Investigation into the heterogeneous photo-Fenton processing of coking wastewater utilizing titanium carbide-enhanced NiFeLDHs
-
摘要: 低成本、易管理、贴实际、稳达标的废水深度处理技术是实现焦化废水稳定达标排放的关键。非均相光芬顿技术运行具有成本低、无铁泥负担、运行要求低的特点，符合替代技术的要求。而该技术的实际应用中，催化剂的开发是核心。近年来，新兴的层状双金属氢氧化物（LDHs）具有比表面积大、层状结构规整、活性位点多、亲水基团丰富的特点，是理想的光芬顿催化剂备选。然而，LDHs光生电子空穴对的快速复合限制了其在水处理领域的应用，具有优异导电性的Ti3C2有助于解决这一弊端。研究通过Ti3C2的介入不仅将NiFeLDHs的比表面积扩大了1.4倍，同时提高了光生载流子的分离效率。TiC@NiFeLDH2展现了良好的光芬顿深度处理焦化废水的性能，120 min内对焦化尾水中COD的去除率达到了76.75%，相对NiFeLDHs提高了1.8倍。Abstract: Low-cost, easy-to-manage, practical, and consistently compliant advanced wastewater treatment technology is the key to ensuring stable compliant discharge of coking wastewater. The heterogeneous photo-Fenton technology, characterized by low operating cost, no iron sludge burden, and low operational requirements, meets the criteria for an alternative technology. The practical application of this technology, however, hinges on the development of catalysts. In recent years, layered double hydroxides (LDHs), with large specific surface area, regular layered structure, abundant active sites, and rich hydrophilic groups, have emerged as ideal candidates for photo-Fenton catalysts. Nevertheless, the rapid recombination of photogenerated electron-hole pairs in LDHs limits their application in water treatment; while Ti3C2, with its excellent electrical conductivity, helps to address this drawback. In this study, the introduction of Ti3C2 not only increased the specific surface area of NiFeLDHs by 1.4 times but also improved the separation efficiency of photogenerated carriers. Consequently, TiC@NiFeLDH2 exhibited excellent performance in the advanced treatment of coking wastewater via photo-Fenton process, achieving a COD removal rate of 76.75% in coking wastewater within 120 min, which was 1.8 times higher than that of NiFeLDHs.
-
Key words:
- Ti3C2 /
- layered double hydroxides (LDHs) /
- coking wastewater /
- photo-Fenton
-
图 1 Ti3C2、NiFeLDH、TiC@NiFeLDH2的XRD谱图
Figure 1. XRD patterns of Ti3C2, NiFeLDH, and TiC@NiFeLDH2
图 2 Ti3C2、NiFeLDH、 TiC@NiFeLDH2的扫描及透射电镜图
（a）Ti3C2 SEM图; （b）NiFeLDH SEM图; （c）TiC@NiFeLDH2 SEM图; （d）TiC@NiFeLDH2 TEM图（200 nm）; （e）TiC@NiFeLDH2 TEM图（50 nm）; （f）TiC@NiFeLDH2 TEM图（5 nm）
Figure 2. FE-SEM and TEM images of Ti3C2, NiFeLDH, and TiC@NiFeLDH2
图 3 Ti3C2、NiFeLDH、 TiC@NiFeLDH2的XPS图
(a) 全谱; (b) Fe 2p精细谱; (c) Ni 2p精细谱; (d) C 1s精细谱; (e) Ti 2p精细谱
Figure 3. XPS spectra of Ti3C2, NiFeLDH, and TiC@NiFeLDH2
图 4 NiFeLDH、TiC@NiFeLDH2的UV-vis DRS和带隙能谱图
（a）NiFeLDH、 TiC@NiFeLDH2的UV-vis DRS图; （b）NiFeLDH、 TiC@NiFeLDH2的带隙能谱图
Figure 4. UV-vis DRS spectra and band-gap analysis of NiFeLDH and TiC@NiFeLDH2
图 6 NiFeLDH、 TiC@NiFeLDH2的N2吸附-脱附等温曲线及孔径分布图
（a）NiFeLDH的N2;（b）TiC@/NiFeLDH2的N2
Figure 6. Nitrogen adsorption-desorption isotherm and pore size distribution diagram of NiFeLDH and TiC@/NiFeLDH2
图 7 NiFeLDH、TiC@NiFeLDH2的降解效果
（a）降解体系；（b）Ti3C2负载量；（c）循环试验
Figure 7. Photodegradation curves of NiFeLDH and TiC@NiFeLDH2
图 8 TiC@NiFeLDH2的自由基捕获试验
Figure 8. The free radical trapping experiments for degradation of phenol over TiC@NiFeLDH2
-
