电子效应精准调控的纳米金催化剂在低碳多元醇选择性氧化研究进展

doi:10.11949/0438-1157.20251015

摘要/Abstract

摘要：

低碳多元醇（来源于石油、煤或生物质）的选择性氧化是制备乙醇酸、甘油酸等高附加值化学品的关键途径。开发以分子氧为氧化剂的高效绿色催化工艺，对实现多元醇高值化转化及促进高端化工产业链绿色升级具有重要意义，其核心在于开发高性能负载型催化剂。本文系统综述了以电子效应精准调控为核心的纳米金催化剂在伯羟基氧化制羧酸、仲羟基氧化制酮及C-C键断裂制短链酸三大路径的研究进展，重点分析载体工程与双金属协同策略如何通过调变金的电子结构解决羟基选择性活化、过度氧化抑制等关键问题，探讨了电子结构与催化性能之间构效关系及反应机理，并对未来催化剂设计方向与潜在应用前景进行了展望，为绿色催化工艺的开发提供理论依据与技术参考。

关键词: 低碳多元醇, 金催化剂, 氧化, 催化剂载体, 电子效应

Abstract:

Selective oxidation of low-carbon polyols (derived from petroleum, coal or biomass) is a key approach for preparing high-value chemicals such as glycolic acid and glyceric acid. The development of efficient and green catalytic processes using molecular oxygen as the oxidant is of great significance for achieving high-value conversion of polyols and promoting the green upgrading of the high-end chemical industry chain. The core lies in the development of high-performance supported catalysts. In this paper, recent advances regarding the nano-gold catalysts with precise electronic effect modulation as the core for conversion of primary hydroxyl groups to carboxylic acids, secondary hydroxyl groups to ketones, and C-C bond cleavage to short-chain acids. The analysis highlights how support engineering and bimetallic synergy strategies tailor the electronic structure of Au to address critical challenges such as hydroxyl selectivity and over-oxidation inhibition. The structure–activity relationships between electronic properties and catalytic performance are discussed, along with associated reaction mechanisms. Future directions for catalyst design and potential applications are also prospected, offering theoretical and practical guidance for the development of sustainable catalytic processes.

Key words: low carbon polyols, nano-Au catalysts, oxidation, catalyst supports, electronic effect

中图分类号:

TQ426

赵明月, 孟凡宇, 闫昊, 冯翔, 刘熠斌, 陈小博, 杨朝合, 陈德. 电子效应精准调控的纳米金催化剂在低碳多元醇选择性氧化研究进展[J]. 化工学报, DOI: 10.11949/0438-1157.20251015.

Mingyue ZHAO, Fanyu MENG, Hao YAN, Xiang FENG, Yibin LIU, Xiaobo CHEN, Chaohe YANG, DE Chen. Progress in Research of Selective Oxidation of Low Carbon Polyols over Nano-Au Catalysts with Precise Electronic Effect Regulation[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251015.

图/表 12

图1 低碳多元醇的生产工艺和氧化产物用途

Fig. 1 Production process of low carbon polyols and uses of oxidation products

图2 多元醇伯羟基氧化、仲羟基氧化和C-C键断裂氧化的反应机理示意图[47].

Fig. 2 Proposed reaction mechanism of primary, secondary hydroxyl and C-C bond cleavage oxidation of polyols[47].

图3 多元醇伯羟基选择性氧化制羧酸相关催化剂载体工程研究：(a) 不同酸碱性质载体负载的AuPt催化剂调控甘油氧化产物[55]；(b) Au1Pt3/CeO2催化剂上甘油氧化的可能反应原理图[56]；(c) 载体的酸/碱性质与反应速率的关系[57]；(d) 5Au/HT、5Au/HAP、5Au/CuO和水滑石（HT）催化剂的CO2程序升温脱附（CO2-TPD）谱图[58]；(e) LaMnO3钙钛矿负载的Au催化剂在甘油氧化制丙醇二酸中的特殊选择性[59]；(f) CeMnO3钙钛矿及Au/CeMnO3催化剂制备过程示意图及催化甘油氧化为甘油酸性能[60].

