Research progress of preparation and application of lignin-based metal nanoparticles composites
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摘要: 木质素是一种最丰富的芳香族天然高分子生物质资源,木质素纳米粒子既具有木质素原本特点,还具有纳米材料的纳米效应等特性,在众多功能材料领域具有很大的潜在应用价值,特别是作为绿色还原剂直接还原金属离子生成木质素基金属纳米粒子复合材料,被广泛应用于催化领域等。本文综述了木质素纳米粒子的制备及其在金属离子还原和金属纳米粒子负载的研究进展,重点综述了木质素基金属纳米粒子复合材料在不同应用领域的研究进展,最后总结并展望了木质素在金属纳米粒子复合材料制备和应用中面临的机遇和挑战。Abstract: Lignin is the most abundant aromatic polymer. Lignin nanoparticles exhibit properties of nanomaterials on the basis of retaining original characteristic, which have great potential in various functional nanomaterial. In especial, lignin nanoparticles can be used as a green reducing agent for the synthesis of metal nanoparticles to prepare the nano composite materials, which are widely used in the application of catalysis. In this paper, the preparation of lignin nanoparticles and their application for reduction of metal ion, and metal nanoparticles loading were reviewed. It's focused on the research progress of lignin-based metal nanoparticles composites in various fields. Finally, the opportunities and challenges of lignin in the preparation and application of metal nanoparticles composites were summarized and prospected.
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图 10 木质素基Ag纳米微球的制备过程: (a) Pickering乳液; (b) 聚脲壳木质素微球; (c)木质素基Ag微球[83]
Figure 10. Preparation of lignin-based Ag nanospheres: (a) Pickering emulsion; (b) Polyurea shell lignin microsphere; (c) Lignin-based Ag microsphere[83]
microPCMs—Phase change microcapsules; EDA/DETA—Ethylene diamine/diethylene triamine; IPDI—Isophorone diisocyanate
表 1 木质素纳米粒子的制备方法及其优缺点
Table 1. Preparation of lignin nanoparticles and their advantages and disadvantages
Preparation method Size/nm Advantage Disadvantage Ref. Sol-gel method 0.7–82 Mild reaction conditions
Simple operation
Controllable sizeUneven size distribution
Long production cycle
Unstable yield[11-13] Mechanical method 15–300 Physical method
Pollution-free
Smaller sizeNanosize and structure instability
Strict process conditions[14-16] pH conversion sedimentation method 100–180 Mature method
Simple operation
Particle stabilityHigh lignin solubility required
Harsh process conditions
Use of toxic/harmful reagents[17-19] Self-assembly method 100–600 Stability in pure water
Controllable size
Get hollow particlesUse of organic chemicals
Agglomerate in low pH
Unstable high salt concentration[20-22] Electrospinning 100–800 Simple equipment
Process controllable
Strong anti-oxidationLow yield
Additional additives needed[23-24] Supercritical method 35–50 Small particle size
Narrow distribution
Evenly distributedAgglomerate when the temperature increases
The particle size increases with the increase of particle size distribution[25-26] 表 2 木质素基纳米粒子复合材料的应用
Table 2. Applications of lignin-based nanoparticles composites
Main effect Lignin-based nanocomposite Size/nm Lignin specie Application Ref. UV absorption and
antibacterialLignin nanoparticles 50 Enzymatic lignin Sunscreen cream [29] Lignin/PVA membrane 216 Enzymatic lignin Membrane [31] Lignin-TiO2 colloid 100–300 Alkali lignin Cosmetics [32] Lignin nanoparticles 25–80 Alkali lignin Antibacterial [33] Enhancer Lignin nanoparticles 85.8 Medium density Hydrogel [34] Lignin nanoparticles 66000–86000 Lignosulfonate Phenolic foam [35] Lignin/PVA membrane 195–197 DES/lignin Membrane [36] Lignin/resveratrol/Fe3O4
