揭示Au/LaMnCuO3催化剂在乙醇选择氧化反应中的Au-Mn-Cu协同作用

doi:10.1016/S1872-2067(25)64686-9

催化学报 ›› 2025, Vol. 75: 34-48.DOI: 10.1016/S1872-2067(25)64686-9

揭示Au/LaMnCuO₃催化剂在乙醇选择氧化反应中的Au-Mn-Cu协同作用

王杰^a^,¹, 陈露露^b^,¹, 岳丽君^a, Ivo A. W. Filot^b, Emiel J. M. Hensen^b^,^*(), 刘鹏^a^,^*()

^a华中科技大学化学与化工学院, 能量转换与存储材料化学教育部重点实验室, 湖北武汉 430074, 中国
^b埃因霍温理工大学化学工程与化学系, 无机材料与催化实验室, 埃因霍温, 荷兰

收稿日期:2025-02-19 接受日期:2025-03-05 出版日期:2025-08-18 发布日期:2025-07-22
通讯作者: *电子信箱: pengliu@hust.edu.cn (刘鹏), e.j.m.hensen@tue.nl (E. Hensen).
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(21972050);华中科技大学学术前沿青年团队项目(2018QYTD03)

Unveiling the Au-Mn-Cu synergy in Au/LaMnCuO₃ catalysts for selective ethanol oxidation

Wang Jie^a^,¹, Chen Lulu^b^,¹, Yue Lijun^a, A. W. Filot Ivo^b, J. M. Hensen Emiel^b^,^*(), Liu Peng^a^,^*()

^aKey Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China
^bLaboratory of Inorganic Materials and Catalysis, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, 5600 MB Eindhoven, the Netherlands

Received:2025-02-19 Accepted:2025-03-05 Online:2025-08-18 Published:2025-07-22
Contact: *E-mail: pengliu@hust.edu.cn (P. Liu), e.j.m.hensen@tue.nl (E. Hensen).
About author:¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21972050);Program for Academic Frontier Youth Team in Huazhong University of Science and Technology(2018QYTD03)

摘要/Abstract

摘要：

生物乙醇高值化利用的一个重要方向是以乙醇选择氧化制乙醛来替代传统乙烯瓦克氧化工艺. 乙醇氧化脱氢制乙醛是放热反应, 在较低温度下反应可有效抑制催化剂烧结或积碳失活, 但选择性调控仍具挑战性. 在已报道的众多催化剂中, 负载型纳米Au表现出较高的乙醛选择性, 其中金属-载体之间的Au-Cu协同催化可获得90%以上的乙醛产率, 但是目前最有效的Au/MgCuCr₂O₄催化剂仍面临使用有害金属、低温(< 250 ^oC)催化效率不高的局限. 合理设计具有特定结构和功能的催化新材料是提升催化剂性能的关键. 鉴于LaMnO₃钙钛矿具有良好的催化氧化性能、热稳定性和环境友好性, 并且其氧化还原性质可通过掺杂过渡金属来调变.

本文尝试将Cu掺杂的LaMnO₃与纳米Au结合, 设计制备出不同Cu和Au含量的Au/LaMnCuO₃催化剂并用于乙醇氧化脱氢制乙醛. 实验研究发现, 在具有不同Cu含量(Cu/Mn = 0/1, 1/3, 1/1, 1/0)及相同Au负载量(1 wt%)的催化剂中, 少量Cu掺杂的Au/LaMn_0.75Cu_0.25O₃对乙醇氧化脱氢表现出很强的Au-Mn-Cu协同作用, 并具有最高的催化效率, 在225 ^oC获得97%的乙醇转化率和98%的乙醛选择性, 并维持至少80 h性能不降低. 该催化剂的低温(100-225 ^oC)催化性能明显高于其它参照催化剂, 不仅具有最低的表观活化能(40.1 kJ mol^-1), 还能通过优化Au负载量来提高乙醛时空收率至1385 g g_Au^-1 h^-1. X射线光电子能谱结果表明, Au/LaMn_0.75Cu_0.25O₃表面的Cu⁺和Mn²⁺物种在反应后均明显增加, 并且没有Cu⁰生成; 而Cu含量更高的Au/LaMn_0.5Cu_0.5O₃和Au/La₂CuO₄催化剂在反应后生成了大量Cu⁰; 程序升温还原结果表明LaMn_0.75Cu_0.25O₃的Mn和Cu物种具有较低的可还原性和较高的稳定性. 结合反应和表征结果, 可将Au/LaMn_0.75Cu_0.25O₃的最佳催化性能归因于其纳米Au颗粒附近存在数量较多并且稳定的Cu⁺-O-Mn²⁺位点, 从而有利于协同活化O₂和乙醇分子.

