Characteristics of Kaolinite and Research Progress of its Composite Catalytic Materials
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摘要:
近年来，高岭石基复合催化材料因成本低廉、化学稳定性好以及具有高效催化性能等优点，而被广泛应用于光/电解水制氢、流化催化裂化、废水废气治理以及环境抗菌，其可再生循环特点及优异性能可有效助力绿水青山的建设以及双碳目标的达成。论文综述了高岭石基催化材料在不同催化领域及其合成应用方面的最新进展，主要介绍了高岭石基光催化材料、高岭石基催化裂化材料、高岭石基过硫酸盐活化材料、高岭石基H2O2活化材料以及电催化材料的应用研究进展，同时介绍了高岭石在各种催化材料中的作用机制及应用方式。最后针对高岭石基催化材料在环境净化、能源领域的发展趋势进行了总结和展望。
Abstract:In recent years, kaolinite-based composite catalytic materials have been widely used in light/electrolytic water hydrogen production, fluidized catalytic cracking, wastewater and waste gas treatment and environmental antibacterial due to their low cost, excellent chemical stability, and high-efficiency catalytic performance. Its renewable cycle characteristics and excellent performance can contribute to the construction of clear waters and green mountains as well as help to achieve the carbon peaking and carbon neutrality goals. In this paper, the latest progress of kaolinite-based catalytic materials in different catalytic fields and their synthesis and application are reviewed. The application of kaolinite-based photocatalytic materials, kaolinite for catalytic cracking, kaolinite-based persulfate active materials, kaolinite-based H2O2 active materials and electrocatalytic materials are mainly introduced. Meanwhile, the action mechanism and application form of kaolinite in various catalytic materials are also introduced. Finally, the development of kaolinite-based catalytic materials in the field of environmental purification and energy was summarized and prospected.
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Key words:
- kaolinite /
- photocatalysis /
- catalytic cracking /
- persulfate activation /
- wastewater treatment
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表 1 高岭石基光催化材料研究进展
Table 1. Research progress of kaolinite-based photocatalytic materials
催化剂种类 污染物 光照条件 反应物质 效果 参考文献 TiO2/高岭石 环丙沙星 400 W UV ·O2-和·OH TiO2/高岭石复合材料反应常数速率可达0.045 49 min-1，是纯TiO2的6.90倍 Chunquan Li[18] C-TiO2/高岭石 环丙沙星 500 W氙灯(λ≥420 nm) ·O2-和·OH C-TiO2/高岭石复合材料反应速率常数为0.005 97 min-1，比纯TiO2提高24.88倍 Chunquan Li[24] g-C3N4/TiO2/高岭石 环丙沙星 500 W氙灯(λ≥420 nm) ·O2-(主)、·OH和h+ g-C3N4/TiO2/高岭土复合材料表观速率常数分别是纯TiO2和g-C3N4的5.35倍、6.35倍 Chunquan Li[22] 天然高岭石-Na2WO4-TiO2-生物质 氨苄西林、磺胺甲恶唑 太阳光 ·O2-和·OH 30 min内去除率可达90%以上 Moses O. Alfred[25] ZnO/高岭石纳米管 左氧氟沙星 金属卤化物灯(λ≥420 nm) ·OH 降解率100%，不含中间化合物 Mostafa R. Abukhadra[26] 聚苯胺/TiO2/偏高岭石 丁基黄药 300 W氙灯(λ≥420 nm) h+和·O2- 禁带宽度从3.10 eV降低到1.93 eV；4 h内可去除94.8%的黄药 Ye Tan[20] 高岭石-BiFeO3 罗丹明B 装有UVA lamb (λ=350 nm)的光反应器 h+(主)和·O2- 光催化活性增强 Bulent Caglar[14] BiOCl/g-C3N4/高岭石 罗丹明B和气态甲醛 500 W氙灯(λ≥420 nm) h+(主)、·O2-和·OH 去除率达95%以上 