生物质基@CuNiOS复合催化剂的制备及其在有机染料还原中的应用

doi:10.16085/j.issn.1000-6613.2025-0434

摘要/Abstract

摘要：

采用水热合成法制备了一种便于回收、易于与水分离且可生物降解的生物质基@CuNiOS复合催化剂，并以亚甲基蓝（MB）和罗丹明B（RhB）为模型污染物评估了其催化活性及重复使用性等性能。研究结果表明，以天然木/竹材为基底的NZ@CuNiOS、NP@CuNiOS和NB@CuNiOS分别于8min、16min和12min内完全还原MB，26min、34min和32min内完全还原RhB。相比之下，脱木素处理显著增强了催化剂的催化效率，DZ@CuNiOS、DP@CuNiOS和DB@CuNiOS仅需4min、8min和6min即可完全还原MB，在18min、26min和24min内完全还原RhB，展现出优异的催化活性。此外，生物质基@CuNiOS复合催化剂多次使用后仍保持84%以上的还原效率，展现出良好的重复使用性。该催化剂不仅绿色环保、可快速回收，而且性能优异以及具有可降解特性，为可持续污染治理提供了新思路。

关键词: 复合材料, 催化剂, 载体, 废水, 废物处理

Abstract:

Biomass-based@CuNiOS composite catalysts with easy recyclability, efficient water separability, and biodegradability were prepared via a hydrothermal synthesis method. The catalytic performance and reusability of the catalyst were evaluated using methylene blue (MB) and rhodamine B (RhB) as model pollutants. The results showed that the NZ@CuNiOS, NP@CuNiOS, and NB@CuNiOS completely reduced MB within 8min, 16min, and 12min, respectively, and RhB within 26min, 34min, and 32min. In contrast, delignification significantly enhanced the catalytic efficiency. DZ@CuNiOS, DP@CuNiOS, and DB@CuNiOS required only 4min, 8min, and 6min for the complete reduction of MB and 18min, 26min, and 24min for RhB reduction, demonstrating excellent catalytic activity. Moreover, the biomass-based@CuNiOS composite catalysts retained over 84% reduction efficiency after multiple cycles, indicating excellent reusability. The catalysts, featuring environmental friendliness, rapid recovery, high catalytic efficiency and biodegradability, offer a promising strategy for sustainable pollution remediation.

Key words: composites, catalyst, support, waste water, waste treatment

中图分类号:

TQ426.82

包新德, 刘必烨, 黄仁伟, 洪宇豪, 关鑫, 林金国. 生物质基@CuNiOS复合催化剂的制备及其在有机染料还原中的应用[J]. 化工进展, 2025, 44(S1): 185-196.

BAO Xinde, LIU Biye, HUANG Renwei, HONG Yuhao, GUAN Xin, LIN Jinguo. Preparation of biomass-based@CuNiOS composite catalysts for the reduction of organic dye[J]. Chemical Industry and Engineering Progress, 2025, 44(S1): 185-196.