Fig. 3 Researches on catalyst support engineering related to selective oxidation of primary hydroxyl groups of polyols to carboxylic acids: (a) Regulation of glycerol oxidation Products by AuPt catalysts loaded on supports with different acid-base properties[55]; (b) Possible reaction mechanism of glycerol oxidation on Au1Pt3/CeO2 catalysts[56]; (c) Relationship between acid/base properties of supports and reaction rates[57]; (d) CO2 temperature programmed desorption (CO2-TPD) spectra of 5Au/HT, 5Au/HAP, 5Au/CuO, and Hydrotalcite (HT) catalysts[58]; (e) Unique selectivity of Au catalysts supported on LaMnO3 perovskite for glycerol oxidation to tartronic acid[59]; (f) Schematic diagram of CeMnO3 perovskite and Au/CeMnO3 catalyst preparation process and performance in catalytic oxidation of glycerol to glyceric acid[60].

表1 多元醇伯羟基选择性氧化中不同载体类型的催化性能总结

Table 1 Summary of catalytic performance of different support types for the selective oxidation of primary hydroxyl groups in polyols

催化剂	温度/℃	时间/h	压力/bar	底物/M	碱/M	转化率/%	产物选择性/%	TOF/ h^-1	参考文献
5Au/HT	60	4	10	0.1/甘油	0.2	89.5	61.2/甘油酸	-	^[58]
AuPt/H-SiO₂	80	4	3	0.3/甘油	0	30.0	61.0/甘油酸	-	^[55]
Au-Pt/HT	60	4	2	0.3/甘油	0	64.0	69.0/甘油酸	-	^[57]
Au-Pt/MgO	60	4	2	0.3/甘油	0	52.0	48.0/甘油酸	-	^[57]
Au₁Pt₃/NC	80	2	1	0.3/甘油	0	83.7	60.5/甘油酸	0.26	^[56]
Au-Pt/Hβ	100	3	3	0.3/甘油	0	68.0	68.0/甘油酸	-	^[61]
Au-Pt/N-TiO₂	100	6	3	0.3/甘油	0	92.1	79.9/甘油酸	-	^[62]
Au/LaMnO₃	100	24	3	0.3/甘油	1.2	92.0	87.0/丙醇二酸	390	^[59]
Au/CeMnO₃	90	10	10	0.4/甘油	1.0	71.0	77.0/甘油酸	2004	^[60]
Au/Mg(OH)₂	60	6	3	0.68/1,2-丙二醇	1.36	94.4	89.4/乳酸	-	^[63]

图4 多元醇伯羟基选择性氧化相关催化剂双金属协同研究：(a) Au-Pd/C催化剂上乙二醇氧化反应原理图及速控步骤[64]；(b)溶胶固定(Sol)和溶剂化金属原子沉积(SMAD)制备AuAg/Al2O3催化剂产物分布图[29]；(c) AuAg-ZnO和AuCu-ZnO催化剂性能对比[66]；(d) Au-Cu/HT和Au/HT催化1,2-丙二醇氧化路径[70]；(e) 2.2AuPd/CeZrOx与单金属性能对比图[65]；(f) Au1Ru0.5/CeZrOx催化剂的Au/Ru比例与活性关系图[67]；(g) Pd-on-Au/C与单金属性能对比图[69]；(h) Cu@Au核/壳纳米颗粒上1,2-丙二醇转化为乳酸[68]；(i) Au/Fe-CeO2与Au/Cu-CeO2性能对比图[28].

Fig. 4 Researches on bimetallic synergy in catalysts related to selective oxidation of primary hydroxyl groups of polyols: (a) Schematic diagram of glycol oxidation reaction mechanism and rate determination step on Au-Pd/C catalyst[64]; (b) Oxidation product distribution over AuAg/Al2O3 catalysts prepared by sol immobilization (Sol) and solvated metal atom deposition (SMAD) methods[29]; (c) Performance comparison between AuAg-ZnO and AuCu-ZnO catalysts[66]; (d) Proposed reaction pathways of 1,2-propanediol over Au-Cu/HT and Au/HT catalysts[70]; (e) Performance comparison between 2.2AuPd/CeZrOx catalyst and its monometallic counterparts[65]; (f) Relationship between Au/Ru ratio of Au1Ru0.5/CeZrOx catalyst and activity[67]; (g) Performance comparison between Pd-on-Au/C and monometallic catalysts[69]; (h) Conversion of 1,2-propanediol to lactic acid on Cu@Au core/shell nanoparticles[68]; (i) Reaction performance comparison between Au/Fe-CeO2 and Au/Cu-CeO2 catalysts[28].