nanoparticles130 Alkali lignin Nanomedicine [37] Antioxidant Lignin nanoparticles 40–60 Low sulfonated lignin Membrane [38] Lignin nanoparticles 0.144±0.03 Organic solvent lignin Free radical scavenging [39] Lignin/PLA membrane 40–60 Primitive lignin Membrane [40] Lignin nanoparticles 40–60 Primitive lignin Hydrogel [41] Emulsifier Lignin nanoparticles 182 Alkali lignin Emulsifier [42] Lignin nanoparticles 200 Kraft lignin Surfactant [43] Lignin nanoparticles 30–30000 Alkali/kraft lignin Emulsion [44] Lignin nanoparticles 90–1000000 Kraft lignin Pickering system [45] Encapsulated Lignin-Fe3O4 nanoparticle 464±15 nm Kraft lignin Coating Fe3O4 [46] lignin-protein particles 210–230 Kraft lignin Protein coating [47] Lignin-cytotoxic 438 ± 56 Kraft lignin Coating cytotoxic [48] Lignin nanocapsules 50–300 Lignosulfonate Coating drug [49] Dye/ion adsorption Lignin microspheres 200 Organic solvent lignin Magnetic nanosphere [50] Lignin-Fe3O4 nanoparticle 20–40 Alkali lignin Magnetic nanoparticle [51] Lignin nanoparticles 450 Lignin in black liquor Phosphate adsorbent [52] Lignin-TiO2 nanoparticle 11.36 Kraft lignin Adsorbents [53] Notes: PVA—Poly(vinyl alcohol); PLA—Poly(lactic acid); DES—Deep eutectic solvent. 表 3 木质素基金属纳米粒子的制备
Table 3. Preparation of lignin-based metal nanoparticles
Lignin-based metal
nanocompositeLignin specie Metal ion precursor Size/nm Ref. Ag nanoparticles Alkali lignin AgNO3 5–100 [54] Acetic acid lignin AgNO3 24 [55] Organic solvent lignin AgNO3 <100 [56] Wheat straw lignin AgNO3 15–20 [57] Sodium lignosulfonate AgNO3 20 [58] Pd nanoparticles Woodchip PdCl2 5 [59] High molecular lignin PdCl2 1–5 [60] Kraft/sulfonate lignin PdCl2 8–20 [61] Alkali lignin PdCl2 <20 [62] Au nanoparticles Recovered lignin HAuCl4 20 [63] Kraft wood pupl HAuCl4 11–16 [64] Sodium lignosulfonate AuClK 28–6440 [65] Alkali lignin HAuCl4 15±7 [66] Pt nanoparticles Alkali lignin H2PtCl6 0.23 [67] Bimetallic Kraft lignin AuCl3/AgNO3 25 [68] Alkali lignin Pd(NH3)Cl2/HAuCl4 20–50 [69] Ni nanoparticles Lignocellulose MIL-77(Ni) 100 [70] Cu2O nanoparticles Lignin in black liquor CuSO4 100–200 [71] Fe nanoparticles Alkali lignin Fe(NO3) 3 50–150 [72] 表 4 木质素基金属纳米粒子复合材料的应用
Table 4. Applications of lignin-based metal nanoparticles composites
Application Lignin-based metal nanocomposite Composite size/nm Material property Product Ref. UV absorption and antibacterial ZnO nanocomposites 3–5/20–30 UV shield/antibacterial Sunscreen cream [77] Ag nanocomposites 5–100 UV shield/antibacterial Membrane [54] Ag nanocomposites <100 UV shield/antibacterial Membrane [56] Ag nanocomposites 11.2 Antibacterial Membrane [78] Ag nanocomposites 5.3 Antibacterial Membrane [79] Detection/adsorption chemical substances Ag nanocomposites 24 Select to Hg2+ Detection Hg2+ [55] Ag nanocomposites 10–50 Sensitive to H2O2 Detection H2O2 [80] Ag nanocomposites 41 Complexation metal ion Detection ion [81] Ag nanocomposites 20 Infrared response Detection Pb2+ [63] Catalysis Pd nanocomposites 1–5 Catalytic activity Heck reaction [60] Pd nanocomposites 8–20 Catalytic activity Heck reaction [61] Lignin/Pd nanospheres <20 Catalytic activity Conversion of aromatic compounds [62] Ni nanocomposites 100 Catalytic activity Dehydrogenation reaction [70] Biological antioxidation Ag nanocomposites 15–20 Antioxidant activity DPPH [57] Au nanocomposites 11–16 Antioxidant activity DPPH [64] Ag nanocomposites 10–15 Antioxidant activity DPPH [82] Au-Ag nanocomposites 25 Antioxidant activity Determination phenolic [68] Improve mechanical property Au nanocomposites 28–6440 Thermal stability Thermogravimetry [65] Ag nanocomposites 473 Thermal stability Thermogravimetry [83] Ag nanocomposites 20 Increase elasticity Hydrogel [58] Ag nanocomposites 125–145 Increase adhesion Hydrogel [84] -
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