Protein-based hydrogel adsorption material and application thereof in repairing heavy metal pollution of water and soil

Abstract

The invention discloses a protein-based hydrogel adsorption material and application thereof in repairing water and soil heavy metal pollution, polysaccharide is doped into protein hydrogel to prepare the hydrogel adsorption material which is good in toughness, high in porosity and rich in surface adsorption functional groups. The heavy metal contaminated water and soil can be effectively adsorbed and efficiently recycled, especially for the heavy metal contaminated soil, the heavy metal contaminated soil is coated with the heavy metal contaminated water and soil adsorbent, the heavy metal contaminated soil is covered with the heavy metal contaminated water and soil adsorbent, in-situ remediation of the contaminated soil is achieved, meanwhile, the thin film is removed after remediation, and the risk of secondary overflow is thoroughly avoided. Results show that the protein-based hydrogel adsorbing material can efficiently remove different heavy metal pollutants, and after different treatments, the corresponding agricultural soil land control level can be reached. Moreover, no nutrient loss is observed in the treated soil, and no secondary toxic product is generated, so that the method has relatively high sustainability and agricultural application feasibility.

Description

Technical Field

[0001] The present invention belongs to the technical field of heavy metal pollution treatment, and specifically relates to a protein-based hydrogel adsorption material, and the use of the adsorption material to achieve the restoration of wastewater and soil contaminated by heavy metals. Background Art

[0002] Heavy metal pollution has increasingly become an ecological and environmental problem that threatens the world. Because of its characteristics of hysteresis, concealment, surface aggregation, irreversibility and long-term nature, the restoration of heavy metal-contaminated soil has long been one of the key research directions for improving the ecosystem. At present, for contaminated soil, many researchers have proposed a variety of biological, physical and chemical restoration methods, including the use of hyperaccumulatory plant restoration, to reduce the content of heavy metals in the soil. Although plant restoration can completely eradicate the harm of heavy metals, absorb and enrich heavy metals from the soil, thereby completely reducing the content of heavy metals in the soil and playing a role in improving the environment, it is time-consuming and the restoration effect is very low; while the cost of physical restoration is too high, it is more likely to cause a decrease in soil fertility and a decrease in crop productivity. Although chemical restoration can avoid the disadvantages of both, the current technology is not yet mature, and the restoration effect of chemical restoration agents is not stable. Once the external environment changes, the passivated heavy metals are likely to be activated, causing secondary pollution of heavy metals.

[0003] Hydrogel is a polymer material with a three-dimensional network structure. It can quickly absorb water and swell in water. It has the characteristics of high adsorption capacity and fast adsorption speed. It is often used as an adsorption material. Cellulose is non-toxic, biodegradable, and contains a large number of reaction sites. It is often used as a synthetic raw material for hydrogels, such as hydroxyl (-OH), carboxyl (-COOH), etc. It has a strong binding ability for heavy metal ions. Its high expansion ratio and hydrophilicity are also conducive to improving the ability of hydrogels to adsorb heavy metal ions and dyes. It is an ideal adsorbent. For example, Hamad et al. (International Journal of Biological Macromolecules, 2020 (151): 1299-1313.) prepared a composite membrane material of acetate nanocellulose and hydroxyapatite by electrospinning. The membrane binds Pb through surface complexation and ion exchange. 2+ However, this method is not only complex in production process but also has a great influence on Pb 2+ The maximum adsorption capacity of Cu was only 49.75 mg / g. Qin et al. (Biomacromolecules, 2019, 20(12): 4466-4475.) modified cellulose nanofibers with carboxyl groups, which provided Cu 2+ adsorption sites to remove Cu by electrostatic attraction, ion exchange and complexation 2+ ions, at pH 5, are2+ The maximum adsorption capacity is only 115.3 mg / g. Wang et al. (New Chemical Materials, 2021, 49(5): 195-199.) used sodium carboxymethyl cellulose and acrylamide as raw materials, N,N-methylenebisacrylamide as a crosslinker, and sodium persulfate as an initiator to synthesize a hydrogel adsorbent by free radical polymerization. This hydrogel has a good adsorption capacity for Pb 2+ The maximum adsorption capacity is 53.2 mg / g. In addition, the surface of amyloid protein-based adsorption materials contains a variety of functional groups: hydroxyl, carboxyl, amino, imidazole, thiol, etc. These functional groups provide binding sites for metal ions. Patent CN110975826A introduces the application of protein-based adsorption materials in precious metal recovery, proving that protein materials have great potential in metal adsorption. The preparation method of the adsorption material is simple, low-cost, and has a good adsorption effect on precious metals, but its adsorption effect on heavy metals has not been disclosed.

[0004] In addition, when using chemical adsorption solidification method to repair heavy metal contaminated soil, a very thorny problem is faced: the curing agent is mostly powder, and after being sprinkled into the soil to adsorb and solidify heavy metal ions, it still remains in the soil. The soil microenvironment changes slightly, and the curing agent will release heavy metal ions again, causing secondary pollution. Although CN116712970A realizes the adsorption of heavy metal ions in the soil by synthesizing aerogel of nano iron skeleton, and separates it from the soil by magnetic field, it can be recycled and reused, avoiding the secondary pollution of heavy metals, but the preparation method of this aerogel involves more complicated processes such as electrostatic spinning, and the separation process of the adsorbent material is realized by magnetic field, which is not very convenient to operate. Therefore, there is an urgent need for a repair material that can realize efficient adsorption of heavy metal ions in soil and is convenient for separation and extraction. Summary of the invention

[0005] In view of the shortcomings of the above-mentioned heavy metal polluted water and soil remediation technology, such as long cycle, high cost, high energy consumption, secondary pollution, and possible soil nutrient loss and soil degradation, the present invention provides a protein-based hydrogel adsorption material, which has good film-forming properties, high adsorption performance, can be recycled and reused, has a certain toughness, and is easy to use.

[0006] The protein-based hydrogel adsorption material provided by the present invention is a polysaccharide-doped protein-based hydrogel formed by doping a polysaccharide compound during the cross-linking process of protein and a cross-linking agent, and then the formed protein-based hydrogel is subjected to a protein phase transition under the induction of an oxidant or a reductant, thereby increasing the toughness of the hydrogel and further improving its adsorption performance.

[0007] The preparation method of the protein-based hydrogel adsorption material of the present invention comprises the following steps: uniformly mixing 50-200 mg / mL crosslinking agent solution, 20-150 mg / mL protein solution and 5-80 mg / mL polysaccharide compound solution at a volume ratio of 1-10:1-10:1-10 to obtain a mixed solution; forming the obtained mixed solution into a film by casting, scraping or spin coating, or pouring or dipping the obtained mixed solution on a plastic carrier film, culturing for 1 minute to 1 hour under the conditions of a temperature of 5-70 DEG C and a humidity of 10% to 90%, then immersing the plastic carrier film in a 0.01-10 mg / mL reducing agent solution or an oxidizing agent solution for 1-30 minutes, rinsing the plastic carrier film with ultrapure water and drying it at room temperature to obtain the protein-based hydrogel adsorption material.

[0008] Further preferably, the preparation method of the protein-based hydrogel adsorption material of the present invention is: 80-180 mg / mL cross-linking agent solution, 50-110 mg / mL protein solution, and 10-50 mg / mL polysaccharide compound solution are mixed uniformly in a volume ratio of 1-5:1-5:1-5 to obtain a mixed solution; the obtained mixed solution is made into a film by casting, scraping or spin coating, or the obtained mixed solution is flow-coated or dip-coated on a plastic carrier film, and cultured for 3 minutes to 30 minutes at a temperature of 10-35°C and a humidity of 30% to 60%, and then the plastic carrier film is immersed in a 0.1-5 mg / mL reducing agent solution or an oxidant solution for 5 to 10 minutes, and then it is rinsed with ultrapure water and dried at room temperature to obtain a protein-based hydrogel adsorption material.

[0009] The cross-linking agent is selected from any one of succinamide ester-activated polyethylene glycol, polyvinyl alcohol, polylactic acid, polylactic acid glycolic acid copolymer, polycaprolactone, polytrimethylene carbonate, terminal hydroxyl polybutadiene, methyl methacrylate, 2-ethylhexyl methacrylate, polyethylene glycol methacrylate, and 3-sulfonate propyl methacrylate potassium salt, and the number average molecular weight of the cross-linking agent is 2000-60000.

[0010] The above-mentioned protein is selected from animal-derived protein or plant-derived protein.