表2 多元醇伯羟基选择性氧化中不同双金属组合的催化性能协同效应总结

Table 2 Summary of catalytic performance and synergistic effects of different bimetallic combinations for selective oxidation of primary hydroxyl groups in polyols

催化剂	温度/℃	时间/h	压力/bar	底物/M	碱/M	转化率/%	产物选择性/%	TOF/h^-1	参考文献
Au-Pd/C	60	5	10	0.1/乙二醇	1	90.0	100/乙醇酸	600	^[64]
0.1Au/Fe-CeO₂	90	4	5	0.3/甘油	0.5	68.0	63.0/甘油酸	0.22	^[28]
AuAg/Al₂O₃-SMAD	50	6	3	0.3/甘油	1.2	66.7	52.0/甘油酸	0.28	^[29]
AuAg/Al₂O₃-Sol	50	2	3	0.3/甘油	1.2	83.3	44.0/甘油酸	0.83	^[29]
2.2AuPd/CeZrO_x	60	3	3	0.3/甘油	0.6	93.6	59.8/甘油酸	0.09	^[65]
Pd-on-Au/C	60	3	-	0.1/甘油	0.4	99.4	42.3/甘油酸	1.7	^[69]
AuCu-ZnO	60	5	6	1.0/甘油	2.0	10.0	77.0/甘油酸	-	^[66]
AuAg-ZnO	60	5	6	1.0/甘油	2.0	95.0	59.0/甘油酸	-	^[66]
AuPd/C	60	5	10	0.3/甘油	0.6	50.0	84.0/甘油酸	4.6	^[71]
Au₁Ru_0.5/CeZrO_x-500	50	2	3	0.3/甘油	0.3	98.0	78.0/甘油酸	0.66	^[67]
Cu_0.985Au_0.015	100	4	10	0.28/1,2-丙二醇	0.56	89.3	76.1/乳酸	917	^[68]
0.5Cu-Au/HT	80	6	10	1.3/1,2-丙二醇	2.6	98.5	88.5/乳酸	-	^[70]
AuPt/H-丝光沸石	100	2	3	0.3/甘油	0	70.0	83.0/甘油酸	-	^[72]
Au₁-Pt₃/MgO	23	24	3	0.3/甘油	0	43.0	85.0/甘油酸	-	^[73]
AuPt/H-SiO₂	80	4	3	0.3/甘油	0	30.0	61.0/甘油酸	-	^[55]
Au-Pt/N-TiO₂	100	6	3	0.3/甘油	0	92.1	79.9/甘油酸	-	^[62]
Au₁Pt₃/NC	80	2	1	0.3/甘油	0	83.7	60.5/甘油酸	-	^[56]
Au-Pt/HT	60	4	2	0.3/甘油	0	64.0	69.0/甘油酸	-	^[57]
Au-Pt/Hβ	100	3	3	0.3/甘油	0	68.0	68.0/甘油酸	-	^[61]

图5 多元醇仲羟基选择性氧化催化剂载体工程研究：(a) Au/MgO-Al2O3载体酸度提高和碱度降低来提高二羟基丙酮选择性[77]；(b)O2在Au/ZnO(001)上吸附模型[26]；(c) Au/CuZnOx@bio-ZSM-5催化剂制备图及甘油催化机理[79]；(d)在甘油选择性氧化生成二羟基丙酮过程中，羟基空位与ZnII-O-Au3+位点的额外协同作用[81]；(e) Au/ZnO-花形催化剂合成图和甘油选择性氧化机理[78]；(f)不同形貌Au/ZnO-Z催化剂制备图和仲羟基氧化机理[80]；(g)由丁香叶提取物S3制备的Au/CuO用于甘油氧化的机理图[76]；(h) Au/ZnO-球、棒、盘上甘油氧化制二羟基丙酮性能[82].

