Mn-Zn-O活性相促进MgO基氧化物的Ni-Co纳米金属析出用于光热甲烷干重整

doi:10.1016/S1872-2067(26)65002-4

催化学报 ›› 2026, Vol. 85: 298-309.DOI: 10.1016/S1872-2067(26)65002-4

Mn-Zn-O活性相促进MgO基氧化物的Ni-Co纳米金属析出用于光热甲烷干重整

闫小凤^a^,^b^,¹, 孟宇璇^a^,¹, 庹越凡^c^,¹, 薛耀^d^,¹, 杨千瑞^b, 罗正坤^b, 严逸珑^a^,^e(), 林蒙^c, 赵宇飞^d, 孟宪光^a()

^a 大湾区大学物质科学学院, 广东东莞 523000
^b 华北理工大学材料科学与工程学院, 河北省无机非金属材料重点实验室, 河北唐山 063210
^c 南方科技大学机械与能源工程系, 广东深圳 518055
^d 北京化工大学, 化工资源有效利用国家重点实验室, 北京 100029
^e 清华大学深圳国际研究生院材料研究院, 广东深圳 518055

收稿日期:2025-08-08 接受日期:2025-10-13 出版日期:2026-06-18 发布日期:2026-05-18
通讯作者: *电子信箱: yanyilong@gbu.edu.cn (严逸珑),
xianguang.meng@gbu.edu.cn (孟宪光).
作者简介:
¹共同第一作者.
基金资助:
国家重点研发计划(2023YFB4104600);国家自然科学基金(52572313);唐山市人才资助项目(A202202007);深圳市科技创新委员会(20231120185819001)

Mn-Zn-O active phase promoted Ni-Co nanometal exsolved from MgO-based oxide for photothermal dry reforming of methane

Xiaofeng Yan^a^,^b^,¹, Yuxuan Meng^a^,¹, Yuefan Tuo^c^,¹, Yao Xue^d^,¹, Qianrui Yang^b, Zhengkun Luo^b, Yilong Yan^a^,^e(), Meng Lin^c, Yufei Zhao^d, Xianguang Meng^a()

^a School of Physical Sciences, Great Bay University, Dongguan 523000, Guangdong, China
^b Hebei Provincial Laboratory of Inorganic Nonmetallic Materials, College of Materials Science and Engineering, North China University of Science and Technology, Tangshan 063210, Hebei, China
^c Department of Mechanical and Energy, Southern University of Science and Technology, Shenzhen 518055, Guangdong, China
^d State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
^e Institute of Materials Research, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, Guangdong, China

Received:2025-08-08 Accepted:2025-10-13 Online:2026-06-18 Published:2026-05-18
Contact: *E-mail: yanyilong@gbu.edu.cn (Y. Yan),
xianguang.meng@gbu.edu.cn (X. Meng).
About author:
¹Contributed equally to this work.
Supported by:
National Key R&D Program of China(2023YFB4104600);National Natural Science Foundation of China(52572313);Tangshan Talent Funding Project(A202202007);Shenzhen Science and Technology Innovation Commission(20231120185819001)

摘要/Abstract

摘要：

随着全球能源消耗的不断增长与化石燃料燃烧所造成的二氧化碳(CO₂)排放增加, 能源与环境问题日益严峻. 甲烷干重整反应(DRM, CH₄ + CO₂ → 2H₂ + 2CO)不仅能同时转化两种主要温室气体, 还可生成可用于费托合成及氢气生产的重要合成气, 因而成为实现“碳中和”目标的重要途径. 然而, 传统镍(Ni)基催化剂在高温DRM中易发生烧结与积炭失活, 严重制约其稳定性与工业化应用. 因此, 开发兼具高活性与抗积炭性能的多组分高稳定性催化剂具有重要科学意义与实际价值.