[0011] The above-mentioned animal source protein is at least one of the proteins contained in the following animals:

[0012] (1) Arthropoda, class Insecta, order Coleoptera: Pederidae, Coleoptera, Scarabaeoidea, Cerambycidae, Chrysomeliformes, Curculionoidea, Dermatophytidae, Cynomoroidea, Hydrocharoidea, Mud Beetles, Cerambycidae, Tiger Beetles, Curculionidae, Coccinellidae, Lampyridae, Cloth Beetles, Cryptolabridae, Thick-horned Coleoptera, and Ground Coleoptera;

[0013] (2) Arthropoda, Insecta, Hymenoptera: Ichneumonidae, Braconidae, Mylidae, Gall-bee Bees, Sphecidae, Vespidae, Formicidae, Apidae, Tenebrioidae, Sawfly, Woodfly, Parasitic Woodfly, Chrysopidae, Enameled Mylidae, Trichogrammatidae, Mylidae, Mylidae, Hammer-horned Mylidae, Marginal Mylidae, and Broad-bellied Mylidae;

[0014] (3) Arthropoda, Insecta, Lepidoptera: Microptera, Acanthidae, Xylotomidae, Superfamily Lycopodia, Rapeworms, Carpiomorpha, Limulidae, Torcula, Sciaenidae, Schizomysidae, Schizomysidae, Gnaphal ...;

[0015] (4) Arthropoda, Crustacea, Macacaridae: Phylum Arthropodidae, Macrophyllidae, Pseudophyllidae, Deep-sea Shrimp, Indian Shrimp, Broad Shrimp, Semi-toed Shrimp, Big-toed Shrimp, Toothed Shrimp, Proto-toed Shrimp, Pseudo-shrimp, Trogidae, Red Shrimp, Crown Shrimp, Lycopodidae, Microshrimp, Square Shrimp, Shrimp, Broad Shrimp, Parashrimp;

[0016] (5) Arthropoda, class Arachnida, order Araneae: Araneidae, Theridiidae, Theridiidae, Lycosauridae, Salticidae, Scorpionidae, Ixodidae, Acaridae, Tickidae, Red Spiders, Theridiidae, Theridiidae, Ocellidae, Theridiidae, Theridiidae, Theridiidae, Theridiidae, Theridiidae, Theridiidae, Theridiidae;

[0017] (6) Arthropoda, Arachnida, Scorpionidae: Pseudo-marsh scorpionidae, Pincer scorpionidae, Microscorpionidae, Pig scorpionidae, Marsh scorpionidae, True scorpionidae, Superstitious mountain scorpionidae, Bliss scorpionidae, Hairy scorpionidae, Fearful scorpionidae, Trapped scorpionidae, Semiscorpionidae, Scorpionidae, Heteroscorpionidae, Diploscorpionidae, Thin scorpionidae;

[0018] (7) Phylum Mollusca, Class Gastropod, Order Cephalopoda: Pseudo-spined Snails, Pseudo-spined Sea Snails, Adidae, Sternidae, Semeno-spined Snails ...

[0019] (8) Phylum Mollusca, Class Gastropod, Order Aplysia: Cylindrica, Aplysia, Hylostomidae, Hylostomidae, Hylostomidae, Hylostomidae, Hylostomidae, Hylostomidae, Hylostomidae, Hylostomidae;

[0020] (9) Phylum Mollusca, Class Gastropod, Order Nudibranch: Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae;

[0021] (10) Phylum Mollusca, Class Cephalopoda, Order Sepiidae: Sepiidae, Subfamily Heteropodinae, Subfamily Sakinocephalae, Subfamily Otocephalae;

[0022] (11) Phylum Mollusca, Class Cephalopoda, Order Octopus: Octopidae, Giant Octopidae, Corydalis, Cuttlefish, Argonautidae, Heptapodidae, Deep-sea Octopus, Brachycopedidae;

[0023] (12) Chordata: Acipenseridae, Hypophthalmichthys, Hypophthalmichthys, Neophthalmichthys, Osteoglossidae, Anguilla, Anguidae, Acanthodontidae, Cypriniformes, Gnaphalinae, Salmoniformes, Salmoninae, Herpidae, Salmoniformes, Ophiodontidae ... , Siluriformes, Siluridae, Silversides, Gnathophoridae, Silversides, Gnathophoridae, Gnathophoridae, Gadformes, Gadidae, Ophiopods, Ophiopods, Chrysopidae, Ophiopods, Ophiopods, Ophiopods, Ophiopods, Sphenodontidae, Syngnathidae, Syngnathidae, Syngnathidae, Perciformes, Wrasseniidae, Perciformes, Rockfish, Perciformes, Pomacanthidae, Perciformes, Cichlidae;

[0024] (13) Chordata, Amphibia, Apodidae: Jellyfish, Anemone, Lumbricidae, Leechidae, Snakes, Sea Cucumbers, Asteridae, Echinoidea, Snails, Mussels, Clams, Calycozoa;

[0025] (14) Chordata, class Amphibia, order Caudata: Cryptobranchidae, Ambystoma, Eusalidae, Hypoderma, Pulmonary Salamanders, Amphibia, Caviidae, Costidae, Eudontidae, Fat Salamanders, Blind-eyed Lumbricidae, and Megalostomidae;

[0026] (15) Chordata, Amphibia, Anura: Toads, Rhacophoridae, Hylacidae, Ceratopogonidae, Mylodactylidae, Microdactylidae;

[0027] (16) Phylum Chordata: Reptiles: Squamata, Testudinidae, Dermatochelydae, Testudinidae, Cheloniformes, Testudinidae, Testudinidae, Crocodilia, Alligators, Alligators, Alligators;

[0028] (17) Chordata: Psittaciformes, Cockatielidae, Psittaciformes, Lorikeetidae, Anseriformes, Anatidae, Anseriformes, Anseriformes, Spheniscidae, Passeriformes, Passeriformes, Corvidae, Passeriformes, and Passeriformes;

[0029] (18) Chordata: Monotremes: Platypus, Echidna, Perissodactyla, Rhinoceros, Proboscidea;

[0030] (19) Chordata, Mammalia, Marsupials: Marmosets, Koalas, Bandicoots, Wombats, and Quetzalcoatlus;

[0031] (20) Chordata, class Mammalia, order Rodentia: Sciuridae, Cricetidae, Bamboo Rhynchomys, Dormouse, Myrmecophaga, Caviidae, Beaver, Flying Squirrel, Porcupine, Lemming, Gerbil, Capybara;

[0032] (21) Chordata, Mammalia, Chiroptera: Pteropus, Rhinolophus, Hippodrome, Myotis, Long-winged Bat, Brachypterygidae, Fruit Bat;

[0033] (22) Chordata, Mammalia, Carnivora: Felidae, Canidae, Ursidae, Mustelidae, Lutradae;

[0034] (23) Chordata, Mammalia, Primates: Hominidae, Gibbon, Loris, Tarsier, Lemuridae;

[0035] (24) Chordata, Mammalia, Artiodactyla: Camelidae, Suidae, Peccary, Giraffidae, Pronghorn, Cervidae, Musk Deer, Bovidae, Hippopotamidae;

[0036] (25) Phylum Chordae, Class Mammalia, Order Cetacea: Dolphins, Sperm Whales, Beaked Whales, Narwhals, Sharp-nosed Dolphins, Delphinidae, Porpoises, Baleen Whales, Gray Whales, Right Whales, Minke Whales, Beaked Whales, and Fin Whales.

[0037] The above-mentioned plant-based protein is at least one of the following animal proteins:

[0038] (1) Ceratophyllum: Ceratophyllums: Ceratophyllums, ...

[0039] (2) True Mosses: Axis order, Axis family, Axis order, Hoary moss family, Axis order, Micro-moss family, Corrugated moss order, Corrugated moss family, Beaded moss order, Beaded moss family, True moss order, True moss family, True moss order, Lantern moss family, Shrimp moss order, Shrimp moss family, Tobacco moss order, Tobacco moss family, Brachycera order, Brachycera family, Opposite leaf order, Opposite leaf order, Anti-neon moss family, Gourd moss order, Big cap moss family, Gourd moss order, Gourd moss family, Purple calyx order, Purple calyx order, Purple calyx order, Purple calyx order, Purple calyx order, Purple calyx order, Stone crack moss Mosses, the order of the purple-calyx mosses, the order of the tiger-tail mosses, the order of the yellow-yellow mosses, the order of the oily mosses, the order of the oily mosses, the order of the white mosses, the order of the oily mosses, the order of the velvet-cap mosses, the order of the tree-lime mosses, the order of the tree-lime mosses, the order of the tree-lime mosses, the order of the straight-toothed mosses, the order of the wood-ling mosses, the order of the wood-ling mosses, the order of the ridge-capped mosses, the order of the juniper mosses, the order of the juniper mosses, the order of the water-lichen mosses, the order of the twisted-stem mosses, the order of the water-lichen mosses, the order of the water-lichen mosses, the order of the cold-lichen mosses, the order of the water-lichen mosses, the order of the beautiful-lichen mosses;

[0040] (3) Eubryophyta, Eubryophyta, Angiospermaceae, Angiospermaceae, Angiospermaceae, Angiospermaceae, Angiospermaceae;

[0041] (4) True mosses: Onagraceae, Bolognaaceae, Reverse hair mossaceae, Green mossaceae, Wetland mossaceae, Wannian mossaceae, Cryptocapsulariaceae, Silk mossaceae, Brocteraceae, Sphagaceae, Soft tooth mossaceae, Tower mossaceae, Gray mossaceae, Peacock mossaceae, Boat leaf mossaceae, Thin Luo mossaceae, White tooth mossaceae, Crepe mossaceae, Tilapia mossaceae, Golden hair mossaceae, Flat mossaceae, Straight mossaceae, Cotton mossaceae, False fine Luo mossaceae, Axillary mossaceae, Pteridaceae, Golden gray mossaceae, Hairy brocade mossaceae, Heterodontaceae, Weeping mossaceae, Heliconia mossaceae, Brocade mossaceae, Pseudo-thin Luo mossaceae, Sclerophyllaceae, Acanthaceae, Lepiophyllaceae, Thick handle mossaceae;

[0042] (5) Eubryophytes, Eubryophytes, and Hypobryophytes: Phyllostachys, Candleleafys, Microhylophytes, Botrychnophytes, Arboretum, Hypobryophytes, Thick Lithophytes, Echinopsaceae, and Light Mosses;

[0043] (6) True mosses: Black mosses, Black mosses, Black mosses, Black mosses, True mosses: Long mosses, Long mosses, Long mosses, True mosses: Golden mosses, Golden mosses, Golden mosses, True mosses: Sphagnum mosses, Sphagnum mosses, True mosses: Sphagnum mosses, True mosses: Sphagnum mosses, True mosses: Algae mosses, Algae mosses, True mosses: Tetradentata mosses, Tetradentata mosses, Tetradentata mosses;

[0044] (7) Chlorophyta, Chlorophyta: Bryophyceae, ...

