CN117482947B - 一种负载单原子金属木质素基碳材料的制备方法及其应用 - Google Patents
一种负载单原子金属木质素基碳材料的制备方法及其应用 Download PDFInfo
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- CN117482947B CN117482947B CN202311849478.7A CN202311849478A CN117482947B CN 117482947 B CN117482947 B CN 117482947B CN 202311849478 A CN202311849478 A CN 202311849478A CN 117482947 B CN117482947 B CN 117482947B
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- Prior art keywords
- lignin
- carbon material
- based carbon
- metal
- loaded
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- 239000002184 metal Substances 0.000 title claims abstract description 54
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 18
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- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 claims description 10
- 229960001699 ofloxacin Drugs 0.000 claims description 10
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- -1 amino compound Chemical class 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
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- OJUDFURAIYFYBP-UHFFFAOYSA-N (dihydrazinylmethylideneamino)azanium;chloride Chemical compound Cl.NNC(NN)=NN OJUDFURAIYFYBP-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
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- AJHDRXSTMDYFOL-UHFFFAOYSA-N benzene-1,3,5-triamine;hydrochloride Chemical compound Cl.NC1=CC(N)=CC(N)=C1 AJHDRXSTMDYFOL-UHFFFAOYSA-N 0.000 claims description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
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- 238000002386 leaching Methods 0.000 description 9
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- 150000002500 ions Chemical class 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
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- 238000001291 vacuum drying Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 125000004429 atom Chemical group 0.000 description 2
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 150000004032 porphyrins Chemical group 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- 239000012692 Fe precursor Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 238000002056 X-ray absorption spectroscopy Methods 0.000 description 1