本文首先基于DRM反应的结构调控与多金属协同机制提出设计思路. 采用共沉淀法制备多金属MgO固溶体, 经煅烧与还原后形成Ni-Co纳米合金和Mn-Zn-O活性相共存的结构. X-射线衍射及Rietveld精修结果表明, Zn的引入可稳定MnO, 使其在还原后形成富Mn的Mn-Zn-O表面相, 同时促进Ni-Co活性金属在界面处析出. H₂-程序升温还原结果表明, 含Mn的样品出现明显的还原温度下降, 表明Mn组分能够促进金属氧化物的还原进程, 加快Ni-Co金属的析出与活性相生成. 透射电子显微镜和高分辨透射电子显微镜分析进一步证实Mn富集于Ni-Co合金与MgO界面. X-射线光电子能谱分析显示Mn⁴⁺被还原为Mn²⁺, 并显著提高表面氧空位浓度(Osur/Olatt由2.54增至4.90), 增强氧迁移与CO₂活化能力. 800 ^oC时NiCoZnMn-MgO催化剂的CH₄和CO₂转化率分别为92.0%和92.6%, H₂/CO比约为0.9, 且经100 h稳定测试几乎无衰减. Raman与热重分析结果表明, 该催化剂碳沉积极低(失重<5%), 积炭以易氧化石墨碳为主, 表现出优异的抗积炭性能. CH₄-程序升温表面反应(TPSR)与CO₂-TPSR证实Mn-Zn-O相可显著降低CO₂活化温度并增强CH₄活化速率; 原位漫反射红外光谱测试表明, 催化表面存在CHₓO*中间体, 证实Mn-Zn-O相可提供丰富的氧物种和氧空位促进CH₄氧化脱氢, 抑制深度裂解产碳. 进一步结合光固化3D打印构筑了多孔结构光热反应器, 实现光-热场分布均匀. NiCoZnMn-MgO在光热干重整中展现出优异性能, 在高流速(1000 mL min^-1)下CO₂转化率仍达约50%, H₂/CO比为0.9, 光能到燃料能量转化效率达20%, 远优于Ni/MgO体系.

综上, Zn诱导形成的Mn-Zn-O活性相在调控Ni-Co纳米金属析出和增强氧迁移中发挥关键作用, 实现了CH₄与CO₂的协同活化与积炭抑制. 本文提出的Mn-Zn-O相协同设计策略揭示了多金属氧化物中可变价组分对DRM活性的调控机理, 为开发高稳定性光热重整催化剂提供了理论与实验依据. 未来对实现碳资源循环利用和低碳合成气绿色制备具有重要指导意义.

关键词: Mn助剂, NiCo催化剂, MgO, 甲烷干重整, 抗积碳, 光热催化

Abstract:

Multicomponent synergistic catalysis offers a promising strategy to address the severe coking in dry reforming of methane (DRM). In this study, a multicomponent Ni_0.05Mn_0.05Co_0.05Zn_0.05Mg_0.8O catalyst was developed, with Zn stabilized MnO (Mn-Zn-O active phase) promotes the DRM performance of exsolved NiCo nanometals from MgO-based oxide. Zn doping improves MnO dispersion and enrichment on MgO support during reduction by forming Mn-Zn-O active phase, in which Mn serves as a redox-active promoter to enhance activation and dissociation of CH₄ and CO₂. The reduction of Mn to a lower valence state can facilitate CO₂ adsorption and dissociation on the surface of catalysts, which also enhanced oxygen mobility to promote CH₄ activation and coke removal. The optimized Ni_0.05Mn_0.05Co_0.05Zn_0.05Mg_0.8O catalyst demonstrates exceptional stability in thermal DRM at 800 °C for 100 h. And in photothermal DRM, the catalyst also achieves outstanding activity under high gas flow rates with well-designed three-dimensional porosity catalytic reactor.