[0045] (8) Chlorophyta, Chlorophyta, Acrophyceae, Acrophyceae, Gymnophyceae, Gymnophyceae, Gymnophyceae, Gymnophyceae, Dauerlys ...

[0046] (9) Marchantia: Bracteaceae, Microphylla, Microphylla, Nanximeiaceae, Forkleaf, Forkleaf, Greenleaf, Bandleaf, Bandleaf, Mossleaf, Bandleaf, Purpleleaf, Purpleleaf, Light-calyx, Ear-leaf, Light-calyx, Hair-ear, Light-calyx, Fine-scale, Light-calyx, Eye-calyx, Light-calyx, Flat-calyx, Hair-leaf, Hair-leaf, New-leaf;

[0047] (10) Phyllophyllous order: Acrocalyceae, Cryptocapsulariaceae, Erectleafaceae, Leptocarpaceae, Pocillopora, Eyelashaceae, Capsulariaceae, Macrocalyceae, Pseudo-macrocalyceae, Geocalyceae, Holocyceae, Fusariumaceae, Shearleafaceae, Longicyceae, Armoraceae, Leafmoss, Complexaceae, Fingerleafmoss, Toothcalyceae, Splitleafmoss, Beardmoss, Microcalyceae, Pseudocalyceae, Feathermoss, Pseudo-complexaceae, Scutellariaceae, Synophyllaceae, Diplocoleaceae, Tubemoss, Horizontalleafmoss, Velvetmoss;

[0048] (11) Phylum Ranunculaceae, Class Ranunculales: Verruco-crown family, Star-hole family, Snake family, Flowery family, Liverwort family, Dioscorea family, Light family, Single-month family, Money family, Leather-leaf family, Wesley family;

[0049] (12) Rhodophyta: Acrophyceae, Acrophyceae, Ignaec ...

[0050] (13) Rhodophyta, Rhodophyta, and Taxodium: Stem-spined algae, Gelatophyceae, Endophyceae, Taxodium, Myxocystis, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae;

[0051] (14) Vascular plants, class Equisetum: Alsophilales, Cyathophytes, family Cyathophytes, family Cyathophytes, family Equisetaceae, family Diplophyllaceae, family Diplophyllaceae, family Diplophyllaceae, family Hymenopterales, family Hymenopterales, family Hymenopterales, family Hymenopteraceae, family Osmanthaceae, family Pinaceae, family Sophora, family Sophora, family Sophora, family Cyperaceae, family Cyperaceae;

[0052] (15) Vascular plants, class Equisetaceae, order Polypodiaceae: Aspleniaceae, Aspleniaceae, Pterid ...

[0053] (16) Vascular plants: Acorusales, Acorus family; Palmaceae; Schisandraceae; Boraginaceae; Buxusales, Buxus family; Celastraceae; Ceratophyllum family; Ceratophyllum family; Chrysanthemum family; Commelinaceae; Commelinaceae; Commelinaceae; Commelinaceae; Commelinaceae; Cornaceae; Cornaceae; Hydrangeaceae; Cornaceae; Cyanophyllum family; Tassel family; Tassel family; Pentacarpaceae; Cucurbitaceae; Cucurbitaceae; Begoniaceae; Cucurbitaceae; Moracaceae; Cucurbitaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; The order Acanthaceae, the order Leguminosae, the order Polygala, the order Merantiaceae, the order Psoralea, the order Psoralea, the order Eucommia, the order Geraniales, the order Decapoda, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Vitis, the order Vitis; the order Vitis;

[0054] (17) Vascular plants: Alismataceae, Araceae, Araceae, Asteraceae, Asteraceae, Asteraceae, Asteraceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae;

[0055] (18) Vascular plants, Magnoliaceae, Apiaceae, Araliaceae, Pittosporaceae, and Coleopsaceae;

[0056] (19) Vascular plants, Magnoliaceae, Aquilegiaceae: Aquilegiaceae, Aquilegiaceae, Aquilegiaceae;

[0057] (20) Vascular plants, Magnoliaceae, Asparagales: Asparagaceae, Amaryllidaceae, Asphodelaceae, Curculigoaceae, Iridaceae, Orchidaceae;

[0058] (21) Vascular plants: Magnoliaceae, Asterales, Asteraceae, Campanulaceae, Menymaceae, Pentaphyllum, Stylophyllum;

[0059] (22) Vascular plants, Magnoliaceae, Cruciferae: Cruciferae, Glechomaea, Carica, Caricaceae, Moringaceae, Meliaceae, Echinopsaceae, Nasturtiumaceae;

[0060] (23) Vascular plants: Caryophyllaceae, Aizoaceae, Amaranthaceae, Uncariaceae, Basella, Cactaceae, Droseraceae, Petalopsis, Pinaceae, Cornaceae, Nepenthesaceae, Mirabilis, Allium, Phytolaccae, Pleurotus, Polygonaceae, Portulaceae, Glechomae, Salicaceae;

[0061] (24) Vascular plants: Ericaceae, Actinidiaceae, Impatiens, Alnus, Ixigera, Diospyros, Ericaceae, Leydigaceae, Cyperaceae, Pentaphyllum, Allium, Primulaceae, Sapotaceae, Costaceae, Styracaceae, Asteraceae, Theaceae;

[0062] (25) Vascular plants, Magnoliaceae, Fagales: Fagaceae, Betulaceae, Casuarinaceae, Fagaceae, Juglandaceae, Myricaceae;

[0063] (26)) Vascular plants, Magnoliaceae, Gentianales: Gentianaceae, Apocynaceae, Gelsemium, Gentianaceae, Loganaceae, Rubiaceae;

[0064] (27) Vascular plants, Magnoliaceae, Labiatae: Lamiaceae, Acanthaceae, Bignoniaceae, Vanillaceae, Gesneriaceae, Utriculariaceae, Matricariaceae, Ceratoniaceae, Aquilegiaceae, Oleaceae, Orobanchaceae, Paulowniaceae, Sesamaceae, Penicillaceae, Plantaginaceae, Scrophulariaceae, Verbenaceae, and Aglaonema;

[0065] (28) Vascular plants, Magnoliaceae, Liliales: Liliaceae, Colchicumaceae, Hostaceae, Veratrum, Smilaxaceae;

[0066] (29) Vascular plants: Malpurinae, Echinopsaceae, Echinopsaceae, Anshenaceae, Garciniaceae, Pomacantha, Stellariaceae, Corydalis, Euphorbiaceae, Hypericaceae, Glutinaceae, Linaceae, Tropaeolaceae, Cyperaceae, Passifloraceae, Arboraceae, Phyllanthaceae, Carexaceae, Drupaceae, Rhizophoraceae, Salicaceae, Violaceae;

[0067] (30) Vascular plants, Magnoliaceae, Malvaceae: Malvaceae, Malvaceae, Helianthaceae, Dipterocarpaceae, Thymelaeaceae;

[0068] (31) Vascular plants, Magnoliaceae, Myrtales: Myrtaceae, Combretaceae, Cryptomeriaceae, Lythraceae, Melastomataceae, Onagraceae;

[0069] (32) Vascular plants, Magnoliales, Pandanaceae: Pandanaceae, Stemonaceae, Mycorrhizae, and Featherleafaceae;

[0070] (33) Vascular plants: Magnoliaceae, Poaceae, Bromeliaceae, Cyperaceae, Cyperaceae, Cyperaceae, Juncaceae, Sphagaceae, Juncaceae, Typhaceae, and Cyperaceae;

[0071] (34) Vascular plants, Magnoliaceae, Proteales: Proteaceae, Nelumboceae, Platanaceae, and Ceropegiaceae;

[0072] (35) Vascular plants, Magnoliaceae, Ranunculales: Ranunculaceae, Berberidaceae, Astrophyllaceae, Akebiaceae, Menispermaceae, Papaveraceae;

[0073] (36) Vascular plants: Magnoliaceae, Rosaceae, Elaeagnaceae, Moraceae, Rhamnaceae, Rosaceae, Ulmaceae, Urticaceae;

[0074] (37) Vascular plants: Magnoliaceae, Santalum orders: Santalaceae, Cyperaceae, Cyperaceae, Cyperaceae, Loranthaceae, Aspergillus family, Citronaceae, Santalaceae, Cyperaceae, and Malvaceae;

[0075] (38) Vascular plants, Magnoliaceae, Sapindaceae: Sapindaceae, Anacardiaceae, Botrytis cinerea, Oleaceae, Meliaceae, Nitraria tanguticaceae, Rutaceae, Simsinaceae;

[0076] (39) Vascular plants: Magnoliaceae, Saxifragales: Saxifragaceae, Mycorrhizaceae, Cynomorium, Sansevieriaceae, Ribesaceae, Echinochloa, Hamamelidaceae, Myristicaceae, Paeoniaceae, Psoralea, Saxifragaceae;

[0077] (40) Vascular plants, Magnoliaceae, Solanales: Solanaceae, Convolvulaceae, Acanthaceae, Sphenopalmataceae;

[0078] (41) Vascular plants, Magnoliaceae, Zingiberales: Zingiberaceae, Cannaceae, Zingiberaceae, Orchidaceae, Marantaceae, Musaceae, Strelitziaceae;

[0079] (42) Vascular plants: Araucariaces, Araucariaceae, Araucariaces, Podocarpaceae, Cupressaceae, Cupressaceae, Cupressaceae, Taxaceae, Cycadales, Cycadaceae, Ephedales, Ephedraceae, Ginkgoales, Ginkgoaceae, Gnetaceae, Pinaceae, Pinaceae, and Machilaceae.