密度泛函理论研究表明, 模型催化剂Au/LaMnO₃, Au/LaMnCuO₃和Au/La₂CuO₄上进行的乙醇氧化脱氢反应均遵循MvK机理, 前半催化循环(S_I)是涉及乙醇与晶格氧反应的前6步基元反应, 而后半催化循环(S_II)是吸附氧与另一乙醇分子反应的后7步基元反应. 乙醇吸附能、O₂吸附能和氧空位(O_V)形成能均是按照Au/LaMnO₃ > Au/LaMnCuO₃ > Au/La₂CuO₄的顺序依次降低. Au/LaMnO₃和Au/LaMnCuO₃上反应的速控步骤是S_II中H₂O的形成, 活化能分别为1.67和0.72 eV; 而Au/La₂CuO₄上反应的速控步骤是S_I中吸附乙氧基的α-C-H键断裂, 活化能为0.91 eV. 微观动力学模拟结果与实验趋势一致, 反应速率顺序为: Au/LaMnO₃ < Au/La₂CuO₄ < Au/LaMnCuO₃. 预测330 °C以下Au/LaMnO₃和Au/La₂CuO₄的速控步骤分别只是S_II中H₂O的形成和S_I中α-C-H键的断裂, 而Au/LaMnCuO₃在180 °C以上除了S_II中形成H₂O是主要的速控步骤外, S_I中的醇O-H和α-C-H键的断裂及S_II中的醇O-H断裂也开始影响反应速率. 晶体轨道哈密顿布居分析表明, Au/LaMnCuO₃中Cu-O键弱于Au/LaMnO₃中Mn-O键, Cu取代Mn后减弱了与表面O原子的相互作用, 从而降低了形成H₂O的活化能. 基于Mn和Cu的电子结构分析进一步证明, Au/LaMnCuO₃表面相邻的Cu²⁺-O-Mn³⁺位点在移除一个晶格氧后会形成Cu⁺-O_V-Mn²⁺位点, O₂在该位点吸附并活化为O₂^2-, 但Cu掺入过量将会形成不稳定的Cu²⁺-O-Cu²⁺位点, 这与实验观察到的高Cu含量催化剂易形成Cu⁰相一致. 因此, 强Au-Mn-Cu协同作用的本质是催化剂中纳米Au附近大量存在的是Cu²⁺-O-Mn³⁺/Cu⁺-O_V-Mn²⁺而不是Cu²⁺-O-Cu²⁺位点, 这对Cu掺入量有较高的要求. 本文对新型多金属中心协同催化剂的设计和理解乙醇氧化脱氢协同催化机制提供了新思路.

关键词: 乙醇氧化, 乙醛, 金催化剂, LaMnO₃钙钛矿, 铜掺杂

Abstract:

Gold nanoparticles (AuNPs) supported on the Cu-doped LaMnO₃ perovskites exhibit strong Au-Mn-Cu synergy in the aerobic oxidation of gaseous ethanol to acetaldehyde (AC). The Au/LaMnCuO₃ catalysts achieve AC yields exceeding 90% and a space-time yield of 715 g_AC g_Au^-1 h^-1 at 225 °C, outperforming reported catalysts. The outstanding performance is attributed to adjacent Cu⁺ and Mn²⁺ ions in the perovskite surface, which, together with nearby AuNPs, contribute to the high activity and stability. The best-performing catalyst contains a Cu/Mn ratio of 1/3 in the perovskite. Doping too much Cu into the perovskite leads to metallic Cu, suppressing catalyst performance. Density functional theory (reaction energetics, electronic structure analysis) and microkinetics simulations aided in understanding the synergy between Cu and Mn and the role of AuNPs. The reaction involves two H abstraction steps: (1) O-H cleavage of adsorbed ethanol by the basic perovskite lattice oxygen atom and (2) α-C-H cleavage by AuNPs, yielding AC and adsorbed water. Molecular O₂ adsorbs in the oxygen vacancy (O_V) formed by water removal, generating a peroxide anion (O₂^2-) as the activated oxygen species. In the second part of the catalytic cycle, the basic O₂^2- species abstracts the H atom from another ethanol molecule, followed by α-C-H cleavage by AuNPs, AC production, and water removal. Water formation in the second part of the catalytic cycle is the rate-controlling step for Au/LaMnO₃ and Au/LaMnCuO₃ models. Moderate Cu doping enhances the essential Cu⁺-O_V-Mn²⁺ sites and lowers the barrier for water formation due to the weaker Cu-O bond than the Mn-O bond. In contrast, excessive Cu doping creates unstable Cu²⁺-O-Cu²⁺ sites and shifts the barrier to the α-C-H cleavage.