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- 125000003172 aldehyde group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 229910052734 helium Inorganic materials 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Classifications
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- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种负载单原子金属木质素基碳材料的制备方法及其应用，属于材料科学技术领域。该制备方法利用醛基木质素的成键特性引入金属配位单元，提高了前驱体和碳材料对金属原子的锚定作用。本发明所用原料成本低廉，制备过程简单，木质素基碳材料产物负载单原子金属含量高、比表面积大、催化活性优异、可重复使用，是一种优良的生物基功能材料，可用于水体净化、工业催化、吸附分离等领域。
Description
技术领域
本发明属于材料科学技术领域，具体涉及一种负载单原子金属木质素基碳材料的制备方法及其应用。
背景技术
负载型催化剂有利于提高催化剂的回收性和稳定性，对于减少环境污染、降低催化剂成本具有积极意义。近年来，金属单原子催化剂实现了金属原子的最大利用效率，在催化反应中显示出高活性和高选择性。作为一类新兴的负载型催化剂，通过调节金属与载体之间的相互作用，将活性金属的尺寸从纳米粒子减小到以单个原子分散在载体上，兼具了均相催化剂活性位点专一和非均相催化剂易于回收的优点，为工业催化、能源转化和环境治理领域带来了革命性升级。然而，原子分散的金属具有高的表面能，容易迁移和聚集成纳米粒子，不利于单原子催化剂的长期稳定使用。因此，合适的单原子金属催化剂载体至关重要。金属有机框架（MOF）材料具有结构周期性和配位功能基团的可设计性，该类结构能够作为理想的载体前驱体有效锚定碳前驱体中的金属单原子。然而，大多数MOF使用2-甲基咪唑等单体原料，这些单体价格昂贵，并且来源于不可再生的化石资源，面临成本高、易造成环境污染等问题。因此，需要寻找环境友好、廉价的前体替代现有碳前驱体。
木质素是构成植物细胞壁的主要成分，占天然木质纤维总质量的15%-35%，是自然界储量最丰富的可再生芳香族大宗资源。全球制浆造纸、生物炼制等工业每年可从植物原料中分离出约6000万吨木质素副产物。木质素分子结构中含有羟基、苯基、羧基等活性基团，可通过改性、复合等手段制备木质素基化学品。另外，木质素芳香化程度和含碳量高（约60%）、价格低廉，是制备碳材料的理想碳源。
近年来，研究者们开始利用木质素制备单原子金属催化剂载体，但目前报道较少，主要方法包括：① 将木质素与金属盐、含氮/硫等杂原子化合物直接共混，经高温碳化处理制得；② 将木质素与MOF共混，经高温碳化处理制得。然而，前一种方法直接使用木质素作为碳源，由于木质素结构中缺少杂原子或配位位点，难以有效锚定金属，容易造成金属易析出、催化位点分布不均等问题；后一种方法仍大量使用化石基原料，易导致环境污染问题。因此，发展杂原子含量丰富、金属锚定性能稳定、三废排放少的木质素基金属配位前驱体制备单原子金属催化剂仍具有挑战。
发明内容
为了克服上述现有技术的缺点，本发明提出了一种负载单原子金属木质素基碳材料的制备方法，该制备工艺简便、金属离子不易析出、三废排放少，有利于规模化工业生产；本发明还提出了一种负载单原子金属木质素基碳材料催化过硫酸盐降解水体中有机污染物的应用，为工业木质素资源的高值化利用提供了新思路。
为了解决上述问题，本发明所采用的技术方案如下：
一种负载单原子金属木质素基碳材料的制备方法为：将醛基木质素、胺基化合物和金属盐在溶液中反应制备金属有机聚合物，经分离、干燥后，得到负载金属材料的前驱体；再将负载金属材料的前驱体在惰性气体保护下经过高温碳化，冷却、研磨、洗涤、干燥后，即得到负载单原子金属木质素基碳材料。
进一步地，所述醛基木质素为木质素经过醛基化预处理后获得的产物；所述木质素为碱木质素、酶解木质素、硫酸盐木质素、木质素磺酸盐、磨木木质素中的任意一种或几种。
进一步地，所述胺基化合物为三聚氰胺、吡咯、对苯二胺、1,3,5-三氨基苯盐酸盐、联苯胺、蜜勒胺、4,4,4,4-甲乙烷四基四苯胺、三氨基胍盐酸盐中的任意一种或几种。
进一步地，所述金属盐为铁盐、钴盐、镍盐、铜盐中的任意一种或几种。
进一步地，所述反应溶液为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃、1,4-二氧六环、二甲亚砜、甲苯、均三甲苯、邻二氯苯、乙醇、丙醇、正丁醇、水中的任意一种或几种。
进一步地，所述惰性气体为氮气、氩气或氦气中的一种或几种；高温碳化时间为0.5-4 h；碳化温度为600-1000 ℃。
进一步地，所述洗涤为使用去离子水或乙醇反复洗涤1-3次。
进一步地，由上述负载单原子金属木质素基碳材料的制备方法制备得到的负载单原子金属木质素基碳材料。
进一步地，所述的负载单原子金属木质素基碳材料在水体净化中的应用，包括以下步骤：
(1) 将负载单原子金属木质素基碳材料作为催化剂，与水中的过硫酸盐和有机污染物，搅拌反应；催化剂用量为0.05-0.15 g/L，过硫酸盐浓度为0.1-0.9 mmol/L，有机污染物浓度为10-100 mg/L；
