Direct synthesis of long-chain primary alcohols from syngas over Na-driven Co2C-Co catalyst

doi:10.1016/S1872-2067(26)64961-3

Abstract

Abstract:

The direct synthesis of high-value-added long-chain primary alcohols (LPAs, C₆₊OH) from syngas (CO + H₂) is highly attractive. However, low selectivity of targeted products is generally obtained due to competitive dissociative and non-dissociative CO adsorption, as well as uncontrollable chain growth that causes a complex reaction network. Herein, we report that Na-driven Co₂C-Co dual active sites could be engineered by loading the Na promoter onto an activated carbon supported Co-based catalyst, achieving total alcohol selectivity of ca. 46% with a remarkable LPAs fraction higher than 65%, which represents the first report of high LPA selectivity in literature. Comprehensive characterizations and experiments indicated that electron-rich state of Co₂C-Co sites was generated through Na promotion, which enhances the surface basicity of the catalyst and favors chain propagation. Moreover, Na promotes the dissociation of CO to form *C species, facilitating the transformation of metallic Co into Co₂C and leading to the formation of Na-driven Co₂C-Co active sites that are closely associated with CO insertion. Density functional theory calculations show that Na significantly also promotes C-C coupling while inhibiting hydrogenation and promoting CO insertion, which is deemed to be the intrinsic mechanism behind the high LPAs selectivity. This work elucidates a dual role of Na in constructing active sites and modulating surface reaction energetics, providing a design paradigm to break the LPAs selectivity barrier in syngas conversion.

Key words: Syngas conversion, Alkali metal, Na-driven Co₂C-Co catalyst, Long-chain primary alcohols, Structure-performance relationship

Zheng Li, Ziang Zhao, Yihui Li, Yuan Lyu, Li Yan, Wenhao Cui, Shunbin Zhu, Yu Meng, Hejun Zhu, Yunjie Ding. Direct synthesis of long-chain primary alcohols from syngas over Na-driven Co₂C-Co catalyst[J]. Chinese Journal of Catalysis, 2026, 85: 371-383.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64961-3

https://www.cjcatal.com/EN/Y2026/V85/I6/371

Figures/Tables 9

Fig. 1. (a) CO conversion and product selectivity of xNa-Co/AC catalyst. (b) Comparison of the selectivity of alcohols and LPAs with other studies (a alcohols with five or more carbon numbers). Product distribution of alcohols, olefins, alkanes and corresponding chain growth probability (α) of Co/AC (c) and 0.3Na-Co/AC (d). Reaction conditions: 220 °C, 3.0 MPa, 4000 h-1, H2/CO = 2.0. (e) ASF behavior for total Cn of the Co/AC and 0.3Na-Co/AC catalysts. (f) Stability test over the 0.3Na-Co/AC catalyst. Reaction conditions: 220 °C, 4.0 MPa, 4000 h-1, H2/CO = 2.0.

Table 1 Chemical content and properties over xNa-Co/AC catalysts.

Catalyst	M_Co^a (wt%)	M_Na^a (wt%)	H₂ uptake^b (μmol/g_cat, STP)	CO uptake^c (μmol/g_cat, STP)	C/H ratio ^d	Reduction degree^e (%)
Co/AC	14.2	—	48.2	144.2	3.0	85.8
0.1Na-Co/AC	14.6	0.10	20.5	136.8	6.7	71.4
0.3Na-Co/AC	15.0	0.23	16.0	118.1	7.4	67.4
0.5Na-Co/AC	15.5	0.46	11.4	98.5	8.6	61.1

Fig. 2. (a) XRD patterns of the calcined catalysts, reduced catalysts, and spent catalysts. (b) In-situ XRD in a syngas (220 °C, 0.6 MPa and H2/CO = 2.0) atmosphere of reduced 0.3Na-Co/AC catalyst.

Fig. 3. HRTEM images and particle size distributions for spent Co/AC (a,c) and 0.3Na-Co2C-Co/AC (b,d) catalysts. HAADF-STEM images of the 0.3Na-Co2C-Co/AC catalyst, along with EDS line scan (e), point scan (f), and elemental distribution mapping for Co, C, and Na (g).

Fig. 4. Co 2p XPS spectra of Co/AC and 0.3Na-Co/AC catalysts. (a) calcined at 350 °C in Ar atmosphere; (b) In-situ reduced at 430 °C in H2 atmosphere for 4 h; (c) Spent after 48 h time on stream at 220 °C, 3.0 MPa, GHSV = 4000 h−1, and H2/CO = 2.0; (d) Surface atom ration of C to Co of spent catalysts with different Na contents.