Key words: Mn promoter, NiCo nanometals, MgO, Dry reforming of methane, Coking resistance, Photothermal

闫小凤, 孟宇璇, 庹越凡, 薛耀, 杨千瑞, 罗正坤, 严逸珑, 林蒙, 赵宇飞, 孟宪光. Mn-Zn-O活性相促进MgO基氧化物的Ni-Co纳米金属析出用于光热甲烷干重整[J]. 催化学报, 2026, 85: 298-309.

Xiaofeng Yan, Yuxuan Meng, Yuefan Tuo, Yao Xue, Qianrui Yang, Zhengkun Luo, Yilong Yan, Meng Lin, Yufei Zhao, Xianguang Meng. Mn-Zn-O active phase promoted Ni-Co nanometal exsolved from MgO-based oxide for photothermal dry reforming of methane[J]. Chinese Journal of Catalysis, 2026, 85: 298-309.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65002-4

https://www.cjcatal.com/CN/Y2026/V85/I6/298

图/表 9

Table 1 Chemical compositions and abbreviations of the samples.

Catalyst	Abbreviations
Ni/MgO	—
Ni_0.05Mg_0.95O	Ni-MgO
Ni_0.05Zn_0.05Mg_0.9O	NiZn-MgO
Ni_0.05Co_0.05Mg_0.9O	NiCo-MgO
Ni_0.05Mn_0.05Mg_0.9O	NiMn-MgO
Ni_0.05Co_0.05Zn_0.05Mg_0.85O	NiCoZn-MgO
Ni_0.05Zn_0.05Mn_0.05Mg_0.85O	NiZnMn-MgO
Ni_0.05Co_0.05Mn_0.05Mg_0.85O	NiCoMn-MgO
Ni_0.05Co_0.05Zn_0.05Mn_0.05Mg_0.8O	NiCoZnMn-MgO

Fig. 1. (a,b) XRD pattern of as-prepared Ni-MgO, NiMn-MgO, NiCoMn-MgO, and NiCoZnMn-MgO catalysts. (c) H2-TPR profiles of Ni-MgO, NiMn-MgO, NiCoMn-MgO and NiCoZnMn-MgO catalysts. Test conditions: the sample after pre-treatment in He was heated from 50 to 1000 °C at a ramp rate of 10 °C min-1 under a 10% H2/N2 gas mixture, with a flow rate of 50 mL min-1.

Fig. 2. (a,b) XRD patterns of reduced catalysts. SEM images of reduced Ni-MgO (c), NiMn-MgO (d), NiCoMn-MgO (e), and NiCoZnMn-MgO (f) catalysts.

Fig. 3. TEM (a), HRTEM (b) and HAADF-mapping (c,d) images for NiCoZnMn-MgO catalyst after reduction.

Fig. 4. CH4 conversion (a), CO2 conversion (b), and H2/CO ratio (c) of the catalysts for 8-h DRM reaction at 800 °C. Continuous DRM operation of Ni/MgO, NiCo/MgO, NiCoMn-MgO and NiCoZnMn-MgO at 800 °C: CH4 conversion (d) and CO2 conversion (e). Reaction parameters: the GHSV was 24000 mL gcat-1 h-1 (total flow rate = 40 mL min-1), utilizing a feed composition of CH4:CO2 at a ratio of 1:1. The dotted line indicates the equilibrium conversion under the reaction conditions.

Fig. 5. The structural models of catalytic chambers for 3D printing. Photographic images of the corresponding catalyst structures can be found in Fig. S13.

Fig. 6. Conversion and H2/CO ratio of Ni/MgO (a) and NiCoZnMn-MgO (b). Production rate and light-to fuel efficiency of Ni/MgO (c) and NiCoZnMn-MgO (d) for photothermal DRM under different total flow. The total flow rates and GHSV of CH4:CO2 feed with a ratio of 1:1 were: (I) 100 mL min-1, 6000 mL gcat-1 h-1; (II) 250 mL min-1, 15000 mL gcat-1 h-1; (III) 500 mL min-1, 30000 mL gcat-1 h-1; and (IV) 1000 mL min-1, 60000 mL gcat-1 h-1. Temperature profiles at different locations were shown in Fig. S19. Light source: 300 W xenon lamp (with power set to maximum).