(2) 反应结束后，对负载单原子金属木质素基碳材料催化剂进行过滤、干燥至恒重，重复使用。
进一步地，过硫酸盐为过二硫酸盐、过一硫酸盐中的任意一种或几种；有机污染物为四环素、双酚A、磺胺二甲嘧啶、氧氟沙星中的任意一种或几种。
进一步地，所述过滤操作为抽滤、离心中的任意一种或几种；干燥操作为冷冻干燥、真空干燥和加热干燥中的任意一种或几种。
相比于现有技术，本发明的优点如下：
（1）本发明所用的醛基木质素可来源于制浆造纸、生物炼制行业的副产物，成本廉价，环境友好，促进木质素废弃物的高值化利用对于保护环境和实现双碳目标具有重要意义。
（2）本发明提供了一种负载单原子金属木质素基碳材料的制备方法，操作简单方便、后处理简单，无需额外使用金属刻蚀剂，设备要求低、三废排放少，利于工业化生产。
（3）本发明所制备的负载单原子金属木质素基碳材料具有形貌规整、单原子金属分布均匀、催化性能优异、可重复使用等优点。
（4）本发明所制备的材料前驱体可直接在木质素本体骨架中引入丰富的配位结构，在碳材料形成过程中利于有效锚定金属单原子，为防止单原子金属团聚和减少金属析出等问题提供了有效的解决方法。
（5）本发明所制备的负载单原子金属木质素基碳材料，能够高效催化过硫酸盐降解水中有机污染物，可应用于水体净化、工业催化、吸附分离等领域。
附图说明
图1为实施例1中负载Fe单原子木质素基碳材料的X射线光电子能谱图；
图2为实施例1中负载Fe单原子木质素基碳材料的扩展X射线吸收光谱图；
图3为实施例2中材料前驱体的红外光谱图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合具体实施例对本发明的具体实施方式做详细的说明。
以下实施例中所用到的原料如：醛基木质素为自制产品，采用现有技术，主要通过木质素原料与醛基化试剂反应制备而成（产率90%，醛基含量约2.0 mmol/g），干燥后保存供实验使用。其余原料包括三聚氰胺、1,4-二氧六环、三氯化铁、盐酸、吡咯、均三甲苯、氯化钴、蜜勒胺、N,N-二甲基乙酰胺、氯化镍、过一硫酸盐、四环素、氧氟沙星和双酚A均为市售产品。
实施例1
在烧瓶中，将2.0 g醛基酶解木质素（实验室自制）和1.0 g三聚氰胺（市售）溶于100 mL1,4-二氧六环（市售）溶液中，加热至100 ℃反应24 h；反应结束后，加入80 mL 500mg/L三氯化铁水溶液，析出粗产物；经离心分离后，将粗产物置于真空干燥箱中干燥24 h以上至恒重，得到2.75 g深绿色负载Fe前驱体产物，得率为90.4%。
将2.0 g的前驱体置于管式炉中，在氮气环境下升温至800 ℃并维持2 h。高温碳化后自然冷却至室温，将材料从炉中取出，研磨均匀后用0.5 mol/L的稀盐酸淋洗3次后去离子水反复洗涤至中性，经真空干燥后获得0.66 g负载Fe单原子木质素基碳材料。
经X射线光电子能谱分析，在710.90 eV和400.10 eV处出现了Fe（Fe 2p）和N（N1s）元素的特征峰（图1）。
经扩展X射线吸收光谱分析，Fe主要以Fe单原子形式分布在碳材料骨架中（图2）。
实施例2
在烧瓶中，将5.0 g醛基碱木质素和2.0 g吡咯分散于500 mL均三甲苯溶液中，加热至100 ℃反应24 h。反应结束后，加入200 mL的500 mg/L氯化钴水溶液，析出粗产物。经离心分离后，将粗产物置于真空干燥箱中干燥至恒重，得到6.75 g紫色负载Co前驱体产物，得率为95%。
将6.0 g负载Co前驱体置于管式炉中，在氮气环境下升温至850 ℃并维持3 h。高温碳化后自然冷却至室温，将材料从炉中取出，研磨均匀后用0.5 mol/L的稀盐酸淋洗3次后去离子水反复洗涤至中性，经真空干燥后获得2.46 g负载Co单原子木质素基碳材料。
经红外光谱分析，在1580 cm-1处出现卟啉结构中C=N伸缩振动峰，在991 cm-1处出现卟啉骨架振动峰（图3）。
实施例3
在反应瓶中，将3.0 g醛基硫酸盐木质素和1.0 g蜜勒胺分散于200 mL N,N-二甲基乙酰胺溶液中，加热至120 ℃反应18 h。反应结束后，加入100 mL的500 mg/L氯化镍水溶液，析出粗产物。经过滤分离后，将粗产物置于冷冻干燥箱中干燥至恒重，得到3.77 g负载Ni前驱体产物，得率为93.2%。
将3.0 g负载Ni前驱体置于管式炉中，在氩气氛围下升温至750 ℃并维持2 h。高温碳化后自然冷却至室温，将材料从炉中取出，研磨均匀后用0.5 mol/L的稀盐酸淋洗3次后去离子水反复洗涤至中性，经真空干燥后获得0.62 g负载Ni单原子木质素基碳材料。
实施例4
分别将实施例1制备的负载Fe单原子木质素基碳材料、实施例2制备的负载Co单原子木质素基碳材料和实施例3中制备的负载Ni单原子木质素基碳材料（使用量均为0.10 g/L）加入到含有0.7 mmol/L过一硫酸盐、pH=8的水溶液中，对四环素（溶液初始浓度为50 mg/L）进行降解，降解率分别分别为93.7%、89.6%和82.3%。负载Fe单原子木质素基碳材料经5次循环使用后，对四环素去除性能下降为初次使用的75.9%，Fe离子浸出小于100 μg/L。负载Co单原子木质素基碳材料经5次循环使用后，对四环素去除性能下降为初次使用的74.6%，Co离子浸出小于50 μg/L。负载Ni单原子木质素基碳材料经5次循环使用后，对四环素去除性能下降为初次使用的78.0%，Ni离子浸出小于100 μg/L。