Fig. 5 Researches on catalyst support engineering related to selective oxidation of secondary hydroxyl groups of polyols: (a) Enhanced acidity and reduced basicity of Au/MgO-Al2O3 support to improve dihydroxyacetone selectivity[77]; (b) Adsorption model of O2 on Au/ZnO(001)[26]; (c) Preparation of Au/CuZnOx@bio-ZSM-5 catalyst and oxidation mechanism[79]; (d) Additional synergistic effect between hydroxyl vacancies and ZnII-O-Au3+sites during oxidation of glycerol to dihydroxyacetone[81]; (e) Synthesis of Au/ZnO-flower catalyst and oxidation mechanism of glycerol[78]; (f) Preparation for Au/ZnO-Z nanocatalysts with different morphologies and mechanism of secondary alcohol oxidation[80]; (g) Reaction mechanism diagram of Au/CuO prepared from S3 clove leaf extract for oxidation of glycerol[76]; (h) Performance of glycerol selective oxidation to dihydroxyacetone over Au/ZnO-sphere, rod, and disk catalysts [82].

表3 多元醇仲羟基选择性氧化中不同载体类型的催化性能总结

Table 3 Summary of catalytic performance of different support types for selective oxidation of secondary hydroxyl groups in polyols

催化剂	温度/℃	时间/h	压力/bar	底物/M	转化率/%	产物选择性/%	TOF /h^-1	参考文献
Au/Al₂O₃	80	3	10	0.1/甘油	11.9	81.7/DHA	43.0	^[77]
Au/MgO-Al₂O₃(0.1)	80	0.5	10	0.1/甘油	16.4	74.1/DHA	358.0	^[77]
Au/CuMgAl-HTs	60	4	3	0.3/甘油	42.0	64.0/DHA	292.0	^[83]
Au/CuO	60	4	5	0.1/甘油	36.6	81.6/DHA	92.0	^[84]
Au/Cu-NPC-15 %-H	60	4	5	0.1/甘油	65.6	92.1/DHA	177.7	^[84]
Au/Cu_0.95Zr_0.05O_1.05	50	4	2	0.1/甘油	72.8	96.2/DHA	32.1	^[85]
Au/CuO-SnO₂-3:1	80	2	10	0.1/甘油	100.0	94.7/DHA	874.8	^[86]
0.98Au/Zn_2.15Ga_1.0-LDHs	60	4	5	0.1/甘油	73.1	63.6/DHA	267.3	^[81]
0.98Au/Mg_2.10Al_1.0-LDHs	60	4	5	0.1/甘油	71.2	57.0/DHA	245.3	^[81]
S3-Au/CuO	100	2	10	0.1/甘油	86.6	82.0/DHA	430.3	^[76]
Au/ZnO-NF	100	1	10	0.1/甘油	92.9	69.5/DHA	-	^[78]
Au/CuZnO_x@bio-ZSM-5	80	2	10	0.1/甘油	93.0	86.3/DHA	-	^[79]
Au/CuZnO_x	80	2	10	0.1/甘油	88.0	83.0/DHA	-	^[79]
Au/ZnO-RF	100	1	1	0.1/甘油	91.1	76.2/DHA	-	^[80]
Au/ZnO-D	60	4	10	0.1/甘油	58.0	68.5/DHA	521	^[82]
Au/CuAlO-3	80	2	10	0.1/甘油	76.7	97.3/DHA	80.4	^[87]

图6 多元醇仲羟基选择性氧化相关催化剂双金属协同研究：(a)铋改性AuPt/AC催化甘油氧化生成二羟基丙酮[88]；(b)不同比例AuCu/ZnO催化剂甘油氧化性能[18]；(c) AuPd合金、Au@Pd核壳、Au-Pd Janus颗粒和不同构型Au+Pd混合催化剂选择性氧化甘油制DHA性能与机理[89]；(d) AuPd/ZnO-CuO界面上甘油仲羟基氧化性能与机理[90].

