Biomass and its derivative glucose are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 180 mL of aqueous solution, 0.4 g of FeCl3·6H2O, and 3 g of NaCl are added to every 1 g of glucose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 50 mA current is passed through for electrolysis, and a light reaction is carried out at 20°C, the light intensity is: 20 W, and the light wavelength is: 480 nm.
[0036] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 98% (calculated based on the C atoms in the feed amount).
[0037] Example 6, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0038] The biomass and its derivative glucose are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 100 mL of aqueous solution, 0.3 g of FeCl3·6H2O, and 2 g of NaCl are added to every 1 g of glucose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 40 mA current is passed through for electrolysis, and a light reaction is carried out at 40°C, the light intensity is 18 W, and the light wavelength is 410 nm.
[0039] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 92% (calculated based on the C atoms in the feed amount).
[0040] Example 7, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0041] The biomass and its derivative glucose are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 120 mL of aqueous solution, 0.2 g of FeCl3·6H2O, and 2 g of NaCl are added to every 1 g of glucose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 30 mA current is passed through for electrolysis, and a light reaction is carried out at 30°C, the light intensity is 10 W, and the light wavelength is 400 nm.
[0042] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12O6+6H2O→12H2+6CO2, the hydrogen yield is 86% (calculated based on the C atoms in the feed amount).
[0043] Example 8, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0044] The biomass and its derivative glucose are placed in an aqueous solution, and an iron salt catalyst Fe(NO3)3·9H2O and an inorganic salt electrolyte NaNO3 are added, wherein 120 mL of aqueous solution, 0.3 g of Fe(NO3)3·9H2O, and 2 g of NaNO3 are added for every 1 g of glucose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Cu electrode as a cathode, a 30 mA current is passed through for electrolysis, and a light reaction is carried out at 30°C, the light intensity is 10 W, and the light wavelength is 400 nm.
[0045] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 77% (calculated based on the C atoms in the feed amount).
[0046] Example 9, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0047] The biomass and its derivative glucose are placed in an aqueous solution, and an iron salt catalyst Fe(NO3)3·9H2O and an inorganic salt electrolyte NaNO3 are added, wherein 120 mL of aqueous solution, 0.3 g of Fe(NO3)3·9H2O, and 2 g of NaNO3 are added for every 1 g of glucose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Mg electrode as a cathode, a 30 mA current is passed through for electrolysis, and a light reaction is carried out at 30°C, the light intensity is 18 W, and the light wavelength is 450 nm.
[0048] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 82% (calculated based on the C atoms in the feed amount).
[0049] Embodiment 10, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0050] Biomass and its derivative glucose are placed in an aqueous solution, and an iron salt catalyst Fe2(SO4)3 and an inorganic salt electrolyte Na2SO4 are added, wherein 120 mL of aqueous solution, 0.224 g of Fe2(SO4)3, and 1 g of Na2SO4 are added for every 1 g of glucose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode as a cathode, a 50 mA current is passed through for electrolysis, and a light reaction is carried out at 30°C, the light intensity is 20 W, and the light wavelength is 450 nm.
[0051] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 94% (calculated based on the C atoms in the feed amount).
[0052] Example 11, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0053] Biomass and its derivative glucose are placed in an aqueous solution, and an iron salt catalyst Fe(acac)3 and an inorganic salt electrolyte NaCl are added, wherein 120 mL of aqueous solution, 0.324 g of Fe(acac)3, and 1 g of NaCl are added for every 1 g of glucose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a graphite electrode as a cathode, a 20 mA current is passed for electrolysis, and a light reaction is carried out at 30°C, the light intensity is 20 W, and the light wavelength is 450 nm.
[0054] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 83% (calculated based on the C atoms in the feed amount).
[0055] Example 12, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0056] Biomass and its derivative glucose are placed in an aqueous solution, and an iron salt catalyst FeCl2·4H2O and an inorganic salt electrolyte NaCl are added, wherein 120 mL of aqueous solution, 0.3 g of FeCl2·4H2O, and 2 g of NaCl are added to every 1 g of glucose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a graphite electrode as a cathode, a 20 mA current is passed for electrolysis, and a light reaction is performed at 30°C, the light intensity is 20 W, and the light wavelength is 450 nm.