Xiongbo Dong[17] 钛掺杂钴(Ⅱ)-金属酞菁/高岭石固体 丙甲氨苄、甲氧苄啶和咖啡因 150 W TQ150-Z0灯 h+和·OH 降解率达90% Tiago H. da Silva[27] g-C3N4/高岭石 罗丹明B 500 W氙灯(λ≥420 nm) —— 光催化速率是纯g-C3N4的4.18倍 孙志明[16] 改性高岭石/g-C3N4 罗丹明B 300 W氙灯(λ≥420 nm) —— PK/GCN-3降解表观反应速率常数是纯GCN的5倍 程宏飞[28] Ag/g-C3N4/高岭石 布洛芬 500 W氙灯(λ≥400 nm) h+(主)、·O2-和·OH 辐照5 h去除率达99.9% Zhiming Sun[29] 三聚氰酸改性g-C3N4/高岭石 罗丹明B 500 W氙灯(λ≥420 nm) h+(主)、·O2-和·OH 改性g-C3N4/高岭石复合材料表观速率常数分别是g-C3N4/高岭石和纯g-C3N4的1.9倍和4.0倍 Zhiming Sun[23] Fe/g-C3N4/高岭石 盐酸四环素 500 W氙灯(λ≥420 nm) ·O2-和·OH(主) 80 min内降解率可达89% Zhou Cao[30] Fe掺杂ZnO/高岭石 大肠杆菌 160 W, 220 V LED光源 ·O2- 细菌细胞完全死亡 Ananyo Jyoti Misra[31] 掺杂Zn和Cu/高岭石 大肠杆菌 荧光灯，λ= 407 nm (λexc= 370 nm) 1O2 细菌完全失活 Chidinma G. Ugwuja[32] 黑色TiO2/ 高岭石 亚甲基蓝 300 W氙灯 —— 去除率达89.7% 程港莉[33] CeO2-CdS/巯基改性高岭石 结晶紫 350 W氙灯 ·O2-和·OH(主) 结晶紫的降解率可达95.1% 徐杰[34] 高岭石-Cu2O 对苯二酚 400 W金卤灯 —— 降解率可达97% 牛凤兴[35] BiOCl/煤系高岭石 亚甲基蓝 300 W氙灯 h+ BiOCl/CK-20%降解速率是BiOCl的2.84倍 杨权成[36] CdS/高岭石 罗丹明B 30 mV/cm2氙灯(λ≥420 nm) —— 改善CdS光催化材料的光腐蚀性能 李雪[15] 
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表 2 高岭石基催化裂化材料应用研究进展
Table 2. Research progress of kaolinite-based catalytic cracking materials
催化剂 硅铝比 反应物 剂油比 应用效果 参考文献 汽油/芳烃收率 转化率 Y型沸石(高岭石) 3.09 丁二酸和乙醇(摩尔比为1：3) — 60% 72% Dolly Gandhi[40] H-ZSM5沸石(高岭石) 41.6 甲醇 — — 90% Ahmad Asghari[42] 锌/沸石(高岭石) 11.1 催化裂化汽油 7 77.77% — Baojian Shen[43] Fe(2.5)改性H-高岭石 4~4.5 PPP真空柴油 — 12% 74.7% O. K. Kim[44] 含沸石的Fe(2.5)改性H-高岭石 — PPP真空柴油 — 22% 92.6% O. K. Kim[44] Y型分子筛/高岭石 3.1 油酸 — — 85% Aidan M. Doyle[45] 氧化镧/高岭石 2.08 重质石油残渣(燃料) 4.5 — 74.13% Abdoulay [41] NaY分子筛/高岭石 6.1 真空汽油 3 64.20% 85.40% 王文凯[39] Y沸石/高岭石 10.6 新疆真空汽油 6.5 41.95% 77.19% Li Ning[38] 原位结晶沸石/高岭石 — 废弃食用油 — — 74.50% Wang Hui[46] USY/偏高岭石 15 真空汽油 1.5 ~ 3.5 ↑ 70% Yorsra Ghrib[47] NaY/高岭石 — 掺30%新疆减压渣油混合原料油 5 63.51% 86.37% 熊晓云[48] 拟薄水铝石/高岭石 — 掺30%新疆减压渣油混合原料油 5 50.45% 80.98% 刘现玉[49] 拟薄水铝石改性高岭石 0.7 大港轻柴油 5 64.44% 81.91% 李雪礼[50] 湛江高岭石 1.19 大港轻柴油 8.04 64.83% 75.08% 李忠[51] 晶化高岭石 — 重质石油 5 71.72% 79.56% 田爱珍[52]
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表 3 高岭石基过硫酸盐活化材料研究进展
Table 3. Research progress of kaolinite-based persulfate activated materials
催化剂 污染物 活性物质 污染物浓度 催化剂浓度 PMS/PS浓度 降解率 参考文献 天然高岭石 阿特拉津 SO4·-和·OH 4.6 μmol 1.0 g/L 1.0 mmol 100% Chunquan Li[11] CuFe2O4/高岭石 双酚A SO4·- 50 mg/L 0.5 g/L 0.5 mmol 100% Xiongbo Dong[54] CuCo2O4/高岭石 非那西丁 1O2(主)、SO4·-和·OH 10 mg/L 0.1 g/L 1 mmol 100% Li Liu[55] N空位g-C3N4/高岭石 双酚A 1O2(主)、SO4·-和·OH 5 mg/L 1 g/L 1 mmol 98% 张祥伟[56] γ-FeOOH/含N空位g-C3N4/高岭石 双酚A ·O2-、1O2、SO4·-、·OH、h+和e- 10 mg/L 1.0 g/L 0.5 mmol 93% Xiangwei Zhang[57] Fe2O3/高岭石 罗丹明B SO4·-和·OH 0.1 mmol 0.4 g/L 7 mmol — Yaowen Gao[58] CoFe2O4/高岭石 亚甲基蓝 1O2和h+(主)、·O2-、SO4·-、·OH、和e- 30 mg/L 0.5 g/L 0.1 g/L 92.40% 张宇[59]
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