Fig. 5. (a) H2-D2 exchange reaction profiles of Co/AC and 0.3Na-Co/AC catalysts in the temperature range of 30-300 °C. (b) CO2-TPD profiles of Co/AC and 0.3Na-Co/AC catalysts. Transient response curves of 1-butene hydrogenation pulse experiments at 220 °C over Co/AC (c) and 0.3Na-Co2C-Co/AC (d). Transient response curves from 1-butene, carbon monoxide and hydrogen experiments at 220 °C for Co/AC (e) and 0.3Na-Co2C-Co/AC (f).

Fig. 6. (a) H2-TPD profiles of 0.3Na-Co/AC and Co/AC catalysts. (b) CO-SR-MS experiments of the catalysts and support. In-situ XRD results of the reduced 0.3Na-Co/AC (c) and Co/AC (d) catalysts in a CO atmosphere.

Fig. 7. Schematic representation of the mechanisms for CO dissociation pathways on Na-Co2C-Co (111) and Co (111) surfaces.

Fig. 8. DFT calculations were performed on Na-Co2C-Co (111), Co (111), and Co2C-Co (111) surfaces. The reaction pathway barriers for the coupling reaction of *C2H4 and *CH2 intermediates (a), *C4H8 hydrogenation (b), and the insertion of *CO into *C4H8 (c).