[0057] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12O6+6H2O→12H2+6CO2, the hydrogen yield is 90% (calculated based on the C atoms in the feed amount).
[0058] Example 13, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0059] Biomass and its derivative glucose are placed in an aqueous solution, and an iron salt catalyst Fe(OTf)3 and an inorganic salt electrolyte LiCl are added, wherein 120 mL of aqueous solution, 0.024 g of Fe(OTf)3, and 1 g of NaCl are added for every 1 g of glucose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a graphite electrode as a cathode, a 20 mA current is passed for electrolysis, and a light reaction is carried out at 30°C, the light intensity is 20 W, and the light wavelength is 450 nm.
[0060] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 85% (calculated based on the C atoms in the feed amount).
[0061] Example 14, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0062] Biomass and its derivative glucose are placed in an aqueous solution, and an iron salt catalyst Fe(OTf)3 and an inorganic salt electrolyte LiNO3 are added, wherein 120 mL of aqueous solution, 0.024 g of Fe(OTf)3, and 1 g of LiNO3 are added for every 1 g of glucose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a graphite electrode as a cathode, a 20 mA current is passed for electrolysis, and a light reaction is carried out at 30°C, the light intensity is 20 W, and the light wavelength is 450 nm.
[0063] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 82% (calculated based on the C atoms in the feed amount).
[0064] Example 15, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0065] Biomass and its derivative glucose are placed in an aqueous solution, and an iron salt catalyst Fe(OTf)3 and an inorganic salt electrolyte Na2CO3 are added, wherein 120 mL of aqueous solution, 0.024 g of Fe(OTf)3, and 1 g of Na2CO3 are added for every 1 g of glucose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode as a cathode, a 10 mA current is passed for electrolysis, and a light reaction is carried out at 20°C, the light intensity is 10 W, and the light wavelength is 480 nm.
[0066] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 68% (calculated based on the C atoms in the feed amount).
[0067] Example 16, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0068] The biomass and its derivative xylose are placed in an aqueous solution, and an iron salt catalyst Fe(OTf)3 and an inorganic salt electrolyte Na2CO3 are added, wherein 100 mL of aqueous solution, 0.024 g of Fe(OTf)3, and 2 g of Na2CO3 are added for every 1 g of xylose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode as a cathode, a 40 mA current is passed through for electrolysis, and a light reaction is carried out at 20°C, the light intensity is 10 W, and the light wavelength is 480 nm.
[0069] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 92% (calculated based on the C atoms in the feed amount).
[0070] Example 17, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0071] The biomass and its derivative arabinose are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 6 mL of aqueous solution, 0.4 g of FeCl3·6H2O, and 3 g of NaCl are added for every 1 g of arabinose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 10 mA current is passed through for electrolysis, and a light reaction is carried out at 20°C, the light intensity is: 20 W, and the light wavelength is: 420 nm.
[0072] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12O6+6H2O→12H2+6CO2, the hydrogen yield is 96% (calculated based on the C atoms in the feed amount).
[0073] Example 18, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0074] The biomass and its derivative erythrose are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 6 mL of aqueous solution, 0.4 g of FeCl3·6H2O, and 3 g of NaCl are added to every 1 g of erythrose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 10 mA current is passed through for electrolysis, and a light reaction is carried out at 20°C, the light intensity is 20 W, and the light wavelength is 420 nm.
[0075] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 86% (calculated based on the C atoms in the feed amount).
[0076] Example 19, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0077] Biomass and its derivative cellobiose are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 6 mL of aqueous solution, 0.4 g of FeCl3·6H2O, and 3 g of NaCl are added to every 1 g of cellobiose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 10 mA current is passed through for electrolysis, and a light reaction is carried out at 40°C, the light intensity is: 20 W, and the light wavelength is: 420 nm.
[0078] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 96% (calculated based on the C atoms in the feed amount).