[0080] It is further preferred that the above-mentioned protein is selected from at least one of lysozyme, bovine serum albumin, human serum albumin, lactoferrin, whey albumin, insulin, α-lactalbumin, fibrinogen, β-lactoglobulin, Aβ peptide, prion protein, α-synuclein, cystatin C, huntingtin protein, immunoglobulin, ribonuclease A, cytochrome c, α-amylase, horseradish peroxidase, pepsin, myoglobin, collagen, keratin, hemoglobin, DNA polymerase, casein, soy protein, pea protein, zein, gliadin, gluten, oat protein, potato protein, hemp kernel protein, walnut protein, rapeseed protein, hazelnut protein, quinoa protein, sunflower seed protein, pumpkin seed protein, black sesame protein, mushroom protein, red algae protein, legumin, barley protein, wheat protein, millet protein, glutenin, kidney bean protein, casein, collagen, and catalase.

[0081] The above-mentioned polysaccharide compound is at least one of nanocellulose, cellulose nanocrystals, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, chitosan, sodium alginate, gelatin, corn starch, potato starch, dextran, mannan, polypectin, low-methylated pectin, gum arabic, guar gum, tragacanth gum, apricot gum, peach gum, konjac glucomannan, galacturonic acid, keratan, chitin, glycogen, hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate, heparin, and heparan sulfate.

[0082] The reducing agent is at least one of tris(2-carboxyethyl)phosphine hydrochloride, cysteine, reduced glutathione, dithiothreitol, β-mercaptoethanol, dimercaptosuccinic acid, 2-mercaptoethanol, and sodium sulfite; the oxidizing agent is at least one of sodium ferrate, trivalent cobalt salt, chlorate, potassium permanganate, persulfate, potassium dichromate, concentrated sulfuric acid, hydrochloric acid, nitric acid, hydrobromic acid, hydroiodic acid, perchloric acid, ozone, hydrogen peroxide, fluorine gas, chlorine gas, sodium bismuthate, periodic acid, lead dioxide, guanidine hydrochloride, urea, trifluoroethanol, hexafluoroisopropanol, and trifluoroacetic acid.

[0083] The above-mentioned plastic carrier film is any one of polyethylene film, polypropylene film, polyvinyl acetate film, polyvinyl chloride film, polystyrene film, polyvinylidene chloride film, ethylene-vinyl acetate copolymer film, polyvinyl alcohol film, polylactic acid film, polytetrafluoroethylene film, nylon film, polyester film, polyamide film, vinyl acetate plastic film, etc.

[0084] The above-mentioned linker solution, protein solution and polysaccharide compound solution are all prepared with dimethyl sulfoxide or a mixed solution of dimethyl sulfoxide and deionized water as solvent.

[0085] The reducing agent solution and the oxidizing agent solution are both prepared with deionized water as solvent.

[0086] The present invention also provides the use of the protein-based hydrogel adsorption material as a heavy metal adsorption material for in-situ repair of water and soil contaminated by heavy metals.

[0087] The present invention uses proteins and polysaccharide compounds enriched with heavy metal adsorption functional groups as raw materials, and forms a polysaccharide-doped protein-based hydrogel through a crosslinking agent. The operation method is simple, the gelation speed is fast, the heavy metal adsorption performance is good, and it is convenient to recycle and reuse after the heavy metals are adsorbed. The specific beneficial effects of the present invention are as follows:

[0088] 1. The present invention uses polysaccharide compounds as additives, which are stably doped in the gelling system of protein and cross-linking agent, and can be cross-linked into gel in a short time. The protein-based hydrogel adsorption material can quickly form a film, and has high mechanical strength and good toughness, which can meet general operating requirements.

[0089] 2. The protein and cellulose in the protein-based hydrogel adsorption material of the present invention have numerous adsorption functional groups, which can efficiently capture heavy metal ions through covalent bonds, hydrophobic interactions, hydrogen bonds and electrostatic interactions. The introduction of the enhancer can not only change the conformation of the protein to form a β-sheet structure, thereby enhancing the mechanical properties of the hydrogel, but also expose the thiol groups of the protein, further improving the adsorption properties of the hydrogel.

[0090] 3. The protein-based hydrogel adsorption material of the present invention has a simple preparation method, low cost, good adsorption effect on heavy metals, and is very easy to recover in wastewater after adsorption. Especially for the remediation of heavy metal-contaminated soil, the protein-based hydrogel adsorption material can remove heavy metal ions in the soil by in-situ covering adsorption and then removing, completely avoiding secondary pollution. BRIEF DESCRIPTION OF THE DRAWINGS

[0091] Figure 1 This is a SEM image of the surface morphology of the protein-based hydrogel adsorption material prepared in Example 1 after absorbing water.

[0092] Figure 2 This is a graph of the transmittance of the protein-based hydrogel adsorption material prepared in Example 2 at visible light 400-800 nm.

[0093] Figure 3 3 is the stress-strain diagram of the protein-based hydrogel adsorption material prepared in Example 3.

[0094] Figure 4 Graph showing the water absorption and swelling rate of the protein-based hydrogel adsorbent material prepared in Example 4 over time.

[0095] Figure 5 This is a graph showing the variation of the storage modulus and loss modulus of the protein-based hydrogel adsorption material prepared in Example 4 with frequency.

[0096] Figure 6 This is a diagram of the selective adsorption of the protein-based hydrogel adsorption material prepared in Example 3 in the liquid phase.

[0097] Figure 7 This is a graph of the adsorption rate of the protein-based hydrogel adsorption material prepared in Example 3 at different pH values.

[0098] Figure 8 This is a graph showing the adsorption capacity of the protein-based hydrogel adsorption material prepared in Example 3 at different heavy metal ion concentrations.

[0099] Fig. 9 This is a graph showing the change in adsorption amount over time of the protein-based hydrogel adsorption material prepared in Example 3.

[0100] Fig.10 This is the adsorption graph of the protein-based hydrogel adsorption material prepared in Example 3 after 5 cycles.

[0101] Fig.11 This is a diagram of the restoration of heavy metal cadmium contaminated soil by the protein-based hydrogel adsorption material prepared in Example 4.

[0102] Fig.12 This is a diagram of the restoration of heavy metal copper contaminated soil by the protein-based hydrogel adsorption material prepared in Example 4.

[0103] Fig.13 This is a diagram of the restoration of heavy metal lead contaminated soil by the protein-based hydrogel adsorption material prepared in Example 4. DETAILED DESCRIPTION

[0104] The present invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments. The following embodiments are only used to illustrate the present invention, but are not used to limit the scope of protection of the present invention.

[0105] Example 1

[0106] At room temperature, 100 mg / mL succinamide ester-activated polyethylene glycol 8000 dimethyl sulfoxide solution, 80 mg / mL lysozyme dimethyl sulfoxide solution, and 20 mg / mL cellulose nanocrystal dimethyl sulfoxide solution were mixed uniformly in a volume ratio of 1:1:1, and the resulting mixed solution was dropped into a culture dish with a diameter of 5 cm, and cultured at a temperature of 25° C. and a humidity of 30% for 2 hours to allow lysozyme and succinamide ester-activated polyethylene glycol 8000 to undergo a coupling reaction and be doped with cellulose nanocrystals to form a hydrogel, and then the hydrogel was immersed in a 0.1 mg / mL tris(2-carboxyethyl)phosphine hydrochloride aqueous solution at pH=7 for 10 minutes, and then rinsed with ultrapure water to obtain an unfolded protein hydrogel, the surface morphology of which is as shown in FIG. Figure 1As shown, after the hydrogel is dried at room temperature, a rollable tough protein-based hydrogel adsorption material with adsorption properties can be obtained.