图/表 8

图1 生物质基@CuNiOS复合催化剂的微观形貌结构对比

图2 木/竹材和不同生物质基@CuNiOS复合催化剂的晶体结构对比

图3 木/竹材和不同生物质基@CuNiOS复合催化剂的FTIR图谱

图4 木/竹材和生物质基@CuNiOS复合催化剂的XPS图谱

图5 不同生物质基@CuNiOS复合催化剂的吸光性能及带隙值对比

图6 不同生物质基底复合催化剂吸光度及对罗丹明B染料的催化还原效率及动力学拟合对比

图7 不同生物质基底复合催化剂吸光度及对亚甲基蓝染料的催化还原效率及动力学拟合对比

图8 DZ@CuNiOS复合催化剂使用前后的重复使用性和结构稳定性对比

参考文献 36

[1]	HUSSAIN Zawar, CHANG Na, SUN Jingqiu, et al. Modification of coal fly ash and its use as low-cost adsorbent for the removal of directive, acid and reactive dyes[J]. Journal of Hazardous Materials, 2022, 422: 126778.
[2]	宋茜, 吴睿, 王玉琳. 磁性纳米金复合材料的合成及催化性能研究[J]. 贵金属, 2025, 46(1): 19-25.
	SONG Xi, WU Rui, WANG Yulin. Study on the synthesis and catalysis performance of magnetic nano gold composites[J]. Precious Metals, 2025, 46(1): 19-25.
[3]	SUTTON Joseph, GRAUSE Guido, HMAYED AL RIDA HMAYED Ali, et al. Organocatalytic glycolysis of polyethylene terephthalate and product separation by membrane filtration[J]. Chemical Engineering Journal, 2025, 512: 162400.
[4]	MAJEED Najwa Sabir, ABDULLAH Samira Najem. Removal of dissolved organic compounds and contaminants from wastewater of a petroleum refinery by ion exchange[J]. Journal of Engineering, 2019, 25(10): 33-49.
[5]	CHENG Zhiyong, GUAN Hao, MENG Junwang, et al. Dual-functional porous wood filter for simultaneous oil/water separation and organic pollutant removal[J]. ACS Omega, 2020, 5(23): 14096-14103.
[6]	WANG Yuxian, AO Zhimin, SUN Hongqi, et al. Activation of peroxymonosulfate by carbonaceous oxygen groups: Experimental and density functional theory calculations[J]. Applied Catalysis B: Environmental, 2016, 198: 295-302.
[7]	SHEN Yafei, FU Yuhong. Advances in in situ and ex situ tar reforming with biochar catalysts for clean energy production[J]. Sustainable Energy & Fuels, 2018, 2(2): 326-344.
[8]	GE Shengbo, WEI Kexin, PENG Wanxi, et al. A comprehensive review of covalent organic frameworks (COFs) and their derivatives in environmental pollution control[J]. Chemical Society Reviews, 2024, 53(23): 11259-11302.
[9]	SHARMA Pankaj, KUMAR Amit, WANG Tongtong, et al. Advances in bimetallic metal organic frameworks (BMOFs) based photocatalytic materials for energy production and waste water treatment[J]. Frontiers of Environmental Science & Engineering, 2024, 18(12): 151.
[10]	ZHANG Fen, ZHANG Yongcai, ZHANG Geshan, et al. Exceptional synergistic enhancement of the photocatalytic activity of SnS₂ by coupling with polyaniline and N-doped reduced graphene oxide[J]. Applied Catalysis B: Environmental, 2018, 236: 53-63.
[11]	ZHOU Zenan, WANG Enfu, LIANG Yipeng, et al. Bio-based PA-grafted bamboo charcoal for improving the flame retardancy of PLA/PCL film without damaging mechanical properties and degradability[J]. Industrial Crops and Products, 2024, 210: 118182.
[12]	BAO Xinde, ZHANG Mengying, LI Ping, et al. Investigating the surface wettability and surface free energy of sodium silicate-impregnated poplar wood[J]. Wood Material Science & Engineering, 2023, 18(1): 141-150.
[13]	ZHENG Guanfeng, LI Xinglin, SONG Chaoyun, et al. Efficient catalytic reduction of dyes by single or agglomerated nano-silver functionalized wood and hydrodynamic simulation of wood channels[J]. Journal of Water Process Engineering, 2023, 56: 104522.
[14]	包新德, 李萍, 余海燕, 等. 硅酸钠改性对杨木力学性能及表面润湿性的影响[J]. 林产工业, 2023, 60(11): 9-13, 30.
	BAO Xinde, LI Ping, YU Haiyan, et al. Study on the effect of mechanical properties and surface wettability of poplar wood modified by sodium-silicate[J]. China Forest Products Industry, 2023, 60(11): 9-13, 30.
[15]	SEGAL L, CREELY J J, MARTIN A E, et al. An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer[J]. Textile Research Journal, 1959, 29(10): 786-794.
[16]	YANG Baoqian, WU Xinru, SU Zhengjie, et al. Heterovalent state and oxygen vacancy defect structure-associated V/S co-doped SnO₂ for catalytic reduction of organic and Cr⁶⁺ pollutants in the dark[J]. Advanced Sustainable Systems, 2024, 8(12): 2400429.
[17]	LU Yi, FAN Deqi, SHEN Ziyi, et al. Design and performance boost of a MOF-functionalized-wood solar evaporator through tuning the hydrogen-bonding interactions[J]. Nano Energy, 2022, 95: 107016.