[0079] Example 20, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0080] The biomass and its derivative xylan are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 100 mL of aqueous solution, 0.4 g of FeCl3·6H2O, and 3 g of NaCl are added to every 1 g of xylan, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 10 mA current is passed through for electrolysis, and a light reaction is carried out at 40°C, the light intensity is: 20 W, and the light wavelength is: 420 nm.
[0081] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 93% (calculated based on the C atoms in the feed amount).
[0082] Example 21, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0083] The biomass and its derivative cellulose are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 180 mL of aqueous solution, 0.4 g of FeCl3·6H2O, and 3 g of NaCl are added to every 1 g of cellulose, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 10 mA current is passed through for electrolysis, and a light reaction is carried out at 40°C, the light intensity is: 20 W, and the light wavelength is: 420 nm.
[0084] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 87% (calculated based on the C atoms in the feed amount).
[0085] Example 22, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0086] The biomass and its derivative sorbitol are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 100 mL of aqueous solution, 0.3 g of FeCl3·6H2O, and 2 g of NaCl are added for every 1 g of sorbitol, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 30 mA current is passed through for electrolysis, and a light reaction is carried out at 40°C, the light intensity is 20 W, and the light wavelength is 420 nm.
[0087] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12O6+6H2O→12H2+6CO2, the hydrogen yield is 88% (calculated based on the C atoms in the feed amount).
[0088] Example 23, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0089] The biomass and its derivative wheat straw are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 100 mL of aqueous solution, 0.3 g of FeCl3·6H2O, and 2 g of NaCl are added to every 1 g of wheat straw, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 30 mA current is passed through for electrolysis, and a light reaction is carried out at 40°C, the light intensity is 20 W, and the light wavelength is 420 nm.
[0090] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 68% (calculated based on the C atoms in the feed amount).
[0091] Example 24, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0092] The biomass and its derivative corn stalks are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 100 mL of aqueous solution, 0.3 g of FeCl3·6H2O, and 2 g of NaCl are added to every 1 g of corn stalks, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 30 mA current is passed through for electrolysis, and a light reaction is carried out at 40°C, the light intensity is 10 W, and the light wavelength is 440 nm.
[0093] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 40% (calculated based on the C atoms in the feed amount).
[0094] Example 25, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0095] The biomass and its derivative rice straw are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 120 mL of aqueous solution, 0.3 g of FeCl3·6H2O, and 2 g of NaCl are added to every 1 g of rice straw, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 50 mA current is passed through for electrolysis, and a light reaction is carried out at 40°C, the light intensity is 10 W, and the light wavelength is 440 nm.
[0096] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 88% (calculated based on the C atoms in the feed amount).
[0097] Example 26, a method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming, comprising the following steps:
[0098] The biomass and its derivative reed stems are placed in an aqueous solution, and an iron salt catalyst FeCl3·6H2O and an inorganic salt electrolyte NaCl are added, wherein 100 mL of aqueous solution, 0.3 g of FeCl3·6H2O, and 2 g of NaCl are added to every 1 g of reed stems, and bubbling deoxygenation is performed; a graphite electrode is used as an anode and a Ni electrode is used as a cathode, a 50 mA current is passed through for electrolysis, and a light reaction is carried out at 40°C, the light intensity is: 20 W, and the light wavelength is: 400 nm.
[0099] After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 12 O6+6H2O→12H2+6CO2, the hydrogen yield is 88% (calculated based on the C atoms in the feed amount).
Claims
1. A method for producing hydrogen from biomass by photoelectric iron synergistic catalysis reforming, It is characterized in that The following steps are involved: The biomass and its derivatives are placed in an aqueous solution, and an iron salt catalyst and an inorganic salt electrolyte are added, wherein 6-180 mL of aqueous solution, 0.00808-0.4 g of iron salt catalyst, and 0.1-3 g of inorganic salt electrolyte are added for every 1 g of biomass and its derivatives, and bubbling deoxygenation is performed; a graphite electrode is used as an anode, and a Ni, Cu, Mg or graphite electrode is used as a cathode, 1-50 mA current is passed for electrolysis, and a light reaction is carried out at 20-40°C, the light intensity is: 3-20 W, and the light wavelength is: 400-480 nm.