Fig. 6 Researches on bimetallic synergy in catalysts related to selective oxidation of secondary hydroxyl groups of polyols: (a) Bismuth-modified AuPt/AC catalyst for glycerol oxidation to dihydroxyacetone[88]; (b) Performance of glycerol oxidation over AuCu/ZnO with different ratios[18]; (c) Catalytic performance and mechanism for glycerol oxidation to DHA over supported AuPd alloy, Au@Pd core-shell, Au-Pd Janus particles, and differently configured Au+Pd mixed catalysts[89]; (d) Performance and mechanism of glycerol secondary hydroxyl oxidation at AuPd/ZnO-CuO interface[90].

表4 多元醇仲羟基选择性氧化中不同双金属组合的催化性能协同效应总结

Table 4 Summary of catalytic performance and synergistic effects of different bimetallic combinations for the selective oxidation of secondary hydroxyl groups in polyols

催化剂	温度/℃	时间/h	压力/bar	底物/M	转化率/%	产物选择性/%	TOF /h^-1	参考文献
AuCu/ZnO	60	5	10	0.105/甘油	90.6	83.4/DHA	402.5	^[18]
0.1Bi-AuPt/AC	80	2	3	0.3/甘油	80.0	63.0/DHA	585.0	^[88]
AuPd/ZnO	110	12	10	0.1/甘油	87.0	70.1/DHA	754.8	^[89]
AuPd/ZnO-CuO	80	2	1	0.05/甘油	75.0	86.0/DHA	687.1	^[90]
Au_0.5-Pt_0.5/MgO	40	4	3	0.6/1,2-丙二醇	40.0	65.0/α-羟基丙酮	400.0	^[91]
Au_0.5-Pt_0.5/C	100	24	10	0.6/1,2-丙二醇	67.0	52.0/α-羟基丙酮	112.0	^[91]
Au_0.5-Pt_0.5/C	100	24	3	0.6/1,2-丁二醇	75.0	42.0/1-羟基-2-丁酮	-	^[92]
Au_0.5-Pt_0.5/C	100	24	3	0.6/1,3-丁二醇	67.0	39.0/4-羟基-2-丁酮	-	^[92]
Au_0.5-Pt_0.5/C	100	24	3	0.6/2,3-丁二醇	62.0	84.0/3-羟基-2-丁酮	-	^[92]

图7 多元醇C-C键断裂相关催化剂研究：(a) 可磁分离Au-Pt@TiO2纳米复合材料的绿色合成及用于甘油选择性氧化和回收测试[93]；(b) 贵金属M (M = Au, Pd或Pt)促进银基甘油液相氧化催化剂[94]；(c) 经高温焙烧处理后的水滑石负载催化活性金纳米颗粒无碱选择性氧化甘油成乙醇酸[98].

Fig. 7 Researches on catalysts for C-C bond cleavage of polyols: (a) Green synthesis of magnetically separable Au-Pt@TiO2 nanocomposites for selective oxidation of glycerol and recycling performance[93]; (b) Noble metal M (M = Au, Pd or Pt) promoted silver-based catalysts for liquid-phase oxidation of glycerol[94]; (c) Selective oxidation of glycerol to glycolic acid over hydrotalcite-supported gold nanoparticles activated by high-temperature calcination[98].

表5 多元醇C-C键断裂相关催化剂性能总结

Table 5 Summary of catalytic performance of catalysts for C-C bond cleavage of polyols

催化剂	温度/℃	时间/h	压力/bar	底物/M	碱/M	转化率/%	产物选择性/%	TOF /h^-1	参考文献
Au-Pt/C	50	0.5	3	0.3/甘油	1.2	90.0	54.2/乙醇酸	1258	^[96]
Au-Pt/C-NaBH₄	50	0.5	3	0.3/甘油	1.2	75.8	59.9/乙醇酸	758	^[97]
Au-Pt/C-H₂	50	0.5	3	0.3/甘油	1.2	98.3	46.9/乙醇酸	878	^[97]
Fe₃O₄@TiO₂-Au	60	4	4	0.3/甘油	1.2	16.5	68.5/乙醇酸	-	^[93]
Ag-Au/CeO₂	60	5	4	0.3/甘油	1.2	43.8	46.2/乙醇酸	115	^[94]
Au/HT	20	72	1	0.1/甘油	0	97.3	73.8/乙醇酸	-	^[98]
Au-Pt/C	50	0.5	3	0.3/甘油	1.2	90.0	54.2/乙醇酸	1258	^[96]

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