[0107] Example 2

[0108] At room temperature, 120 mg / mL succinamide ester-activated polyethylene glycol 8000 dimethyl sulfoxide solution, 100 mg / mL lysozyme dimethyl sulfoxide solution, and 20 mg / mL cellulose nanocrystal dimethyl sulfoxide solution were mixed uniformly in a volume ratio of 1:1:1, and the resulting mixed solution was dropped into a culture dish with a diameter of 5 cm, and cultured at a temperature of 25°C and a humidity of 30% for 2 hours to allow lysozyme and succinamide ester-activated polyethylene glycol 8000 to undergo a coupling reaction and be doped with cellulose nanocrystals to form a hydrogel, and then the hydrogel was immersed in a 0.1 mg / mL tris(2-carboxyethyl)phosphine hydrochloride dimethyl sulfoxide solution with a pH of 7 for 10 minutes, and then rinsed with ultrapure water and dried at room temperature to obtain an adsorbent, curlable, tough protein-based hydrogel adsorption material. The transmittance of the obtained protein-based hydrogel adsorption material in the visible light region was measured using a UV-visible-near infrared spectrophotometer, and the measurement wavelength range was 400-800 nm. Due to the light absorption characteristics of cellulose nanocrystals, e.g. Figure 2 As shown, the average light transmittance of the hydrogel in the wavelength range of 400 to 800 nm is about 96.2%.

[0109] Example 3

[0110] At room temperature, 160 mg / mL succinamide ester-activated polyethylene glycol 8000 dimethyl sulfoxide solution, 100 mg / mL lysozyme dimethyl sulfoxide solution, and 30 mg / mL cellulose nanocrystal dimethyl sulfoxide solution were mixed uniformly in a volume ratio of 1:2:1.5, and the resulting mixed solution was scraped onto a 5 cm×10 cm polytetrafluoroethylene plate, and incubated at 25°C and 30% humidity for 3 hours to allow lysozyme and succinamide ester-activated polyethylene glycol 8000 to undergo a coupling reaction and be doped with cellulose nanocrystals to form a hydrogel, and then the hydrogel was immersed in a 0.1 mg / mL pH=7 tris(2-carboxyethyl)phosphine hydrochloride aqueous solution for 5 minutes, and then rinsed with ultrapure water and dried at room temperature to obtain an adsorbent, rollable, tough protein-based hydrogel adsorption material. This protein-based hydrogel adsorption material has high strength and toughness, and its stress-strain curve was tested using a universal testing machine, as shown in FIG. Figure 3 As shown, the fracture strength of the protein-based hydrogel adsorption material is about 33.2MPa, the fracture strain is about 400%, and the toughness is about 12.3MJ / m 3 , and from the figures before and after stretching, it can be seen that the protein-based hydrogel adsorption material has excellent mechanical strength and can meet general operating requirements.

[0111] Example 4

[0112] At room temperature, 160 mg / mL succinamide ester-activated polyethylene glycol 8000 dimethyl sulfoxide solution, 100 mg / mL lysozyme dimethyl sulfoxide solution, and 30 mg / mL cellulose nanocrystal dimethyl sulfoxide solution were mixed uniformly in a volume ratio of 1:2:1.5, and a 5 cm×5 cm vinyl acetate plastic film was immersed in the obtained mixed solution by dip coating and then taken out, and then cultured for 3 hours at a temperature of 25°C and a humidity of 30%, so that lysozyme and succinamide ester-activated polyethylene glycol 8000 undergo a coupling reaction and are doped with cellulose nanocrystals to form a hydrogel, and then the hydrogel was immersed in a 0.1 mg / mL pH=7 tris(2-carboxyethyl)phosphine hydrochloride aqueous solution for 5 minutes, and then rinsed with ultrapure water and dried at room temperature to obtain an adsorbent, rollable, tough protein-based hydrogel adsorption material. The swelling properties of the obtained protein-based hydrogel adsorption material were tested, and its swelling rate at different time periods was tested, such as Figure 4 As shown in Figure 2, the adsorption equilibrium can be reached after about 3 hours, and the swelling ratio is about 1650%. The swollen hydrogel is subjected to rheological tests, as shown in Figure 2. Figure 5 As shown, at a frequency of 0.1 to 10 rad Hz, the storage modulus (G') and loss modulus (G") of the hydrogel network did not change significantly, indicating that the hydrogel network has extremely high stability.

[0113] Example 5

[0114] At room temperature, 160 mg / mL succinamide ester-activated polyethylene glycol 10000 dimethyl sulfoxide solution, 100 mg / mL lysozyme dimethyl sulfoxide solution, and 30 mg / mL hydroxyethyl methylcellulose dimethyl sulfoxide solution are mixed uniformly in a volume ratio of 1:2:1.5, and a 5 cm×5 cm vinyl acetate plastic film is immersed in the obtained mixed solution by dip coating and then taken out, and is statically cultured for 3 hours at a temperature of 25° C. and a humidity of 30% to allow lysozyme and succinamide ester-activated polyethylene glycol 10000 to undergo a coupling reaction and be doped with hydroxyethyl methylcellulose to form a hydrogel, and then the hydrogel is immersed in a 0.1 mg / mL tris(2-carboxyethyl)phosphine hydrochloride aqueous solution at pH=7 for 5 minutes, and then it is rinsed with ultrapure water and dried at room temperature to obtain an adsorbent, curlable, tough protein-based hydrogel adsorption material.

[0115] Example 6

[0116] Selective adsorption of heavy metal ions by protein-based hydrogel adsorbents in mixed ion solutions

[0117] At room temperature, the Cu 2+ 、Cd2+ Cr 3+ , Pb 2+ 、As 3+ 、Au + 、Ni 2+ 、Zn 2+ 、Al 3+ , Ca 2+ 、Na + Mg 2+ and Mn 2+ A mixed solution of metal ions, wherein the concentration of each metal ion is 1 mg / L, and the pH value is adjusted to 6.5, and then the protein-based hydrogel adsorption material in Example 3 is added, and the amount of adsorption material added is 0.1 mg / mL. After being placed in an oscillator for 24 hours, the content of each metal ion in the solution is tested by ICP-MS. The results show that the adsorption material has a significant effect on the content of Cu in the mixed metal ions. 2+ 、Cd 2+ Cr 3+ , Pb 2+ 、As 3+ 、Au + The adsorption rate reached more than 90% (see Figure 6 ), in the mixed ion solution, the adsorption capacity of each metal ion is Cu 2+ >Cd 2+ >Cr 3+ >Pb 2+ >As 3+ >Au + >Ni 2+ >Zn 2+ >Al 3+ >Ca 2+ >Na + >Mg 2+ >Mn 2+ It can be seen that it has good selective adsorption for heavy metal ions.

[0118] Example 7

[0119] Application of protein-based hydrogel adsorption materials in adsorption of heavy metal ions in a single system solution

[0120] 1. Effect of pH on the adsorption properties of protein-based hydrogel adsorption materials

[0121] At room temperature, 1 mg / L Cu 2+ 、Cd 2+ Cr 3+ , Pb 2+ 、As 3+The pH value of the heavy metal ion solution was adjusted to 4.5-8.5, and then the protein-based hydrogel adsorption material in Example 3 was added, and the amount of adsorption material added was 0.4 mg / mL. After being placed in an oscillator at 25°C for 12 hours, the content of heavy metal ions in the solution was tested by ICP-MS. Figure 7 As shown, when the pH value of the adsorption material is greater than 6.5, the adsorption rate of the above heavy metal ions can reach more than 95%.

[0122] 2. Effect of heavy metal ion concentration on the adsorption properties of protein-based hydrogel adsorption materials

[0123] At room temperature, different concentrations of Cu 2+ 、Cd 2+ Cr 3+ , Pb 2+ 、As 3+ The pH value of the heavy metal ion solution was adjusted to 6.5, and then the protein-based hydrogel adsorption material in Example 3 was added. After being shaken in an oscillator for 24 hours, the content of heavy metal ions in the solution was tested by ICP-MS. Figure 8 As shown, based on the single metal isotherm adsorption model under 50-1000 mg / L conditions, the Cu 2+ 、Cd 2+ , Pb 2+ Cr 3+ and As 3+ The maximum adsorption amounts were 253.8 mg / g, 225.3 mg / g, 150.3 mg / g, 101.3 mg / g and 95.2 mg / g respectively.

[0124] 3. Effect of adsorption time on the adsorption performance of protein-based hydrogel adsorption materials at different gold ion concentrations

[0125] At room temperature, the concentration of Cu was 100 mg / L. 2+ 、Cd 2+ Cr 3+ , Pb 2+ 、As 3+ The pH value of the heavy metal ion solution was adjusted to 6.5, and then the protein-based hydrogel adsorption material in Example 3 was added, and the solution was placed in an oscillator for oscillation. Samples were taken at intervals from 0 to 1000 minutes, and the content of heavy metal ions in the solution was tested by ICP-MS. Fig. 9 As shown, the adsorption equilibrium can be reached at 300 minutes.

[0126] Example 8

[0127] Desorption-adsorption experiment of heavy metals by protein-based hydrogel adsorption materials

[0128] At room temperature, the heavy metal ions Cu in Example 3 were adsorbed 2+ 、Cd 2+ , Pb 2+ The protein-based hydrogel adsorption material was added to a 1 mol / L HNO3 aqueous solution and slowly shaken for 12 hours to perform a desorption experiment. The desorption experiment was performed again on the adsorption material after desorption, and the desorption-adsorption was repeated 3 times. Fig.10 As shown, after 5 cycles of adsorption-desorption, the adsorption of heavy metals can still reach more than 90%.

