Organic nitrogen promotes stability of metallic catalysts in conversion of bamboo pulp to low carbon polyols
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摘要: 采用等体积浸渍法制备了一系列多孔竹炭负载的有机氮掺杂的镍钨催化剂，并将其应用于催化竹浆纤维氢解制C2，3多元醇反应。有机氮源与催化剂前驱体中Ni2+络合，高温煅烧时载体表面碳、氮和金属离子相互作用后生成一定量的C3N4、氮化物和合金物相。通过XRD、XPS和TEM等表征手段分析了催化剂Ni-W/MBC表面物理化学性质与催化活性间的关系。结果表明，除了金属镍、氧化钨物相外，表面还含有Ni-W合金（NiWO4为主）；金属粒子表面包围了一层石墨化C3N4物相。XPS分析表明，有机氮源高温分解反应后形成了C3N4物相。在反应条件下，15% Ni-20% W/MBC@M-0.25催化剂得到乙二醇收率为55.8%，而未添加有机氮源的催化剂15% Ni-20% W/MBC获得的乙二醇收率仅为36.9%。催化剂稳定性实验结果表明，Ni-W合金和C3N4物相的形成显著增强了Ni-W/MB催化剂的稳定性，延长了催化剂寿命。Abstract: Herein, the synthesis and performance of a novel and stable catalyst capable of facile hydrolysis of bamboo pulp were reported. Based on adopting complex agent to have a complex reaction with Ni2+ cations, the graphitic g-C3N4 phase and nitride phases were formed eventually. The interaction among metals and C, N atoms was analyzed by XRD and XPS. Some Ni-W alloys (mainly NiWO4 was included) were formed besides metallic Ni0 and tungsten species characterized. Particles on the surface of 15%Ni-20%W/MBC@M-0.25 catalyst exhibited homogeneous distribution and surrounded by disordered C3N4 layer characterized by TEM. Besides, the organic N sources were decomposed and the C3N4 phase with high hydrothermal property was formed simultaneously. For catalytic efficiency, 15%Ni-20%W/MBC@M-0.25 catalyst acquired the highest EG yield of 55.8% compared to 36.9% via 15%Ni-20%W/MBC catalysts. The carbon supports and organic nitrogen sources demonstrated great influence on catalytic efficiency. Catalyst recycle experiments implied that Ni-W/MBC@M-0.25 could remain relative stable under this catalytic reaction condition. The Ni-W alloys and the C3N4 phase were deduced as the main contributors to maintain the catalyst stability.
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Key words:
- bamboo pulp /
- organic nitrogen /
- metallic catalysts /
- hydrogenolysis /
- polyols
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Figure 1 Representative bio-based chemicals derived from lignin, hemicellulose and cellulose
Figure 2 N2 adsorption-desorption isotherms and the pore size distribution of MBC with various nitrogen sources and quantities
Figure 3 XRD patterns of different catalysts and MBC
(a): amount of melamine as the variable;
(b): the catalysts prepared by addition of multifarious nitrogen sources;
(c): MBC was pretreated by ethanol, alkali and water, respectively
Figure 5 TEM images of (a) Ni-W/MBC@M-0.25, (b) Ni-W/MBC@ARG-0.25, (c) Ni-W/MBC@CAR-0.25 catalysts and (d) the structure of metallic particles surrounded by C3N4 layer in high resolution
Figure 6 X-ray photoelectron spectra of (a) W 4f region and (b) Ni 2p of various 15%Ni-20%W/MBC@M-0.25 catalysts
Figure 7 X-ray photoelectron spectra of (a) C 1s and (b) N 1s on different nickel-tungsten catalysts
Figure 8 Effect of melamine addition on distribution of C2, 3 polyols: M-x represented the mass ratio of melamine based on the weight of MBC
Figure 9 Performance of nickel-tungsten catalysts influenced by adopting various nitrogen sources
Figure 10 Recycling experiments on the conversion of bamboo pulp into polyols over 15%Ni-20%W/MBC@M-0.25 catalyst: 5.0 MPa H2, 240 ℃ for 1.5 h
Figure 11 Concentrations of Ni cations in reaction liquids catalyzed by 15%Ni-20%W/MBC (with no N source, used for one time) and 15%Ni-20%W/MBC catalysts @M-0.25 (recycle use for five times)
Figure 12 Ni-W alloys and the C3N4 layer were identified as the main contributors to maintain the catalyst stability in the proposal reaction pathway
Table 1 Physical properties of different supported 15%Ni-20%W catalysts measured by BET
Sample ABET/(m2·g-1) vtotal/(cm3·g-1) Average pore size d/nm MBC@M-0.15 280.7 0.12 7.1 MBC@M-0.20 276.1 0.12 6.1 MBC@M-0.25 271.6 0.12 6.6 MBC@M-0.30 262.9 0.12 5.4 MBC@EDA-0.25 164.2 0.07 5.2 MBC@CAR-0.25 256.1 0.12 9.3 MBC@ARG-0.25 264.1 0.11 4.1 
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Table 2 Distribution of polyol products from bamboo pulp via nickel-tungsten catalysts a
Entry Catalyst Yield of product/% Conv. x/% EG b Gly 1, 2-PG glucose sor 1 15%Ni-20%W/MBC@M-0.15 29.4 4.1 6.1 5.4 5.1 83 2 15%Ni-20%W/MBC@M-0.20 46.2 3.5 7.6 3.5 4.3 100 3 15%Ni-20%W/MBC@M-0.25 55.8 5.6 10.5 4.8 6.1 100 4 15%Ni-20%W/MBC@M-0.25 b 25.4 3.3 2.1 1.3 trace 76 5 15%Ni-20%W/MBC@M-0.30 51.2 4.7 8.1 3.5 5.3 100 6 15%Ni-20%W/MBC 36.9 6.1 7.2 2.9 3.9 95 7 15%Ni-20%W/AC 21.6 2.3 7.8 3.1 trace 84 8 15%Ni-20%W/SWCNTs c 33.1 8.1 5.6 3.6 4.6 100 9 15%Ni/MBC@M-0.25 10.3 trace 1.2 6.1 1.4 78 10 20%W/MBC@M-0.25 6.5 trace trace 1.2 UD.g 95 11 15%Ni-20%W/MBC@EDA-0.25 d 44.6 4.5 5.3 5.7 4.1 100 12 15%Ni-20%W/MBC@CAR-0.25 e 31.0 5.6 3.2 4.3 0.9 91 13 15%Ni-20%W/MBC@ARG-0.25 f 54.1 6.1 3.0 4.1 3.2 100 a : reaction conditions: bamboo pulp 0.5 g, 5.0 MPa H2, 240 ℃ for 1.5 h; b: feedstock: raw bamboo powder; c: SWNTs: single-walled carbon nanotubes; d: EDA: ethanediamine; e: CAR: carbamide; f: ARG: arginine; g: undetected
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