表1：负载Fe单原子木质素基碳材料5次循环使用中四环素的降解率与Fe离子浸出率对比表
表2：负载Co单原子木质素基碳材料5次循环使用中四环素的降解率与Co离子浸出率对比表
表3：负载Ni单原子木质素基碳材料5次循环使用中四环素的降解率与Ni离子浸出率对比表
实施例5
将实施例2制备的负载Co单原子木质素基碳材料（使用量为0.08 g/L）、实施例1制备的负载Fe单原子木质素基碳材料（使用量为0.08 g/L）和实施例3制备的负载Ni单原子木质素基碳材料（使用量为0.08 g/L）加入到含有0.5 mmol/L过硫酸盐、pH=8的水溶液中，对氧氟沙星（溶液初始浓度为20 mg/L）进行降解，负载Co单原子木质素基碳材料降解率为81.5%，经5次循环使用后，对氧氟沙星去除性能下降为初次使用的67.2%。负载Fe单原子木质素基碳材料降解率为75.4%，经5次循环使用后，对氧氟沙星去除性能下降为初次使用的64.5%。负载Ni单原子木质素基碳材料降解率为 77.6%，经5次循环使用后，对氧氟沙星去除性能下降为初次使用的66.7%。
表4：负载Co单原子木质素基碳材料5次循环使用中氧氟沙星的降解率对比表
表5：负载Fe单原子木质素基碳材料5次循环使用中氧氟沙星的降解率对比表
表6：负载Ni单原子木质素基碳材料5次循环使用中氧氟沙星的降解率对比表
实施例6
将实施例3制备的负载Ni单原子木质素基碳材料（使用量为0.12 g/L）、将实施例1制备的负载Fe单原子木质素基碳材料（使用量为0.12 g/L）和实施例2制备的负载Co单原子木质素基碳材料（使用量为0.12 g/L）加入到含有0.3 mmol/L过一硫酸盐、pH=6的水溶液中，对双酚A（溶液初始浓度为25 mg/L）进行降解，负载Ni单原子木质素基碳材料对双酚A的降解率为90.2%，经5次循环使用后，对双酚A去除性能下降为初次使用的62.1%。负载Fe单原子木质素基碳材料对双酚A的降解率为84.4%，经5次循环使用后，对双酚A去除性能下降为初次使用的65.3%。负载Co单原子木质素基碳材料对双酚A的降解率为82.6%，经5次循环使用后，对双酚A去除性能下降为初次使用的63.4%。
表7：负载Ni单原子木质素基碳材料5次循环使用中双酚A的降解率对比表
表8：负载Fe单原子木质素基碳材料5次循环使用中双酚A的降解率对比表
表9：负载Co单原子木质素基碳材料5次循环使用中双酚A的降解率对比表
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (8)
1.一种负载单原子金属木质素基碳材料的制备方法，其特征在于，先将载体醛基木质素与胺基化合物溶于有机溶液中加热反应后，再加入金属盐溶液析出粗产物，经分离、干燥后，得到负载金属材料的前驱体；再将负载金属材料的前驱体经过高温碳化，冷却、研磨、洗涤、干燥后，即得到负载单原子金属木质素基碳材料；
所述醛基木质素为木质素经过醛基化预处理后获得的产物；所述木质素为碱木质素、酶解木质素、硫酸盐木质素、木质素磺酸盐、磨木木质素中的任意一种或几种；所述金属盐为铁盐、钴盐、镍盐、铜盐中的任意一种或几种。
2.根据权利要求1所述负载单原子金属木质素基碳材料的制备方法，其特征在于，所述胺基化合物为三聚氰胺、吡咯、对苯二胺、1,3,5-三氨基苯盐酸盐、联苯胺、蜜勒胺、4,4,4,4-甲乙烷四基四苯胺、三氨基胍盐酸盐中的任意一种或几种。
3.根据权利要求1所述负载单原子金属木质素基碳材料的制备方法，其特征在于，所述有机溶液为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃、1,4-二氧六环、二甲亚砜、甲苯、均三甲苯、邻二氯苯、乙醇、丙醇、正丁醇、水中的任意一种或几种。
4.根据权利要求1所述负载单原子金属木质素基碳材料的制备方法，其特征在于，高温碳化时间为2-4h；碳化温度为700-1000℃。
5.根据权利要求1所述负载单原子金属木质素基碳材料的制备方法，其特征在于，所述洗涤为使用去离子水或乙醇反复洗涤，洗涤次数为1-3次。
6.根据权利要求1-5任一所述负载单原子金属木质素基碳材料的制备方法制备得到的负载单原子金属木质素基碳材料。
7.根据权利要求6所述的负载单原子金属木质素基碳材料在水体净化中的应用，其特征在于，包括以下步骤：
(1)将负载单原子金属木质素基碳材料作为催化剂，与水中的过硫酸盐和有机污染物，搅拌反应；催化剂用量为0.05-0.15g/L，过硫酸盐浓度为0.1-0.9mmol/L，有机污染物浓度为10-100mg/L；
(2)反应结束后，对负载单原子金属木质素基碳材料催化剂进行过滤、干燥至恒重，重复使用。
8.根据权利要求7所述的应用，其特征在于，过硫酸盐为过二硫酸盐、过一硫酸盐中的任意一种或几种；有机污染物为四环素、双酚A、磺胺二甲嘧啶、氧氟沙星中的任意一种或几种。
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016207351A2 (en) * | 2015-06-24 | 2016-12-29 | Genencor International B.V. | Polypeptides having demethylating activity |