[1] AN N, HAO Y Y, HU S W, et al. Photocatalytic treatment of coking wastewater by cerium oxide loading with nitrogen-doping co-modified graphite carbon nitride[J]. Industrial Water Treatment, 2024, 44(12): 186-193,206. (安宁, 郝玉莹, 胡绍伟, 等. 二氧化铈/氮掺杂氮化碳光催化处理焦化废水[J]. 工业水处理, 2024, 44(12): 186-193,206. doi: 10.19965/j.cnki.iwt.2023-1096AN N, HAO Y Y, HU S W, et al. Photocatalytic treatment of coking wastewater by cerium oxide loading with nitrogen-doping co-modified graphite carbon nitride[J]. Industrial Water Treatment, 2024, 44（12）: 186-193,206. doi: 10.19965/j.cnki.iwt.2023-1096 [2] SHI Y, ZHAO Y, ZHAO X, et al. Effect of microwave-assisted silicon carbide on pH/COD of coking wastewater[J]. Iron Steel Vanadium Titanium, 2018, 39(5): 106-110. (石焱, 赵莹, 赵鑫, 等. 微波协同碳化硅对焦化废水pH/COD的影响[J]. 钢铁钒钛, 2018, 39(5): 106-110.SHI Y, ZHAO Y, ZHAO X, et al. Effect of microwave-assisted silicon carbide on pH/COD of coking wastewater[J]. Iron Steel Vanadium Titanium, 2018, 39（5）: 106-110. [3] ZHAO Y, SHI Y, ZHAO X, et al. Microwave-absorbing media cooperative treatment of PAHs in coking wastewater[J]. Iron Steel Vanadium Titanium, 2020, 39(3): 75-79. (赵莹, 石焱, 赵鑫, 等. 微波—吸波介质协同处理焦化废水中 PAHs[J]. 钢铁钒钛, 2020, 39(3): 75-79.ZHAO Y, SHI Y, ZHAO X, et al. Microwave-absorbing media cooperative treatment of PAHs in coking wastewater[J]. Iron Steel Vanadium Titanium, 2020, 39（3）: 75-79. [4] ZHOU M. Wastewater application of advanced treatment of coking wastewater by ozone catalytic oxidation[J]. Iron Steel Vanadium Titanium, 2025, 41(3): 95-98. (周梅. 焦化废水臭氧催化氧化深度处理及应用[J]. 钢铁钒钛, 2025, 41(3): 95-98. doi: 10.13789/j.cnki.wwe1964.2020.10.012ZHOU M. Wastewater application of advanced treatment of coking wastewater by ozone catalytic oxidation[J]. Iron Steel Vanadium Titanium, 2025, 41（3）: 95-98. doi: 10.13789/j.cnki.wwe1964.2020.10.012 [5] AN N, HU S W, WANG F, et al. Carbon self-doping coupled with cerium oxide co-modified graphite carbon nitride for photocatalytic treatment of coking wastewater[J]. Industrial Water Treatment, 2025, 45(8): 167-173. (安宁, 胡绍伟, 王飞, 等. 碳掺杂耦合氧化铈共修饰氮化碳光催化处理焦化尾水[J]. 工业水处理, 2025, 45(8): 167-173.AN N, HU S W, WANG F, et al. Carbon self-doping coupled with cerium oxide co-modified graphite carbon nitride for photocatalytic treatment of coking wastewater[J]. Industrial Water Treatment, 2025, 45（8）: 167-173. [6] LAI C, AN N, LI B S, et al. Future roadmap on nonmetal-based 2D ultrathin nanomaterials for photocatalysis[J]. Chemical Engineering Journal, 2021, 406: 126780. doi: 10.1016/j.cej.2020.126780 [7] GU Z, ATHERTON J J, XU Z P. Hierarchical layered double hydroxide nanocomposites: structure, synthesis and applications[J]. Chemical Communications, 2015, 51(15): 3024-3036. doi: 10.1039/C4CC07715F [8] ZHONG P, YU Q Q, ZHAO J W, et al. Degradation of bisphenol A by Fe-Al layered double hydroxides: A new synergy of homo- and heterogeneous Fenton systems[J]. Journal of Colloid and Interface Science, 2019, 552: 122-133. doi: 10.1016/j.jcis.2019.05.040 [9] ZHOU H, WU F, FANG L, et al. Layered NiFeLDH/MXene nanocomposite electrode for high-performance supercapacitor[J]. International Journal of Hydrogen Energy, 2020, 45(23): 13080-13089. doi: 10.1016/j.ijhydene.2020.03.001 [10] ZHANG D D, CAO J, ZHANG X Y, et al. NiMn layered double hydroxide nanosheets in-situ anchored on ti3c2 mxene via chemical bonds for superior supercapacitors[J]. ACS Applied Energy Materials, 2020, 3(6): 5949-5964. doi: 10.1021/acsaem.0c00863 [11] ANJUM D H, GOGOTSI Y, ALSHAREEFF H N. Atomic layer deposition of SnO2 on MXene for Li-ion battery anodes[J]. Nano Energy, 2017, 34: 249-256. doi: 10.1016/j.nanoen.2017.02.043 [12] LI H Y, WEN Y Y, ZHU X X, et al. Novel heterostructure of a MXene@NiFeLDH nanohybrid with superior peroxidase-like activity for sensitive colorimetric detection of glutathione[J]. ACS Sustainable Chemistry & Engineering, 2019, 8(1): 520-526. doi: 10.1021/acssuschemeng.9b05987.s001 [13] LI B S, LIU S Y, LAI C, et al. Unravelling the interfacial charge migration pathway at atomic level in 2D/2D interfacial Schottky heterojunction for visible-light-driven molecular oxygen activation[J]. Applied Catalysis B: Environmental, 2020, 266: 118650. doi: 10.1016/j.apcatb.2020.118650 [14] ZHANG Y, GUO B, HU L, et al. Synthesis of SnS nanoparticle-modified MXene (Ti3C2Tx) composites for enhanced sodium storage[J]. J. Alloys. Compd, 2018, 732: 448-453. doi: 10.1016/j.jallcom.2017.10.223 [15] GONG M, LI Y G, WANG H L, et al. An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation[J]. J. Am. Chem. Soc, 2013, 135: 8452-8455. doi: 10.1021/ja4027715 [16] SU W, WU F, FANG L, et al. NiCo-LDH nanowires@nanosheets core-shell structure grown on carbon fiber cloth for high performance flexible supercapacitor electrode[J]. J Alloys Compd 2019;799: 15e25. [17] WU X, WANG L, CHEN C, et al. Water-dispersible magnetite-graphene-LDH composites for efficient arsenate removal[J]. J. Mater. Chem, 2011: 17353–17359. [18] KHATAEE A, SADEGHI RAD T, NIKZAT S, et al. Fabrication of NiFe layered double hydroxide/reduced graphene oxide (NiFeLDH/rGO) nanocomposite with enhanced sonophotocatalytic activity for the degradation of moxifloxacin[J]. Chemical Engineering Journal, 2019, 375: 122102. doi: 10.1016/j.cej.2019.122102 [19] ZHANG R, XUE Z, QIN J Q, et al. NiCo-LDH/Ti3C2 MXene hybrid materials for lithium ion battery with high-rate capability and long cycle life[J]. Journal of Energy Chemistry, 2020, 50: 143-153. doi: 10.1016/j.jechem.2020.03.018 [20] LI M H, FANG L, ZHOU H, et al. Three-dimensional porous MXene/NiCo-LDH composite for high performance non-enzymatic glucose sensor[J]. Applied Surface Science, 2019, 495: 143554. doi: 10.1016/j.apsusc.2019.143554 [21] ZHANG M M, LAI C, LI B S, et al. Ultrathin oxygen-vacancy abundant WO3 decorated monolayer Bi2WO6 nanosheet: A 2D/2D heterojunction for the degradation of ciprofloxacin under visible and NIR light irradiation[J]. Journal of Colloid and Interface Science, 2019, 556: 557-567. doi: 10.1016/j.jcis.2019.08.101 [22] ZUO W Y, LIANG L, YE F G, et al. Construction of visible light driven silver sulfide/graphitic carbon nitride p-n heterojunction for improving photocatalytic disinfection[J]. Chemosphere, 2021, 283: 131167. doi: 10.1016/j.chemosphere.2021.131167 -
下载:
计量
- 文章访问数: 0
- HTML全文浏览量: 0
- PDF下载量: 0
- 被引次数: 0