Key words: Ethanol oxidation, Acetaldehyde, Gold catalyst, LaMnO₃ perovskite, Copper doping

王杰, 陈露露, 岳丽君, Ivo A. W. Filot, Emiel J. M. Hensen, 刘鹏. 揭示Au/LaMnCuO₃催化剂在乙醇选择氧化反应中的Au-Mn-Cu协同作用[J]. 催化学报, 2025, 75: 34-48.

Wang Jie, Chen Lulu, Yue Lijun, A. W. Filot Ivo, J. M. Hensen Emiel, Liu Peng. Unveiling the Au-Mn-Cu synergy in Au/LaMnCuO₃ catalysts for selective ethanol oxidation[J]. Chinese Journal of Catalysis, 2025, 75: 34-48.

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图/表 14

Table 1 Textural, structural and chemical properties of perovskite-supported Au catalysts.

Catalyst	S_BET (m² g^-1)	d_Au ^a (nm)	[Au] ^b (wt%)	XPS peak area ratio (%)			H₂ uptake ^c (mmol g^-1)	Acid amount ^d (μmol g^-1)	Base amount ^e (μmol g^-1)
Catalyst	S_BET (m² g^-1)	d_Au ^a (nm)	[Au] ^b (wt%)	(O_A+O_V)/O_L	Mn³⁺/Mn	Cu⁺/Cu	H₂ uptake ^c (mmol g^-1)	Acid amount ^d (μmol g^-1)	Base amount ^e (μmol g^-1)
Au/LaMnO₃	5.3	3.0	0.96	48.4	69.6	—	3.3 (3.3)	80.7	150.8
Au/LaMn_0.75Cu_0.25O₃	2.2	3.5	0.95	60.3	63.6	10.0	3.6 (3.5)	15.3	50.7
Au/LaMn_0.5Cu_0.5O₃	1.0	4.0	0.99	80.0	58.1	9.3	3.8 (3.9)	13.6	39.1
Au/La₂CuO₄	0.5	6.5	0.98	481.3	—	0	4.5 (4.6)	12.1	31.5

Fig. 1. SEM images (A), TEM images (B), AuNP size distributions (C), and XRD patterns (D) of (a) Au/LaMnO3, (b) Au/LaMn0.75Cu0.25O3, (c) Au/LaMn0.5Cu0.5O3, and (d) Au/La2CuO4.

Fig. 2. XPS spectra of the Au/LaMnO3 (a), Au/LaMn0.75Cu0.25O3 (b) and Au/La2CuO4 (c) catalysts. (A) La 3d; (B) Au 4f, Mn 3s; (C) O 1s; (D) Mn 2p; (E) Cu 2p; (F) Auger Cu LMM.

Fig. 3. H2-TPR profiles of various perovskite-supported Au catalysts and the corresponding perovskite supports (the dashed line).

Table 2 Catalytic performance of supported Au catalysts in the aerobic ethanol oxidation.

Catalyst	Conv. ^a (%)	Selec. ^a (%)	STY ^b (h^-1)	TOF ^c (h^-1)	E_a ^d (kJ mol^-1)
Au/LaMnO₃	99	1	4	162	76.1
Au/LaMn_0.75Cu_0.25O₃	97	98	378	1580	40.1
Au/LaMn_0.5Cu_0.5O₃	67	97	248	368	47.7
Au/La₂CuO₄	50	99	191	517	51.9
Au/MgCuCr₂O₄	82	99	329	1039	45.0
Au/La₂O₃	28	81	93	205	83.2
Au/β-MnO₂	99	1	4	421	56.5
Au/CuO	48	96	181	406	78.7

Fig. 4. Ethanol conversion (A), AC selectivity (B) and yield (C) as a function of the reaction temperature, and (D) Arrhenius plots for ethanol oxidation, and (E) a stability test for Au/LaMn0.75Cu0.25O3. Reaction conditions: catalyst 0.06 g, ethanol 5.0 μL min-1, ethanol/O2/N2 = 1/3/36, GHSV = 100000 mL gcat-1 h-1).

Fig. 5. XPS spectra of fresh (a) and used (b) Au/LaMn0.75Cu0.25O3 catalysts. (A) La 3d; (B) Au 4f and Mn 3s; (C) O 1s; (D) Mn 2p; (E) Cu 2p; (F) Auger Cu LMM.