Fig. 7. (a) Raman spectra of spent catalysts after thermal DRM. CH4-TPSR (b) and CO2-TPSR (c) profiles of reduced Ni/MgO and NiCoZnMn-MgO. (d) DRIFTs curves for Ni/MgO and NiCoZnMn-MgO at 500 °C under dark and light conditions.

Fig. 8. (a) Schematic of structural changes of Ni-MgO, NiMn-MgO, NiCoMn-MgO and NiCoZnMn-MgO after calcination and after reduction. The gray blocks are metal (Ni/Co/Mn/Zn) doped MgO. (b) The proposed mechanism of the reduction and thermal DRM over NiCoZnMn-MgO.

参考文献

[1]	X. Meng, X. Cui, N. P. Rajan, L. Yu, D. Deng, X. Bao, Chem, 2019, 5, 2296-2325.
[2]	B. Cen W,. Wang P,. Zhao C,. Liu J,. Chen J,. Lu M. Luo, Catal. Lett., 2022, 152, 863-871.
[3]	W. Xu Z,. Wang C,. Huang X. Wang, ChemCatChem, 2024, 16, e202400692.
[4]	C. Palmer, D. C. Upham, S. Smart, M. J. Gordon, H. Metiu, E. W. McFarland, Nat. Catal., 2020, 3, 83-89.
[5]	I. de Dios García, A. Stankiewicz, H. Nigar, Catal. Today, 2021, 362, 72-80.
[6]	I. V. Yentekakis, G. Goula M,. Hatzisymeon I,. Betsi-Argyropoulou G,. Botzolaki K,. Kousi D. I., Kondarides M. J., Taylor C. M. A., Parlett A,. Osatiashtiani G,. Kyriakou J. P., Holgado R. M. Lambert, Appl. Catal. B, 2019, 243, 490-501.
[7]	F. G. M,. de Medeiros F. W. B., Lopes B. Rego de Vasconcelos, Catalysts, 2022, 12, 363.
[8]	G. Wu C,. Zhang S,. Li Z,. Han T,. Wang X,. Ma J. Gong, ACS Sustainable Chem. Eng., 2013, 1, 1052-1062.
[9]	I. Wysocka, J. Hupka, A. Rogala, Catalysts, 2019, 9, 540.
[10]	P. K. Chaudhary, N. Koshta, G. Deo, Int. J. Hydrogen Energy, 2020, 45, 4490-4500.
[11]	M. Jafarbegloo, A. Tarlani, A. W. Mesbah, J. Muzart, S. Sahebdelfar, Catal. Lett., 2016, 146, 238-248.
[12]	S. De J,. Zhang R,. Luque N. Yan, Energy Environ. Sci., 2016, 9, 3314-3347.
[13]	I. V. Yentekakis, P. Panagiotopoulou G. Artemakis, Appl. Catal. B, 2021, 296, 120210.
[14]	K. Sheng, D. Luan, H. Jiang, F. Zeng, B. Wei, F. Pang, J. Ge, ACS Appl. Mater. Interfaces, 2019, 11, 24078-24087.
[15]	S. Zhang, Y. Gao, Q. Niu, P. Zhang, J. Catal., 2024, 440, 115819.
[16]	X. Liu H,. Shi X,. Meng C,. Sun K,. Zhang L,. Gao Y,. Ma Z,. Mu Y,. Ling B,. Cheng Y,. Li Y,. Xuan Y. Ding, Sol. RRL, 2021, 5, 2100185.
[17]	S.-H. Seok, S. H. Choi, E. D. Park, S. H. Han, J. S. Lee, J. Catal., 2002, 209, 6-15.
[18]	N. Zhang, A. Naden, L. Zhang, X. Yang, P. Connor, J. Irvine, Adv. Mater., 2024, 36, 2308481.