[0129] Example 9

[0130] Application of protein-based hydrogel adsorption materials in the remediation of heavy metal contaminated soil

[0131] 1. Remediation of soil contaminated by heavy metal cadmium

[0132] At room temperature, the protein-based hydrogel adsorption material in Example 4 was covered in simulated soil with a cadmium pollution concentration of 9.7 mg / kg at different weight percentages (0%, 1%, 2%, 3%, 4%, 5%, and 6% of the soil weight), and the soil was watered to make the soil moisture reach saturated water holding capacity. After standing for 24 hours, the adsorption material was taken out, the soil was dried and digested, and the cadmium content in the soil was tested by ICP-MS. Fig.11 As shown, with the increase of the content of adsorption material, the cadmium content in the soil after restoration gradually decreased. When the content of adsorption material was 6%, it could be restored within the screening value of agricultural land (1.7 mg / kg).

[0133] 2. Remediation of soil contaminated by heavy metal copper

[0134] At room temperature, the protein-based hydrogel membrane adsorption material in Example 4 was covered in simulated soil with a copper pollution concentration of 446.9 mg / kg at different weight percentages (0%, 1%, 2%, 3%, 4%, 5%, and 6% of the soil weight), and the soil was watered to make the soil moisture reach the saturated water holding capacity. After standing for 24 hours, the adsorption material was taken out, the soil was dried and digested, and the copper content in the soil was tested by ICP-MS. Fig.12 As shown, with the increase of the content of adsorption material, the copper content in the soil after restoration gradually decreases. When the content of adsorption material is 5%, it can be restored within the safety value of agricultural land (150 mg / kg).

[0135] 3. Remediation of soil contaminated by heavy metal lead

[0136] At room temperature, the protein-based hydrogel membrane adsorption material in Example 4 was covered in simulated soil with a lead pollution concentration of 254.5 mg / kg at different weight percentages (0%, 1%, 2%, 3%, 4%, 5%, and 6% of the soil weight), and the soil was watered to make the soil moisture reach the saturated water holding capacity. After standing for 24 hours, the adsorption material was taken out, dried and digested, and the lead content in the soil was tested by ICP-MS. Fig.13 As shown, with the increase of the adsorption material content, the lead content in the soil after restoration gradually decreases. When the adsorption material content is 5%, it can be restored within the safety value of agricultural land (80 mg / kg).

Claims

1. A protein-based hydrogel adsorption material, characterized in that: The adsorption material is a polysaccharide-doped protein-based hydrogel formed by doping a polysaccharide compound during the cross-linking process of protein and a cross-linking agent, and then the formed protein-based hydrogel is subjected to a protein phase transition under the induction of an oxidant or a reductant, thereby increasing the toughness of the hydrogel and further improving its adsorption performance.

2. The protein-based hydrogel adsorption material according to claim 1, characterized in that: The adsorption material is prepared by the following method: 50-200 mg / mL crosslinking agent solution, 20-150 mg / mL protein solution and 5-80 mg / mL polysaccharide compound solution are uniformly mixed at a volume ratio of 1-10:1-10:1-10 to obtain a mixed solution; the obtained mixed solution is made into a film by casting, scraping or spin coating, or the obtained mixed solution is flow-coated or dip-coated on a plastic carrier film, and cultured for 1 minute to 1 hour under the conditions of temperature of 5-70 DEG C and humidity of 10% to 90%, and then the plastic carrier film is immersed in a 0.01-10 mg / mL reducing agent solution or oxidizing agent solution for 1 to 30 minutes, and then the plastic carrier film is rinsed with ultrapure water and dried at room temperature to obtain a protein-based hydrogel adsorption material.

3. The protein-based hydrogel adsorption material according to claim 2, characterized in that: The adsorption material is prepared by the following method: 80-180 mg / mL cross-linking agent solution, 50-110 mg / mL protein solution and 10-50 mg / mL polysaccharide compound solution are uniformly mixed at a volume ratio of 1-5:1-5:1-5 to obtain a mixed solution; the obtained mixed solution is made into a film by casting, scraping or spin coating, or the obtained mixed solution is flow-coated or dip-coated on a plastic carrier film, and cultured for 3-30 minutes under the conditions of temperature of 10-35 DEG C and humidity of 30%-60%, and then the plastic carrier film is immersed in a 0.1-5 mg / mL reducing agent solution or oxidizing agent solution for 5-10 minutes, and then the plastic carrier film is rinsed with ultrapure water and dried at room temperature to obtain a protein-based hydrogel adsorption material.

4. The protein-based hydrogel adsorption material according to any one of claims 1 to 3, characterized in that: The cross-linking agent is selected from any one of succinamide ester-activated polyethylene glycol, polyvinyl alcohol, polylactic acid, polylactic acid glycolic acid copolymer, polycaprolactone, polytrimethylene carbonate, terminal hydroxyl polybutadiene, polymethyl methacrylate, poly2-ethylhexyl methacrylate, polyethylene glycol methacrylate, and poly3-sulfonate propyl methacrylate, and the number average molecular weight of the cross-linking agent is 2000-60000.