| CN108246330A (zh) * | 2018-01-12 | 2018-07-06 | 北京化工大学 | 一种基于木质素/金属超分子组装构筑单原子催化剂的方法 |
| CN114950387A (zh) * | 2022-05-31 | 2022-08-30 | 周海滨 | 一种防污染土壤修复剂及其制备方法 |
| CN115228476A (zh) * | 2022-07-13 | 2022-10-25 | 广东工业大学 | 一种金属负载木质素碳材料及其制备方法和应用 |
| CN115779955A (zh) * | 2023-01-18 | 2023-03-14 | 国际竹藤中心 | 一种木质素碳负载的Fe-N单原子催化剂 |
| CN115970732A (zh) * | 2023-03-20 | 2023-04-18 | 河北工业大学 | 木质素衍生炭锚定单原子催化剂的制备方法及应用 |
| CN116162263A (zh) * | 2023-02-10 | 2023-05-26 | 中国林业科学研究院林产化学工业研究所 | 一种醛基化木质素及其制备方法和应用 |
| CN117199405A (zh) * | 2023-08-22 | 2023-12-08 | 广州大学 | 一种高效的orr电催化剂及其制备方法 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130117776A (ko) * | 2010-09-23 | 2013-10-28 | 토호 테낙스 오이로페 게엠베하 | 탄소 섬유의 제조를 위한 열가소성 리그닌 |
| BR112021017090A2 (pt) * | 2019-03-06 | 2021-11-03 | Wisconsin Alumni Res Found | Métodos de despolimerização de lignina |
| US20220332673A1 (en) * | 2019-06-26 | 2022-10-20 | University Of Florida Research Foundation, Inc. | Catalytic depolymerization of lignin to high value hydrocarbons |
-
2023
- 2023-12-29 CN CN202311849478.7A patent/CN117482947B/zh active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016207351A2 (en) * | 2015-06-24 | 2016-12-29 | Genencor International B.V. | Polypeptides having demethylating activity |
| CN108246330A (zh) * | 2018-01-12 | 2018-07-06 | 北京化工大学 | 一种基于木质素/金属超分子组装构筑单原子催化剂的方法 |
| CN114950387A (zh) * | 2022-05-31 | 2022-08-30 | 周海滨 | 一种防污染土壤修复剂及其制备方法 |
| CN115228476A (zh) * | 2022-07-13 | 2022-10-25 | 广东工业大学 | 一种金属负载木质素碳材料及其制备方法和应用 |
| CN115779955A (zh) * | 2023-01-18 | 2023-03-14 | 国际竹藤中心 | 一种木质素碳负载的Fe-N单原子催化剂 |
| CN116162263A (zh) * | 2023-02-10 | 2023-05-26 | 中国林业科学研究院林产化学工业研究所 | 一种醛基化木质素及其制备方法和应用 |
| CN115970732A (zh) * | 2023-03-20 | 2023-04-18 | 河北工业大学 | 木质素衍生炭锚定单原子催化剂的制备方法及应用 |
| CN117199405A (zh) * | 2023-08-22 | 2023-12-08 | 广州大学 | 一种高效的orr电催化剂及其制备方法 |
Non-Patent Citations (3)
| Title |
|---|
| Ni-N-C单原子催化剂活化过硫酸盐降解苯酚;彭小明等;《高等学校化学学报》;20210810;第42卷(第08期);第2581-2591页 * |
| Novel lignin-based single atom catalysts as peroxymonosulfate activator for pollutants degradation: Role of single cobalt and electron transfer pathway;Yuanfeng Qi等;《Applied Catalysis B: Environmental》;20210121;第286卷;文献号119910 * |
| 催化剂形态与酚类化合物加氢反应活性构效关系的研究进展;鲁金芝;魏雪梅;马占伟;胡斌;;《化工进展》;20191108;第39卷(第03期);第1000-1011页 * |
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