[19]	N. Wang, W. Chu, T. Zhang, X.-S. Zhao, Chem. Eng. J., 2011, 170, 457-463.
[20]	G. Lv S,. Li H,. Zhang C,. Zhu J,. Cheng P. Qian, Sep. Purif. Technol., 2025, 353, 128613.
[21]	M. Biesuz, L. Spiridigliozzi, G. Dell’Agli, M. Bortolotti, V. M. Sglavo, J. Mater. Sci., 2018, 53, 8074-8085.
[22]	D. Rein, K. Friedel Ortega, C. Weidenthaler, E. Bill, M. Behrens, Appl. Catal. A, 2017, 548, 52-61.
[23]	L. Yao J,. Zhu X,. Peng D,. Tong C. Hu, Int. J. Hydrog. Energy, 2013, 38, 7268-7279.
[24]	R. D. Shannon, Acta Crystallogr. Sect. A, 1976, 32, 751-767.
[25]	L. Huang, P. Zhong, Y. Ha, Z. Cai, Y.-W. Byeon, T.-Y. Huang, Y. Sun, F. Xie, H.-M. Hau, H. Kim, M. Balasubramanian, B. D. McCloskey, W. Yang, G. Ceder, Adv. Energy Mater., 2023, 13, 2202345.
[26]	X. Song, M. Schrade, N. Masó, T. G. Finstad, J. Alloys Compd., 2017, 710, 762-770.
[27]	S. M. Sajjadi, M. Haghighi, A. A. Eslami, F. Rahmani, J. Sol Gel Sci. Technol., 2013, 67, 601-617.
[28]	J. Li J,. Hu M. Lin, Renew. Sustain. Energy Rev., 2022, 157, 112084.
[29]	J. Li J,. Zhao S,. Wang K.-S., Peng B,. Su K,. Liu S.-F., Hung M,. Huang G,. Zhang H,. Zhang X. Wang, J. Am. Chem. Soc., 2025, 147, 14705-14714.
[30]	L. Bokobza, J.-L. Bruneel, M. Couzi, Vib. Spectrosc., 2014, 74, 57-63.
[31]	D. Wang, P. Littlewood, T. J. Marks, P. C. Stair, E. Weitz, ACS Catal., 2022, 12, 8352-8362.
[32]	N. D. Charisiou, L. Tzounis V,. Sebastian S. J., Hinder M. A., Baker K,. Polychronopoulou M. A. Goula, Appl. Surf. Sci., 2019, 474, 42-56.
[33]	M. Zakrzewski, O. Shtyka, R. Ciesielski, A. Kedziora, W. Maniukiewicz, N. Arcab, T. Maniecki, Materials, 2021, 14, 7581.
[34]	Y. Wang, Q. Hu, X. Wang, Y. Huang, Y. Wang, F. Wang, Catalysts, 2022, 12, 606.
[35]	L. Yao M. E., Galvez C,. Hu P. Da Costa, Ind. Eng. Chem. Res., 2018, 57, 16645-16656.
[36]	Q. Cheng, X. Yao, L. Ou, Z. Hu, L. Zheng, G. Li, N. Morlanes, J. L. Cerrillo, P. Castaño, X. Li, J. Gascon, Y. Han, J. Am. Chem. Soc., 2023, 145, 25109-25119.
[37]	J. Wang, Y. Xing, W. Su, K. Li, W. Zhang, Fuel, 2022, 321, 124050.

Mn-Zn-O活性相促进MgO基氧化物的Ni-Co纳米金属析出用于光热甲烷干重整

Mn-Zn-O active phase promoted Ni-Co nanometal exsolved from MgO-based oxide for photothermal dry reforming of methane

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