2. The method according to claim 1, Features: After the reaction, the hydrogen yield was determined by GC. The hydrogen yield was calculated based on the hydrogen production from photocatalytic glucose reforming. 6 H 12 O 6 +6H 2 O→12H 2 +6CO 2 .
3. The method according to claim 1, Features: The biomass and its derivatives are glucose, xylose, arabinose, rhamnose, erythrose, glyceraldehyde, glycoaldehyde, cellobiose, xylan, cellulose, fructose, sorbitol, glycerol, and wheat straw, corn straw, rice straw or reed stalk.
4. The method according to claim 1, Features: The iron salt catalyst is FeCl 2 ·4H 2 O, FeCl 3 6H 2 O, Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 9H 2 O, Fe(acac) 3 or Fe(OTf) 3 .
5. The method according to claim 1, Features: The inorganic salt electrolyte is NaCl, NaNO 3 、Na 2 SO 4 、Na 2 CO 3 、LiCl、LiNO 3 or LiClO 4 .
6. The method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming according to claim 1, It is characterized in that The following steps are involved: Biomass and its derivative glucose were placed in aqueous solution and iron salt catalyst FeCl was added 3 6H 2 O and inorganic electrolyte NaCl, of which 6 mL of aqueous solution and 0.00808 g of FeCl 3 6H 2 O, 0.1gNaCl, and bubbling deoxygenation; using a graphite electrode as an anode and a Ni electrode as a cathode, a 1mA current is passed for electrolysis, and a light reaction is carried out at 20°C, the light intensity is 3W, and the light wavelength is 400nm.
7. The method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming according to claim 1, It is characterized in that The following steps are involved: Biomass and its derivative glucose were placed in aqueous solution and iron salt catalyst FeCl was added 3 6H 2 O and inorganic electrolyte NaCl, where 12 mL of aqueous solution is added for every 1 g of glucose, 0.016 g of FeCl 3 6H 2 O, 0.2gNaCl, and bubbling deoxygenation; using a graphite electrode as an anode and a Ni electrode as a cathode, a 5mA current was passed for electrolysis, and a light reaction was carried out at 20°C, the light intensity was 10W, and the light wavelength was 410nm.
8. The method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming according to claim 1, It is characterized in that The following steps are involved: Biomass and its derivative glucose were placed in aqueous solution and iron salt catalyst FeCl was added 3 6H 2 O and inorganic electrolyte NaCl, of which 30 mL aqueous solution and 0.048 g FeCl 3 6H 2 O, 0.6gNaCl, and bubbling deoxygenation; using a graphite electrode as an anode and a Ni electrode as a cathode, passing a 10mA current for electrolysis, and performing light irradiation reaction at 20°C, light intensity: 20W, light wavelength: 440nm.
9. The method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming according to claim 1, It is characterized in that The following steps are involved: The biomass and its derivative glucose were placed in aqueous solution and an iron salt catalyst FeCl was added. 3 6H 2 O and inorganic electrolyte NaCl, of which 60 mL of aqueous solution and 0.081 g of FeCl were added per 1 g of glucose. 3 6H 2 O, 3gNaCl, and bubbling deoxygenation; using a graphite electrode as an anode and a Ni electrode as a cathode, a 50mA current is passed for electrolysis, and a light reaction is carried out at 20°C, the light intensity is 20W, and the light wavelength is 480nm.
10. The method for producing hydrogen by photoelectric iron synergistic catalytic biomass reforming according to claim 1, It is characterized in that The following steps are involved: The biomass and its derivative glucose were placed in aqueous solution and an iron salt catalyst FeCl was added. 3 6H 2 O and inorganic electrolyte NaCl, where 180 mL of aqueous solution and 0.4 g of FeCl are added per 1 g of glucose. 3 6H 2 O, 3gNaCl, and bubbling deoxygenation; using a graphite electrode as an anode and a Ni electrode as a cathode, a 50mA current is passed for electrolysis, and a light reaction is carried out at 20°C, the light intensity is 20W, and the light wavelength is 480nm.