秸秆纤维素基水凝胶负载Fe<sub>3</sub>O<sub>4</sub>/Cu催化剂还原硝基苯甲酸

doi:10.19965/j.cnki.iwt.2022-0693

摘要/Abstract

摘要：

利用废弃小麦秸秆为原料，通过离子液体法制备了小麦秸秆纤维素基水凝胶（SCH），合成了磁性秸秆纤维素基水凝胶负载Fe₃O₄（SCH@Fe₃O₄）催化剂。将SCH@Fe₃O₄催化剂经原位固定铜离子和化学还原法合成了原位负载的SCH @Fe₃O₄/Cu催化剂，并研究了该催化剂活化NaBH₄催化还原硝基苯甲酸（NA）的性能。同时，优化了催化剂投加量、NaBH₄投加量、NA初始浓度和反应温度对NA催化还原效果的影响。SCH@Fe₃O₄/Cu催化剂活化NaBH₄还原NA的性能优于商品纳米零价铁，该过程能够抵抗水体背景阴离子的干扰，具有优异的稳定性。此外，SCH@Fe₃O₄/Cu催化剂饱和磁化强度为13.1 emu/g，说明其具有强磁性，易于从水体中分离，实现催化剂的回收利用。利用农作物固体废弃物为原料制备功能性生物质催化剂，并用于水体污染物的治理，实现了“以废治废”的目标。

关键词: 小麦秸秆纤维素, 水凝胶, 催化还原, 硼氢化钠, 硝基苯甲酸

Abstract:

Taking waste wheat straw as raw material，wheat straw cellulose-based hydrogel （SCH） was prepared by ionic liquid method，and a magnetic straw cellulose-based hydrogel-supported Fe₃O₄（SCH@Fe₃O₄） catalyst was synthesized. Furthermore，the SCH@Fe₃O₄/Cu catalysts were in situ synthesized by copper stabilization and chemical reduction on the SCH@Fe₃O₄ catalysts. The performance of the SCH@Fe₃O₄/Cu catalysts was investigated with the activation of NaBH₄ for catalytic reduction of nitrobenzoic acid（NA）. The effects of catalyst dosage，NaBH₄ dosage，initial concentration of NA，and reaction temperature on the removal ratio of NA were optimized. The NA reduction catalyzed by SCH@Fe₃O₄/Cu catalyst was superior than that of commercial nano zero-valent iron，and could resist the interference of anions in the background of water，exhibiting excellent stability. Moreover，the saturation magnetization of the SCH@Fe₃O₄/Cu catalysts was 13.1 emu/g，indicating its strong magnetism and ease of separation to realize the recovery of the catalyst. In this study，we utilized crop solid waste as raw material to prepare functional biomass catalysts and applied them to treat water pollutants，achieving the goal of “treating waste with waste”.

Key words: wheat straw cellulose, hydrogel, catalytic reduction, sodium borohydride, nitrobenzoic acid

中图分类号:

X703.1

李增强. 秸秆纤维素基水凝胶负载Fe₃O₄/Cu催化剂还原硝基苯甲酸[J]. 工业水处理, 2023, 43(5): 141-148.

Zengqiang LI. Straw-based hydrogel supported Fe₃O₄/Cu catalysts for the reduction of nitronitrobenzoic acid[J]. Industrial Water Treatment, 2023, 43(5): 141-148.

https://www.iwt.cn/CN/Y2023/V43/I5/141

图/表 12

图1 SCH@Fe₃O₄/Cu催化剂的SEM（a）、SEM mapping（b）、TEM（c~d）

Fig. 1 SEM（a），SEM mapping（b），and TEM（c-d） of SCH@Fe₃O₄/Cu catalysts

图2 SCH@Fe₃O₄和SCH@Fe₃O₄/Cu催化剂的XRD

Fig. 2 XRD patterns of SCH@Fe₃O₄ and SCH@Fe₃O₄/Cu catalysts

图3 SCH@Fe₃O₄和SCH@Fe₃O₄/Cu催化剂的FTIR

Fig. 3 FTIR spectra of SCH@Fe₃O₄ and SCH@Fe₃O₄/Cu catalysts

图4 SCH@Fe₃O₄/Cu催化剂的XPS

Fig. 4 XPS spectra of SCH@Fe₃O₄/Cu catalysts

图5 SCH@Fe₃O₄和SCH@Fe₃O₄/Cu催化剂的VSM

Fig. 5 VSM of SCH@Fe₃O₄ and SCH@Fe₃O₄/Cu catalysts

图6 SCH@Fe₃O₄/Cu催化剂投加量对NA去除效果的影响

Fig. 6 Effect of dosages of SCH@Fe₃O₄/Cu catalyst on the removal efficiency of NA

图7 NaBH₄投加量对NA去除效果的影响

Fig. 7 Effect of dosages of NaBH₄ on the removal efficiency of NA

图8 NA初始质量浓度对NA去除率的影响

Fig. 8 Effect of initial concentrations of NA on the removal efficiency of NA

图9 反应温度对NA去除效果的影响

Fig. 9 Effect of temperatures on the removal efficiency of NA

图10 Cl^-、NO₃^-、SO₄^2-和HCO₃^-对NA去除率的影响

Fig. 10 Effect of Cl^-，NO₃^-，SO₄^2-，HCO₃^- on the removal ratio of NA

图11 SCH@Fe₃O₄/Cu催化剂催化还原NA的循环稳定性测试

Fig. 11 Cyclic stability test of SCH@Fe₃O₄/Cu catalyst for catalytic reduction of NA

图12 SCH@Fe₃O₄/Cu活化NaBH₄过程还原NA与nZVI直接还原NA的性能对比

Fig. 12 Comparison of performanceon NA reduction by the NaBH₄ activation process catalyzed by SCH@Fe₃O₄/Cu and the nano zero-valent iron（nZVI）

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秸秆纤维素基水凝胶负载Fe₃O₄/Cu催化剂还原硝基苯甲酸

Straw-based hydrogel supported Fe₃O₄/Cu catalysts for the reduction of nitronitrobenzoic acid

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秸秆纤维素基水凝胶负载Fe3O4/Cu催化剂还原硝基苯甲酸

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秸秆纤维素基水凝胶负载Fe₃O₄/Cu催化剂还原硝基苯甲酸

Straw-based hydrogel supported Fe₃O₄/Cu catalysts for the reduction of nitronitrobenzoic acid