5. The protein-based hydrogel adsorption material according to any one of claims 1 to 3, characterized in that: The protein is selected from animal-derived protein or plant-derived protein; The animal-derived protein is at least one of the following animal proteins: (1) Arthropoda, class Insecta, order Coleoptera: Pederidae, Coleoptera, Scarabaeoidea, Cerambycidae, Chrysomeliformes, Curculionoidea, Dermatophytidae, Cynomoroidea, Hydrocharoidea, Mud Beetles, Cerambycidae, Tiger Beetles, Curculionidae, Coccinellidae, Lampyridae, Cloth Beetles, Cryptolabridae, Thick-horned Coleoptera, and Ground Coleoptera; (2) Arthropoda, Insecta, Hymenoptera: Ichneumonidae, Braconidae, Mylidae, Gall-bee Bees, Sphecidae, Vespidae, Formicidae, Apidae, Tenebrioidae, Sawfly, Woodfly, Parasitic Woodfly, Chrysopidae, Enameled Mylidae, Trichogrammatidae, Mylidae, Mylidae, Hammer-horned Mylidae, Marginal Mylidae, and Broad-bellied Mylidae; (3) Arthropoda, Insecta, Lepidoptera: Microptera, Acanthidae, Xylotomidae, Superfamily Lycopodia, Rapeworms, Carpiomorpha, Limulidae, Torcula, Sciaenidae, Schizomysidae, Schizomysidae, Gnaphal ...; (4) Arthropoda, Crustacea, Macacaridae: Phylum Arthropodidae, Macrophyllidae, Pseudophyllidae, Deep-sea Shrimp, Indian Shrimp, Broad Shrimp, Semi-toed Shrimp, Big-toed Shrimp, Toothed Shrimp, Proto-toed Shrimp, Pseudo-shrimp, Trogidae, Red Shrimp, Crown Shrimp, Lycopodidae, Microshrimp, Square Shrimp, Shrimp, Broad Shrimp, Parashrimp; (5) Arthropoda, class Arachnida, order Araneae: Araneidae, Theridiidae, Theridiidae, Lycosauridae, Salticidae, Scorpionidae, Ixodidae, Acaridae, Tickidae, Red Spiders, Theridiidae, Theridiidae, Ocellidae, Theridiidae, Theridiidae, Theridiidae, Theridiidae, Theridiidae, Theridiidae, Theridiidae; (6) Arthropoda, Arachnida, Scorpionidae: Pseudo-marsh scorpionidae, Pincer scorpionidae, Microscorpionidae, Pig scorpionidae, Marsh scorpionidae, True scorpionidae, Superstitious mountain scorpionidae, Bliss scorpionidae, Hairy scorpionidae, Fearful scorpionidae, Trapped scorpionidae, Semiscorpionidae, Scorpionidae, Heteroscorpionidae, Diploscorpionidae, Thin scorpionidae; (7) Phylum Mollusca, Class Gastropod, Order Cephalopoda: Pseudo-spined Snails, Pseudo-spined Sea Snails, Adidae, Sternidae, Semeno-spined Snails ... (8) Phylum Mollusca, Class Gastropod, Order Aplysia: Cylindrica, Aplysia, Hylostomidae, Hylostomidae, Hylostomidae, Hylostomidae, Hylostomidae, Hylostomidae, Hylostomidae, Hylostomidae; (9) Phylum Mollusca, Class Gastropod, Order Nudibranch: Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae; (10) Phylum Mollusca, Class Cephalopoda, Order Sepiidae: Sepiidae, Subfamily Heteropodinae, Subfamily Sakinocephalae, Subfamily Otocephalae; (11) Phylum Mollusca, Class Cephalopoda, Order Octopus: Octopidae, Giant Octopidae, Corydalis, Cuttlefish, Argonautidae, Heptapodidae, Deep-sea Octopus, Brachycopedidae; (12) Chordata: Acipenseridae, Hypophthalmichthys, Hypophthalmichthys, Neophthalmichthys, Osteoglossidae, Anguilla, Anguidae, Acanthodontidae, Cypriniformes, Gnaphalinae, Salmoniformes, Salmoninae, Herpidae, Salmoniformes, Ophiodontidae ... , Siluriformes, Siluridae, Silversides, Gnathophoridae, Silversides, Gnathophoridae, Gnathophoridae, Gadformes, Gadidae, Ophiopods, Ophiopods, Chrysopidae, Ophiopods, Ophiopods, Ophiopods, Ophiopods, Sphenodontidae, Syngnathidae, Syngnathidae, Syngnathidae, Perciformes, Wrasseniidae, Perciformes, Rockfish, Perciformes, Pomacanthidae, Perciformes, Cichlidae; (13) Chordata, Amphibia, Apodidae: Jellyfish, Anemone, Lumbricidae, Leechidae, Snakes, Sea Cucumbers, Asteridae, Echinoidea, Snails, Mussels, Clams, Calycozoa; (14) Chordata, class Amphibia, order Caudata: Cryptobranchidae, Ambystoma, Eusalidae, Hypoderma, Pulmonary Salamanders, Amphibia, Caviidae, Costidae, Eudontidae, Fat Salamanders, Blind-eyed Lumbricidae, and Megalostomidae; (15) Chordata, Amphibia, Anura: Toads, Rhacophoridae, Hylacidae, Ceratopogonidae, Mylodactylidae, Microdactylidae; (16) Phylum Chordata: Reptiles: Squamata, Testudinidae, Dermatochelydae, Testudinidae, Cheloniformes, Testudinidae, Testudinidae, Crocodilia, Alligators, Alligators, Alligators; (17) Chordata: Psittaciformes, Cockatielidae, Psittaciformes, Lorikeetidae, Anseriformes, Anatidae, Anseriformes, Anseriformes, Spheniscidae, Passeriformes, Passeriformes, Corvidae, Passeriformes, and Passeriformes; (18) Chordata: Monotremes: Platypus, Echidna, Perissodactyla, Rhinoceros, Proboscidea; (19) Chordata, Mammalia, Marsupials: Marmosets, Koalas, Bandicoots, Wombats, and Quetzalcoatlus; (20) Chordata, class Mammalia, order Rodentia: Sciuridae, Cricetidae, Bamboo Rhynchomys, Dormouse, Myrmecophaga, Caviidae, Beaver, Flying Squirrel, Porcupine, Lemming, Gerbil, Capybara; (21) Chordata, Mammalia, Chiroptera: Pteropus, Rhinolophus, Hippodrome, Myotis, Long-winged Bat, Brachypterygidae, Fruit Bat; (22) Chordata, Mammalia, Carnivora: Felidae, Canidae, Ursidae, Mustelidae, Lutradae; (23) Chordata, Mammalia, Primates: Hominidae, Gibbon, Loris, Tarsier, Lemuridae; (24) Chordata, Mammalia, Artiodactyla: Camelidae, Suidae, Peccary, Giraffidae, Pronghorn, Cervidae, Musk Deer, Bovidae, Hippopotamidae; (25) Phylum Chordae, Class Mammalia, Order Cetacea: freshwater dolphins, sperm whales, beaked whales, narwhals, sharp-nosed dolphins, dolphins, porpoises, baleen whales, gray whales, right whales, minke whales, beaked whales, fin whales; The plant-derived protein is at least one of the following animal proteins: (1) Ceratophyllum: Ceratophyllums: Ceratophyllums, ... (2) True Mosses: Axis order, Axis family, Axis order, Hoary moss family, Axis order, Micro-moss family, Corrugated moss order, Corrugated moss family, Beaded moss order, Beaded moss family, True moss order, True moss family, True moss order, Lantern moss family, Shrimp moss order, Shrimp moss family, Tobacco moss order, Tobacco moss family, Brachycera order, Brachycera family, Opposite leaf order, Opposite leaf order, Anti-neon moss family, Gourd moss order, Big cap moss family, Gourd moss order, Gourd moss family, Purple calyx order, Purple calyx order, Purple calyx order, Purple calyx order, Purple calyx order, Purple calyx order, Stone crack moss Mosses, the order of the purple-calyx mosses, the order of the tiger-tail mosses, the order of the yellow-yellow mosses, the order of the oily mosses, the order of the oily mosses, the order of the white mosses, the order of the oily mosses, the order of the velvet-cap mosses, the order of the tree-lime mosses, the order of the tree-lime mosses, the order of the tree-lime mosses, the order of the straight-toothed mosses, the order of the wood-ling mosses, the order of the wood-ling mosses, the order of the ridge-capped mosses, the order of the juniper mosses, the order of the juniper mosses, the order of the water-lichen mosses, the order of the twisted-stem mosses, the order of the water-lichen mosses, the order of the water-lichen mosses, the order of the cold-lichen mosses, the order of the water-lichen mosses, the order of the beautiful-lichen mosses; (3) Eubryophyta, Eubryophyta, Angiospermaceae, Angiospermaceae, Angiospermaceae, Angiospermaceae, Angiospermaceae; (4) True mosses: Onagraceae, Bolognaaceae, Reverse hair mossaceae, Green mossaceae, Wetland mossaceae, Wannian mossaceae, Cryptocapsulariaceae, Silk mossaceae, Brocteraceae, Sphagaceae, Soft tooth mossaceae, Tower mossaceae, Gray mossaceae, Peacock mossaceae, Boat leaf mossaceae, Thin Luo mossaceae, White tooth mossaceae, Crepe mossaceae, Tilapia mossaceae, Golden hair mossaceae, Flat mossaceae, Straight mossaceae, Cotton mossaceae, False fine Luo mossaceae, Axillary mossaceae, Pteridaceae, Golden gray mossaceae, Hairy brocade mossaceae, Heterodontaceae, Weeping mossaceae, Heliconia mossaceae, Brocade mossaceae, Pseudo-thin Luo mossaceae, Sclerophyllaceae, Acanthaceae, Lepiophyllaceae, Thick handle mossaceae; (5) Eubryophytes, Eubryophytes, and Hypobryophytes: Phyllostachys, Candleleafys, Microhylophytes, Botrychnophytes, Arboretum, Hypobryophytes, Thick Lithophytes, Echinopsaceae, and Light Mosses; (6) True mosses: Black mosses, Black mosses, Black mosses, Black mosses, True mosses: Long mosses, Long mosses, Long mosses, True mosses: Golden mosses, Golden mosses, Golden mosses, True mosses: Sphagnum mosses, Sphagnum mosses, True mosses: Sphagnum mosses, True mosses: Sphagnum mosses, True mosses: Algae mosses, Algae mosses, True mosses: Tetradentata mosses, Tetradentata mosses, Tetradentata mosses; (7) Chlorophyta, Chlorophyta: Bryophyceae, ... (8) Chlorophyta, Chlorophyta, Acrophyceae, Acrophyceae, Gymnophyceae, Gymnophyceae, Gymnophyceae, Gymnophyceae, Dauerlys ... (9) Marchantia: Bracteaceae, Microphylla, Microphylla, Nanximeiaceae, Forkleaf, Forkleaf, Greenleaf, Bandleaf, Bandleaf, Mossleaf, Bandleaf, Purpleleaf, Purpleleaf, Light-calyx, Ear-leaf, Light-calyx, Hair-ear, Light-calyx, Fine-scale, Light-calyx, Eye-calyx, Light-calyx, Flat-calyx, Hair-leaf, Hair-leaf, New-leaf; (10) Phyllophyllous order: Acrocalyceae, Cryptocapsulariaceae, Erectleafaceae, Leptocarpaceae, Pocillopora, Eyelashaceae, Capsulariaceae, Macrocalyceae, Pseudo-macrocalyceae, Geocalyceae, Holocyceae, Fusariumaceae, Shearleafaceae, Longicyceae, Armoraceae, Leafmoss, Complexaceae, Fingerleafmoss, Toothcalyceae, Splitleafmoss, Beardmoss, Microcalyceae, Pseudocalyceae, Feathermoss, Pseudo-complexaceae, Scutellariaceae, Synophyllaceae, Diplocoleaceae, Tubemoss, Horizontalleafmoss, Velvetmoss; (11) Phylum Ranunculaceae, Class Ranunculales: Verruco-crown family, Star-hole family, Snake family, Flowery family, Liverwort family, Dioscorea family, Light family, Single-month family, Money family, Leather-leaf family, Wesley family; (12) Rhodophyta: Acrophyceae, Acrophyceae, Ignaec ... (13) Rhodophyta, Rhodophyta, and Taxodium: Stem-spined algae, Gelatophyceae, Endophyceae, Taxodium, Myxocystis, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae; (14) Vascular plants, class Equisetum: Alsophilales, Cyathophytes, family Cyathophytes, family Cyathophytes, family Equisetaceae, family Diplophyllaceae, family Diplophyllaceae, family Diplophyllaceae, family Hymenopterales, family Hymenopterales, family Hymenopterales, family Hymenopteraceae, family Osmanthaceae, family Pinaceae, family Sophora, family Sophora, family Sophora, family Cyperaceae, family Cyperaceae; (15) Vascular plants, class Equisetaceae, order Polypodiaceae: Aspleniaceae, Aspleniaceae, Pterid ... (16) Vascular plants: Acorusales, Acorus family; Palmaceae; Schisandraceae; Boraginaceae; Buxusales, Buxus family; Celastraceae; Ceratophyllum family; Ceratophyllum family; Chrysanthemum family; Commelinaceae; Commelinaceae; Commelinaceae; Commelinaceae; Commelinaceae; Cornaceae; Cornaceae; Hydrangeaceae; Cornaceae; Cyanophyllum family; Tassel family; Tassel family; Pentacarpaceae; Cucurbitaceae; Cucurbitaceae; Begoniaceae; Cucurbitaceae; Moracaceae; Cucurbitaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; The order Acanthaceae, the order Leguminosae, the order Polygala, the order Merantiaceae, the order Psoralea, the order Psoralea, the order Eucommia, the order Geraniales, the order Decapoda, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Vitis, the order Vitis; the order Vitis; (17) Vascular plants: Alismataceae, Araceae, Araceae, Asteraceae, Asteraceae, Asteraceae, Asteraceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae; (18) Vascular plants, Magnoliaceae, Apiaceae, Araliaceae, Pittosporaceae, and Coleopsaceae; (19) Vascular plants, Magnoliaceae, Aquilegiaceae: Aquilegiaceae, Aquilegiaceae, Aquilegiaceae; (20) Vascular plants, Magnoliaceae, Asparagales: Asparagaceae, Amaryllidaceae, Asphodelaceae, Curculigoaceae, Iridaceae, Orchidaceae; (21) Vascular plants: Magnoliaceae, Asterales, Asteraceae, Campanulaceae, Menymaceae, Pentaphyllum, Stylophyllum; (22) Vascular plants, Magnoliaceae, Cruciferae: Cruciferae, Glechomaea, Carica, Caricaceae, Moringaceae, Meliaceae, Echinopsaceae, Nasturtiumaceae; (23) Vascular plants: Caryophyllaceae, Aizoaceae, Amaranthaceae, Uncariaceae, Basella, Cactaceae, Droseraceae, Petalopsis, Pinaceae, Cornaceae, Nepenthesaceae, Mirabilis, Allium, Phytolaccae, Pleurotus, Polygonaceae, Portulaceae, Glechomae, Salicaceae; (24) Vascular plants: Ericaceae, Actinidiaceae, Impatiens, Alnus, Ixigera, Diospyros, Ericaceae, Leydigaceae, Cyperaceae, Pentaphyllum, Allium, Primulaceae, Sapotaceae, Costaceae, Styracaceae, Asteraceae, Theaceae; (25) Vascular plants, Magnoliaceae, Fagales: Fagaceae, Betulaceae, Casuarinaceae, Fagaceae, Juglandaceae, Myricaceae; (26)) Vascular plants, Magnoliaceae, Gentianales: Gentianaceae, Apocynaceae, Gelsemium, Gentianaceae, Loganaceae, Rubiaceae; (27) Vascular plants, Magnoliaceae, Labiatae: Lamiaceae, Acanthaceae, Bignoniaceae, Vanillaceae, Gesneriaceae, Utriculariaceae, Matricariaceae, Ceratoniaceae, Aquilegiaceae, Oleaceae, Orobanchaceae, Paulowniaceae, Sesamaceae, Penicillaceae, Plantaginaceae, Scrophulariaceae, Verbenaceae, and Aglaonema; (28) Vascular plants, Magnoliaceae, Liliales: Liliaceae, Colchicumaceae, Hostaceae, Veratrum, Smilaxaceae; (29) Vascular plants: Malpurinae, Echinopsaceae, Echinopsaceae, Anshenaceae, Garciniaceae, Pomacantha, Stellariaceae, Corydalis, Euphorbiaceae, Hypericaceae, Glutinaceae, Linaceae, Tropaeolaceae, Cyperaceae, Passifloraceae, Arboraceae, Phyllanthaceae, Carexaceae, Drupaceae, Rhizophoraceae, Salicaceae, Violaceae; (30) Vascular plants, Magnoliaceae, Malvaceae: Malvaceae, Malvaceae, Helianthaceae, Dipterocarpaceae, Thymelaeaceae; (31) Vascular plants, Magnoliaceae, Myrtales: Myrtaceae, Combretaceae, Cryptomeriaceae, Lythraceae, Melastomataceae, Onagraceae; (32) Vascular plants, Magnoliales, Pandanaceae: Pandanaceae, Stemonaceae, Mycorrhizae, and Featherleafaceae; (33) Vascular plants: Magnoliaceae, Poaceae, Bromeliaceae, Cyperaceae, Cyperaceae, Cyperaceae, Juncaceae, Sphagaceae, Juncaceae, Typhaceae, and Cyperaceae; (34) Vascular plants, Magnoliaceae, Proteales: Proteaceae, Nelumboceae, Platanaceae, and Ceropegiaceae; (35) Vascular plants, Magnoliaceae, Ranunculales: Ranunculaceae, Berberidaceae, Astrophyllaceae, Akebiaceae, Menispermaceae, Papaveraceae; (36) Vascular plants: Magnoliaceae, Rosaceae, Elaeagnaceae, Moraceae, Rhamnaceae, Rosaceae, Ulmaceae, Urticaceae; (37) Vascular plants: Magnoliaceae, Santalum orders: Santalaceae, Cyperaceae, Cyperaceae, Cyperaceae, Loranthaceae, Aspergillus family, Citronaceae, Santalaceae, Cyperaceae, and Malvaceae; (38) Vascular plants, Magnoliaceae, Sapindaceae: Sapindaceae, Anacardiaceae, Botrytis cinerea, Oleaceae, Meliaceae, Nitraria tanguticaceae, Rutaceae, Simsinaceae; (39) Vascular plants: Magnoliaceae, Saxifragales: Saxifragaceae, Mycorrhizaceae, Cynomorium, Sansevieriaceae, Ribesaceae, Echinochloa, Hamamelidaceae, Myristicaceae, Paeoniaceae, Psoralea, Saxifragaceae; (40) Vascular plants, Magnoliaceae, Solanales: Solanaceae, Convolvulaceae, Acanthaceae, Sphenopalmataceae; (41) Vascular plants, Magnoliaceae, Zingiberales: Zingiberaceae, Cannaceae, Zingiberaceae, Orchidaceae, Marantaceae, Musaceae, Strelitziaceae; (42) Vascular plants: Araucariaces, Araucariaceae, Araucariaces, Podocarpaceae, Cupressaceae, Cupressaceae, Cupressaceae, Taxaceae, Cycadales, Cycadaceae, Ephedales, Ephedraceae, Ginkgoales, Ginkgoaceae, Gnetaceae, Pinaceae, Pinaceae, and Machilaceae.