Fig. 6. Effect of Au loading of the Au/LaMn0.75Cu0.25O3 catalyst (I: 0.95 wt% Au, II: 0.47 wt% Au, III: 0.17 wt% Au) on the activity and selectivity (A) and STY value (B) for the ethanol oxidation. Reaction conditions: catalyst 0.06 g, ethanol 5.0 μL min-1, ethanol/O2/N2 = 1/3/36, GHSV = 100000 mL gcat-1 h-1).

Fig. 7. Surface models of optimized Au8 clusters on the (001) surfaces of LaMnO3 (A), LaMnCuO3 (B) and La2MnO4 (C). color coding: blue for La, purple for Mn, red for O, gold for Au, and olive for Cu.

Fig. 8. The Mars-van Krevelen mechanism of selective oxidation of ethanol (color codes: dark gray round rectangular: supports; gold: Au; black: C; red: O in ethanol; white: H; pink circle with black border: lattice O; pink circle with white border: absorbed O). The activation energy of each elementary step is indicated, with black, red and green representing values for Au/LaMnO3, Au/LaMnCuO3, and Au/La2CuO4, respectively. Values to the left and right of the vertical bars denote the activation energies in eV of the forward and backward reactions, respectively.

Table 3 DFT-computed activation energies of elementary reaction steps in selective ethanol oxidation on the Au/LaMnO3, Au/LaMnCuO3 and Au/La2CuO4 surface models (all energies in eV and corrected for the zero-point energy).

Reaction step		Au/LaMnO₃		Au/LaMnCuO₃		Au/La₂CuO₄
Reaction step		Forward	Backward	Forward	Backward	Forward	Backward
R1	CH₃CH₂OH + * ⇋ CH₃CH₂OH*	0	0.79	0	0.94	0	0.72
R2	CH₃CH₂OH* ⇋ CH₃CH₂OOHO_v*	0.06	0.04	0.28	0.30	0.33	0.24
R3	CH₃CH₂OOHO_v ⇋ CH₃CHOHOHO_v	0.67	0.50	0.39	0.32	0.91	0.82
R4	CH₃CHO* + HOHO_v* ⇋ CH₃CHOHOHO_v	0	0.93	0	0.97	0	0.27
R5	HOHO_v ⇋ H₂OO_v	0.97	1.06	0.70	0.60	0.79	0.91
R6	H₂O + O_v* ⇋ H₂OO_v	0	0.86	0	0.17	0	0.57
R7	O₂ + O_v* ⇋ O₂O_v	0	1.85	0	1.27	0	0.95
R8	CH₃CH₂OH + O₂O_v ⇋ CH₃CH₂OHO₂O_v	0	1.18	0	0.86	0	0.76
R9	CH₃CH₂OHO₂O_v* ⇋ CH₃CH₂OOH	0.06	2.00	0.38	1.21	0.73	0.98
R10	CH₃CH₂OOH ⇋ CH₃CHOHOH*	1.28	0.24	0.68	1.35	0.83	1.90
R11	CH₃CHO* + HOH ⇋ CH₃CHOHOH*	0	0.48	0	0.79	0	0.84
R12	HOH ⇋ H₂O*	1.67	2.81	0.72	1.59	0.57	1.91
R13	H₂O + * ⇋ H₂O*	0	0.57	0	0.54	0	0.43

Fig. 9. Microkinetics simulations of the ethanol conversion rate (conditions: ethanol/O2/N2 = 1/3/36, P = 1 atm) (A) and the degree of rate control as a function of temperature on Au/LaMnO3 (B), Au/LaMnCuO3 (C) and Au/La2CuO4 (D).

Fig. 10. Steady-state surface coverages, reaction orders and apparent activation energy as a function of temperature for Au/LaMnO3 (A,D), Au/LaMnCuO3 (B,E), and Au/La2CuO4 (C,F).

Table 4 iCOHP and ?iCOHP values for the key interactions in H2O formation reaction over Au/LaMnO3 and Au/LaMnCuO3 models.

Interaction	Au/LaMnO₃			Au/LaMnCuO₃
Interaction	iCOHP_IS	iCOHP_TS	∆iCOHP	iCOHP_IS	iCOHP_TS	∆iCOHP
Mn-O/Cu-O	-1.65	-1.53	0.12	-1.47	-0.68	0.79
Au-O	-1.28	-0.36	0.92	-1.43	-0.76	0.67
Au-H	-2.49	-2.48	0.01	-3.68	-2.81	0.87
HO-H	-0.10	-1.24	-1.22	-0.09	-1.57	-1.48

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揭示Au/LaMnCuO₃催化剂在乙醇选择氧化反应中的Au-Mn-Cu协同作用

Unveiling the Au-Mn-Cu synergy in Au/LaMnCuO₃ catalysts for selective ethanol oxidation

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