纳米氧化铬的制备与应用研究进展

doi:10.19964/j.issn.1006-4990.2023-0007

Abstract

Abstract:

Chromium oxide（Cr₂O₃），as one of the main products of inorganic salt industry，is widely used in chemical industry，metallurgy，machinery and other industries，and plays an important role in the national economy.A large number of studies showed that when the particle size of Cr₂O₃ was nanoscale，it would have more unique effects（such as small size effect，surface effect，etc.），which provided new ideas for the development and application of new materials.Based on the latest progress of the research and application of nano Cr₂O₃ both domestically and internationally in recent years，the preparation methods of nano Cr₂O₃ were reviewed in detail，including gas-phase method（chemical vapor deposition，microwave plasma method，laser vapor deposition），wet-chemical method（precipitation method，microemulsion method，sol-gel method，hydrothermal/solvothermal method，template method） and solid-phase method（solid-state thermal decomposition，high-energy ball milling）.In addition to traditional application scenarios such as pigments，wear and corrosion resistance coatings，gas sensors，the application progress of nano-sized Cr₂O₃ in emerging fields such as high efficiency catalysis，new energy materials was introduced.Through summarizing and comparing，the suggestion of combination of wet-chemical method andsolid-phase method to achieve large-scale preparation of highly stable nano-sized Cr₂O₃ was put forward.Moreover，it was pointed out that the transformation of energy structure in China was expected to lead to a new application scenario ofnano-sized Cr₂O₃ in key materials for energy storage systems under the background of carbon peaking and carbon neutralitygoals.

Key words: chromium oxide, nanoparticles, gas-phase method, wet-chemical method, solid-phase method, energy storage

CLC Number:

TQ136.11

XU Enhao, WU Kaipeng. Research progress of preparation and application of nano-sized chromium oxide[J]. Inorganic Chemicals Industry, 2023, 55(10): 24-34.

Figures/Tables 7

Fig.1

Fig.2

Fig.3

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Fig.5

Table 1

Table 2

Comparison and summary of preparation methods of nano-sized Cr2O3"

方法类别		典型原料	主要工艺	产品特性及应用领域	优缺点及产业化状况
气相法	化学气相沉积法^［9-12］	Cr（CO）₆/三乙酰丙酮铬	低温下对反应物进行预热，然后在气氛保护下（如N₂、H₂等）高温反应，冷却沉积。	一般呈小尺度纳米颗粒或薄膜，可应用于耐磨防腐蚀材料。	优点：粉体材料颗粒均匀、纯度高、分散良好；薄膜表面平整、结构致密、膜基结合性能优异；重复性好。缺点：对设备要求苛刻、成本高。产业化情况：很少有企业采用。
	微波等离子体法^［13-14］	Cr（CO）₆	通入保护气（如80%Ar+20%O₂）和反应气，在微波作用下形成等离子体进行反应，冷却沉积。	粒径在10 nm左右的纳米颗粒。
	激光气相沉积法^［15-17］	Cr₃C₂/金属铬	在氧气或真空条件下利用激光（KrF 248 nm、Nd：YAG 1 062 nm）瞬间激活原料，冷却沉积。	一般呈小尺度纳米颗粒或薄膜，可应用于光学器件。
湿化学法	沉淀法^［18-20］	Cr（NO₃）₃/氨水溶液	控制沉淀pH，经搅拌、陈化、干燥处理，最后在500~600 ℃空气煅烧。	一般呈小尺度纳米颗粒，可应用于催化剂和能源材料。	优点：平均粒径小、粒径分布窄；纯度高、均匀性好、成本低；设备简单，易于实现。缺点：单次产量较低。产业化情况：企业多采用沉淀法和溶胶-凝胶法制备纳米Cr₂O₃。卜微应用材料制备的高纯度纳米Cr₂O₃的粒径控制在20~ 1 000 nm；亚美纳米制备的材料平均粒径为100 nm，年产量在公斤级到吨级；乃欧纳米生产的球形颗粒粒径为50~500 nm，年产量可达到吨级以上。
	微乳液法^［22-23］	Cr（NO₃）₃/乙二胺/助剂	将水相和油相混匀，Cr（NO₃）₃加入后进行长时间搅拌，最后通过热处理或煅烧获得产物。	粒径小于100 nm的超细粉体或组装的特殊结构，可应用于催化剂。
	溶胶-凝胶法^［25-26］	Cr（NO₃）₃/NaOH	首先制备成溶胶，陈化后得到凝胶，经过低温干燥后在高温下煅烧。	粒径在13~20 nm的纳米颗粒，可用作颜料。
	水热/溶剂热法^［27-30］	CrO₃/醇类/Na₂CrO₄	在150~300 ℃反应并经干燥处理后，在高温下煅烧。	粒径在几十纳米的细微颗粒，可用作颜料、磨料及能源材料等。
	模板法^［31-33］	Cr（NO₃）₃/模板剂	200 ℃左右进行高温反应后通过酸浸或煅烧去除模板剂，得到最终产物。	具有高比表面积的特殊纳米结构，如纳米线、介孔结构等，多用于催化剂。
固相法	固相热分解法^{［35，37-38］}	Cr（NO₃）₃/（NH₄）₂Cr₂O₇	将原料按比例研磨混合或经过液相干燥处理（升华、喷雾干燥等）后在空气中进行煅烧。	大尺度纳米颗粒，经过预先液相干燥处理后可减小粒径，可用作颜料或催化剂。	优点：操作方便，设备简单；单次产量较高，能耗较低。缺点：产品纯度较低、均匀性差，可通过液相干燥工艺改善。产业化情况：随未来市场需求量增大，将液相干燥工艺与固相热分解结合的多元化制备将是工业量产的有效途径。
固相法	高能球磨法^［39-40］	Na₂Cr₂O₇/多晶Cr₂O₃	在机械活化条件下，诱发低温化学反应或直接对晶粒进行物理研磨。	多为大尺度纳米颗粒。

Table 2

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溶剂（4 mL+80 mL）	粒径/ nm（600 ℃）	比表面积/ （m²·g^-1）
水+甲醇	25	45.97
水+乙醇	28	41.05
水+丁醇	34	33.80
甲醇+水	35	32.84
乙醇+水	40	28.73
丁醇+水	45	25.54

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Research progress of preparation and application of nano-sized chromium oxide

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