[18]	GUO Ruixue, CAI Xiaohui, LIU Hanwen, et al. In situ growth of metal-organic frameworks in three-dimensional aligned lumen arrays of wood for rapid and highly efficient organic pollutant removal[J]. Environmental Science & Technology, 2019, 53(5): 2705-2712.
[19]	MENG Fanyang, LI Ning, YANG Haiyan, et al. Investigation of hydrogen peroxide-acetic acid pretreatment to enhance the enzymatic digestibility of bamboo residues[J]. Bioresource Technology, 2022, 344: 126162.
[20]	SUN Huizhi, ABDETA Adugna Boke, ZELEKEW Osman Ahmed, et al. Spherical porous SiO₂ supported CuVOS catalyst with an efficient catalytic reduction of pollutants under dark condition[J]. Journal of Molecular Liquids, 2020, 313: 113567.
[21]	LU Mengting, HE Wen, LI Ze, et al. Effect of lignin content on properties of flexible transparent poplar veneer fabricated by impregnation with epoxy resin[J]. Polymers, 2020, 12(11): 2602.
[22]	LI Kaiqian, ZHANG Xupeng, LI Xianghong, et al. Controllable adjustment of loading capacity of Cu-Zr bimetallic MOF on wood substrate to promote flame retardancy[J]. Journal of Thermal Analysis and Calorimetry, 2025, 150(7): 4995-5006.
[23]	ZHOU Haiyang, WEN Dongxian, HAO Xiaolong, et al. Nanostructured multifunctional wood hybrids fabricated via in situ mineralization of zinc borate in hierarchical wood structures[J]. Chemical Engineering Journal, 2023, 451: 138308.
[24]	包新德, 黄仁伟, 刘必烨, 等. CuMgOS/木基复合催化材料的制备及其还原染料性能[J]. 复合材料学报, 2025: 1-11. (2025-03-11). .
	BAO Xinde, HUANG Renwei, LIU Biye, et al. Preparation and dye reduction properties of CuMgOS/wood-based composite catalytic materials[J]. Acta Materiae Compositae Sinica, 2025, 1-11. (2025-03-11). .
[25]	YANG Li, LI Caifu, SONG Chen, et al. Spatial migration of lattice oxygen for copper-iron based oxygen carriers in chemical looping combustion[J]. Energy, 2023, 285: 129348.
[26]	WEI Cong, FANG Yanyan, LIU Bo, et al. Lattice oxygen-mediated electron tuning promotes electrochemical hydrogenation of acetonitrile on copper catalysts[J]. Nature Communications, 2023, 14: 3847.
[27]	CHEN Xiaoyun, KUO Dong-Hau. Nanoflower bimetal CuInOS oxysulfide catalyst for the reduction of Cr(Ⅵ) in the dark[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(5): 4133-4143.
[28]	GUO Jingjing, PENG Xiaoluo, WANG Shihuai, et al. Tailorable multi-photoresponsive behavior triggered by different sulfur oxidation states[J]. CCS Chemistry, 2024, 6(10): 2465-2475.
[29]	WU Binghong, YANG Baoqian, WU Xinru, et al. Synergistic tuning of heterovalent states and oxygen-vacancy defect engineering in hydrophilic W-doped Sb₂OS₂ for enhanced nitrogen photoreduction to ammonia[J]. ACS Applied Materials & Interfaces, 2024, 16(43): 58764-58779.
[30]	BIESINGER Mark C, PAYNE Brad P, GROSVENOR Andrew P, et al. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni[J]. Applied Surface Science, 2011, 257(7): 2717-2730.
[31]	JAFARI Vahid, NIEMINEN Kaarlo, SIXTA Herbert, et al. Delignification and cellulose degradation kinetics models for high lignin content softwood Kraft pulp during flow-through oxygen delignification[J]. Cellulose, 2015, 22(3): 2055-2066.
[32]	ABDETA Adugna Boke, WU Qinhan, KUO Dong-Hau, et al. Activated carbon-supported AgMoOS bimetallic oxysulfide as a catalyst for the photocatalytic hydrogen evolution and pollutants reduction[J]. Journal of Alloys and Compounds, 2022, 913: 165287.
[33]	WU Binghong, WU Xinru, KUO Dong-Hau, et al. W/Br co-doped Zn(O, S) with Zn/O bi-vacancy defects and heterovalent states for enhanced photocatalytic hydrogen evolution[J]. Materials Today Energy, 2025, 49: 101828.
[34]	WANG Xin, HU Jihang, GUAN Hao, et al. Wood-based catalytic filter decorated with ZIF-67 for highly efficient and continuous organic pollutant removal[J]. Chemical Engineering Journal, 2024, 479: 147580.
[35]	GE Chengcheng, SHU Fan, GUO Xinyu, et al. Comparison of Pd nanoparticle-decorated softwood and hardwood activated carbon in catalytic reduction of high-concentrated industrial 4-nitrophenol[J]. Separation and Purification Technology, 2024, 343: 127149.
[36]	MOSISA Mengistu Tadesse, WU Binghong, CHEN Longyan, et al. Ternary-heterojunction In₂S₃/Bi₂S₃/BiOBr catalyst with interfacial effect to enhance the photocatalytic degradation of organic dyes[J]. Journal of Water Process Engineering, 2025, 70: 107050.