原子级分散催化剂的通用合成及其在热催化中的应用

doi:10.11949/0438-1157.20240753

摘要/Abstract

摘要：

原子级分散催化剂（ADCs）结合了均相催化剂和非均相催化剂的优点，具有高比表面积、高原子利用率、结构明确等特点，使其表现出优异催化性能的同时又易于分离回收，故在工业催化领域得到了广泛关注，被认为是最有潜力的催化剂。对原子级分散催化剂的通用合成方法进行了分类总结，此外，调研了原子级分散催化剂在选择性加氢、羰基化、脱氢化学反应的催化应用。最后，总结了ADCs所面临的机遇和挑战，为其后续的发展与应用提供借鉴。

关键词: 原子级分散, 催化剂, 合成, 化学反应

Abstract:

Atomically dispersed catalysts (ADCs) combine the advantages of both homogeneous and heterogeneous catalysts, with high specific surface area, high atomic utilization, and clear structure. They exhibit excellent catalytic performance while being easy to separate and recover. Therefore, they have received widespread attention in the field of industrial catalysis and are considered the most promising catalysts. This review categorizes and summarizes the general synthesis methods of atomic level dispersed catalysts. In addition, it investigates the catalytic applications of atomic level dispersed catalysts in selective hydrogenation, carbonylation, dehydrogenation and other chemical reactions. Finally, the opportunities and challenges faced by the current application of ADCs were summarized, providing reference for its future development and application.

Key words: atomically dispersed, catalyst, synthesis, chemical reaction

中图分类号:

TQ 426

马越, 曹东, 程道建. 原子级分散催化剂的通用合成及其在热催化中的应用[J]. 化工学报, 2024, 75(11): 4048-4064.

Yue MA, Dong CAO, Daojian CHENG. General synthesis and application of atomically dispersed catalysts[J]. CIESC Journal, 2024, 75(11): 4048-4064.

图/表 12

图1 原子级分散催化剂的通用合成和热催化应用的说明

Fig.1 Illustration of general synthesis and thermocatalytic applications of atomically dispersed catalysts

图2 各种金属单原子催化剂的HAADF-STEM图片（比例尺：5 nm）[26]

Fig.2 HAADF-STEM images for various metal single-atom catalysts （scale bar: 5 nm）[26]

图3 Co-N5/ HNPCSs合成示意图与表征 [30]

Fig.3 Schematic illustration and SEM, TEM, HAADF-STEM, AC-STEM of Co-N5/HNPCSs [30]

图4 使用二元（AB）前体系统的ALD技术的示意图：(a) 具有所有活性位点的底物；(b) 暴露于第一前体蒸气；(c) 清除残留的前体分子和副产物；(d) 暴露于第二前体蒸气（逆反应物）；(e) 清除残留的第二前体蒸气和副产物；(f)由几个ALD循环产生的膜 [34]

Fig.4 Schematic representation of the ALD technique using a binary (AB) precursor system: (a) Substrate with all active sites available; (b)Exposure to the first precursor vapor; (c) Purging of residual precursor molecules and byproducts; (d) Exposure to the second precursor vapor (counter-reactant); (e) Purging of the residuals of the second precursor vapor and byproducts; (f) Film resulting from several ALD cycles [34]

图5 纳米片状石墨烯上Pt的原子层沉积机理示意图 [35]

Fig.5 Schematic illustrations of Pt ALD mechanism on graphene nanosheets [35]

图6 Ru SAs/N-C、Ru Sas/N-C的TEM和HAADF-STEM图像[42]

Fig.6 TEM and magnified HAADF-STEM images of Ru SAs/N-C and Ru NCs/C [42]

图 7 W-SAC的形成过程说明 [43]

Fig.7 Illustration of the formation of W-SAC [43]

图8 合成SACs的电化学沉积方法的通用性[50]

Fig.8 Generality of electrochemical deposition for synthesizing SACs[50]

表1 原子级分散催化剂在选择性加氢应用的性能总结

Table 1 Summary of the performance of atomically dispersed catalysts in selective hydrogenation

催化剂	反应体系	反应温度/℃	反应压力/MPa	转化率/%	选择性/%	TOF/h^-1	正异比
Pd-SAs^[69]	乙炔选择性加氢	120	—	96.0	93.4	—	—
ISA-Pd/MPNC^[70]	乙炔选择性加氢	110	—	83	81	—	—
0.01%-Pd₁/ZnO^[71]	乙炔选择性加氢	80	—	100	80	—	—
0.2Pt/m-Al₂O₃-H₂^[72]	苯乙酮加氢	50	—	69.3	98.7	—	—
0.2Pt/m-Al₂O₃-H₂^[72]	1,3-丁二烯加氢	100	1.0	92.6	100	432	—
0.2Pt/m-Al₂O₃-H₂^[72]	硝基苯选择性加氢	25	1.0	99.8	100	—	—
Fe₁/C-N^[73]	硝基苯选择性加氢	60	—	99	99	748	—
Pt₁@MIL^[74]	CO₂选择性加氢	150	—	—	90.3	117	—
Pt _n @MIL^[74]	CO₂选择性加氢	150	—	—	13.3	20.9	—

图9 烯烃羰基化反应的反应途径及相应副反应 [75]

Fig.9 Reaction pathway of olefin hydroformylation and corresponding side reactions [75]

表2 原子级分散催化剂在羰基化应用的性能总结

Table 2 Summary of the performance of atomically dispersed catalysts in hydroformylation

催化剂	反应体系	反应温度/℃	反应压力/MPa	转化率/%	选择性/%	TOF/h^-1	正异比
Rh/2.9ReO _x -Al₂O₃^[78]	乙烯羰基化反应	150	0.1	—	33.3	10.8	—
Rh-CPOL-1bp＆10P ^[79]	丙烯羰基化反应	70	0.5	—	93	1209	24.2
Rh@POP-PTBA-HA-50^[80]	丙烯羰基化反应	120	6	83	—	396	5.67
Rh@POP-PTBA-HA-50^[80]	1-己烯羰基化反应	120	6	91	—	434	10.1
Rh@POP-PTBA-HA-50^[80]	1-辛烯羰基化反应	120	6	88	99	801	11.5

表3 原子级分散催化剂在脱氢应用的性能总结

Table 3 Summary of the performance of atomically dispersed catalysts in dehydrogenation

催化剂	反应体系	反应温度/℃	反应压力/MPa	转化率/%	选择性/%	TOF/h^-1	正异比
Pd/N-MSC-30 ^[85]	甲酸脱氢	60	—	—	—	8414	—
Co_1.0-N-C(800)^[86]	甲酸脱氢	—	—	—	—	47.1	—
R-PtNi/NiO@SiO₂^[87]	氨硼烷脱氢	—	—	—	—	74418	—
Pt₁/Co₃O₄-c^[88]	氨硼烷脱氢	—	—	—	—	362100	—
Ni₁/A-TiO₂^[89]	丙烷脱氢	580	0.1	—	90	115	—
Pt/Cu SAA^[90]	丙烷脱氢	520	0.1	—	90	622.2	—

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