6. The protein-based hydrogel adsorption material according to any one of claims 1 to 3, characterized in that: The protein is selected from at least one of lysozyme, bovine serum albumin, human serum albumin, lactoferrin, whey albumin, insulin, α-lactalbumin, fibrinogen, β-lactoglobulin, Aβ peptide, prion protein, α-synuclein, cystatin C, huntingtin protein, immunoglobulin, ribonuclease A, cytochrome c, α-amylase, horseradish peroxidase, pepsin, myoglobin, collagen, keratin, hemoglobin, DNA polymerase, casein, soy protein, pea protein, zein, gliadin, gluten, oat protein, potato protein, hemp seed protein, walnut protein, rapeseed protein, hazelnut protein, quinoa protein, sunflower seed protein, pumpkin seed protein, black sesame protein, mushroom protein, red algae protein, legumin, barley protein, wheat protein, millet protein, gluten, kidney bean protein, casein, collagen, and catalase.

7. The protein-based hydrogel adsorption material according to any one of claims 1 to 3, characterized in that: The polysaccharide compound is at least one of nanocellulose, cellulose nanocrystals, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, chitosan, sodium alginate, gelatin, corn starch, potato starch, dextran, mannan, polypectin, low-methylated pectin, gum arabic, guar gum, tragacanth gum, apricot gum, peach gum, konjac glucomannan, galacturonic acid, keratan, chitin, glycogen, hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate, heparin, and heparan sulfate.

8. The protein-based hydrogel adsorption material according to any one of claims 1 to 3, characterized in that: The reducing agent is at least one of tris(2-carboxyethyl)phosphine hydrochloride, cysteine, reduced glutathione, dithiothreitol, β-mercaptoethanol, dimercaptosuccinic acid, 2-mercaptoethanol, and sodium sulfite; the oxidizing agent is at least one of sodium ferrate, trivalent cobalt salt, chlorate, potassium permanganate, persulfate, potassium dichromate, concentrated sulfuric acid, hydrochloric acid, nitric acid, hydrobromic acid, hydroiodic acid, perchloric acid, ozone, hydrogen peroxide, fluorine gas, chlorine gas, sodium bismuthate, periodic acid, lead dioxide, guanidine hydrochloride, urea, trifluoroethanol, hexafluoroisopropanol, and trifluoroacetic acid.

9. The protein-based hydrogel adsorption material according to any one of claims 1 to 3, characterized in that: The plastic carrier film is any one of polyethylene film, polypropylene film, polyvinyl acetate film, polyvinyl chloride film, polystyrene film, polyvinylidene chloride film, ethylene-vinyl acetate copolymer film, polyvinyl alcohol film, polylactic acid film, polytetrafluoroethylene film, nylon film, polyester film, polyamide film, and vinyl acetate plastic film.

10. The protein-based hydrogel adsorption material according to claim 2 or 3, characterized in that: The linker solution, protein solution and polysaccharide compound solution are all prepared with dimethyl sulfoxide or a mixed solution of dimethyl sulfoxide and deionized water as solvent; the reducing agent solution and oxidizing agent solution are all prepared with deionized water as solvent.

11. Use of the protein-based hydrogel adsorption material according to claim 1 in remediating water contaminated by heavy metals.

12. Use of the protein-based hydrogel adsorption material according to claim 1 in remediating soil contaminated by heavy metals.

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