References

[1]	Y. Xiang, V. Chitry, P. Liddicoat, P. Felfer, J. Cairney, S. Ringer, N. Kruse, J. Am. Chem. Soc., 2013, 135, 7114-7117.
[2]	X. Luan, Z. Ren, X. Dai, X. Zhang, J. Yong, Y. Yang, H. Zhao, M. Cui, F. Nie, X. Huang, ACS Catal., 2020, 10, 2419-2430.
[3]	H. Shen, K. Liu, J. Li, R. Zhang, K. Gong, Y. An, T. Lin, L. Zhong, ACS Catal., 2025, 15, 6173-6185.
[4]	H. T. Luk, C., Mondelli D. C., Ferré J. A., Stewart J. Pérez-Ramírez, Chem. Soc. Rev., 2017, 46, 1358-1426.
[5]	Y. Li Z,. Zhao W,. Lu M,. Jiang C,. Li M,. Zhao L,. Gong S,. Wang L,. Guo Y,. Lyu L,. Yan H,. Zhu Y. Ding, ACS Catal., 2021, 11, 14791-14802.
[6]	X. Qi T,. Lin Y,. An X,. Wang D,. Lv Z,. Tang L. Zhong, ACS Catal., 2023, 13, 11566-11579.
[7]	S. Wang, P. Wang, D. Shi, S. He, L. Zhang, W. Yan, Z. Qin, J. Li, M. Dong, J. Wang, U. Olsbye, W. Fan, ACS Catal., 2020, 10, 2046-2059.
[8]	X. Yu J,. Zhang X,. Wang Q,. Ma X,. Gao H,. Xia X,. Lai S,. Fan T.-S. Zhao, Appl. Catal. B, 2018, 232, 420-428.
[9]	J. Li Y,. He L,. Tan P,. Zhang X,. Peng A,. Oruganti G,. Yang H,. Abe Y,. Wang N. Tsubaki, Nat. Catal., 2018, 1, 787-793.
[10]	T. Lin Y,. An F,. Yu K,. Gong H,. Yu C,. Wang Y,. Sun L. Zhong, ACS Catal., 2022, 12, 12092-12112.
[11]	S. Guo Z,. Li R,. Yin J,. Li Z,. Zeng Z,. Hu G,. Luo J,. Lv S,. Huang Y,. Wang X. Ma, ACS Catal., 2023, 13, 14404-14414.
[12]	Z. Zhao, Y. Li, H. Zhu, Y. Lyu, Y. Ding, Chem. Commun., 2023, 59, 3827-3837.
[13]	S. Liu D,. Wu Y,. Zhao Y,. Liang L,. Zhang J,. Sun J,. Lin S,. Wang Y,. Yao S,. Wan N. J., Coville Y,. Wang H. Xiong, Energy Fuels, 2024, 38, 14769-14796.
[14]	T. Qin T,. Lin X,. Qi C,. Wang L,. Li Z,. Tang L,. Zhong Y. Sun, Appl. Catal. B, 2021, 285, 119840.
[15]	Y. Chen, J. Wei, M. S. Duyar, V. V. Ordomsky, A. Y. Khodakov, J. Liu, Chem. Soc. Rev., 2021, 50, 2337-2366.
[16]	W. Zhou, K. Cheng, J. Kang, C. Zhou, V. Subramanian, Q. Zhang, Y. Wang, Chem. Soc. Rev., 2019, 48, 3193-3228.
[17]	Y. Li W,. Lu Z,. Zhao M,. Zhao Y,. Lyu L,. Gong H,. Zhu Y. Ding, Appl. Catal. A, 2021, 613, 118017.
[18]	Y. Ge T,. Zou A. J., Martín J. Pérez-Ramírez, ACS Catal., 2023, 13, 9946-9959.
[19]	J. Xu J,. Wei J,. Zhang N,. Liu Q,. Ge J. Sun, Chem. Catal., 2023, 3, 100584.
[20]	Z. Zhao, M. Jiang, C. Li, Y. Li, H. Zhu, R. Lin, S. Yuan, L. Yan, Y. Ding, Chin. J. Catal., 2025, 73, 16-38.
[21]	Y. Xiang, R. Barbosa, N. Kruse, ACS Catal., 2014, 4, 2792-2800.
[22]	Y. Yang, X. Qi, X. Wang, D. Lv, F. Yu, L. Zhong, H. Wang, Y. Sun, Catal. Today, 2016, 270, 101-107.
[23]	Z. Ferencz, A. Erdőhelyi, K. Baán, A. Oszkó, L. Óvári, Z. Kónya, C. Papp, H.-P. Steinrück, J. Kiss, ACS Catal., 2014, 4, 1205-1218.
[24]	Z. Zeng, Z. Li, L. Kang, X. Han, Z. Qi, S. Guo, J. Wang, A. Rykov, J. Lv, Y. Wang, X. Ma, ACS Catal., 2022, 12, 6016-6028.
[25]	G. Prieto, S. Beijer, M. L. Smith, M. He, Y. Au, Z. Wang, D. A. Bruce, K. P. De Jong, J. J. Spivey, P. E. De Jongh, Angew. Chem. Int. Ed., 2014, 53, 6397-6401.
[26]	W.-G. Cui, Y.-T. Li, H. Zhang, Z.-C. Wei, B.-H. Gao, J.-J. Dai, T.-L. Hu, Appl. Catal. B, 2020, 278, 119262.
[27]	G. Jiao, Y. Ding, H. Zhu, X. Li, J. Li, R. Lin, W. Dong, L. Gong, Y. Pei, Y. Lu, Appl. Catal. A, 2009, 364, 137-142.
[28]	Y.-P. Pei, J.-X. Liu, Y.-H. Zhao, Y.-J. Ding, T. Liu, W.-D. Dong, H.-J. Zhu, H.-Y. Su, L. Yan, J.-L. Li, W.-X. Li, ACS Catal., 2015, 5, 3620-3624.
[29]	H. Du H,. Zhu X,. Chen W,. Dong W,. Lu W,. Luo M,. Jiang T,. Liu Y. Ding, Fuel, 2016, 182, 42-49.
[30]	Z. Zhao, W. Lu, R. Yang, H. Zhu, W. Dong, F. Sun, Z. Jiang, Y. Lyu, T. Liu, H. Du, Y. Ding, ACS Catal., 2018, 8, 228-241.
[31]	P. Zhai, C. Xu, R. Gao, X. Liu, M. Li, W. Li, X. Fu, C. Jia, J. Xie, M. Zhao, X. Wang, Y.-W. Li, Q. Zhang, X.-D. Wen, D. Ma, Angew. Chem. Int. Ed., 2016, 55, 9902-9907.
[32]	J. Xie P. P., Paalanen T. W., van Deelen B. M., Weckhuysen M. J., Louwerse K. P. de Jong, Nat. Commun., 2019, 10, 167.
[33]	Z. Li L,. Zhong F,. Yu Y,. An Y,. Dai Y,. Yang T,. Lin S,. Li H,. Wang P,. Gao Y,. Sun M. He, ACS Catal., 2017, 7, 3622-3631.
[34]	H. Yu C,. Wang T,. Lin Y,. An Y,. Wang Q,. Chang F,. Yu Y,. Wei F,. Sun Z,. Jiang S,. Li Y,. Sun L. Zhong, Nat. Commun., 2022, 13, 5987.
[35]	H. Yu Y,. Wei T,. Lin C,. Wang Y,. An F,. Yu F,. Sun Z,. Jiang Y,. Sun L. Zhong, ACS Catal., 2023, 13, 3949-3959.
[36]	H. Zhang, H. Zhang, W. Qian, X. Wu, H. Ma, Q. Sun, W. Ying, Catal. Today, 2022, 388-389, 199-207.
[37]	J. Xie H. M., Torres Galvis A. C. J., Koeken A,. Kirilin A. I., Dugulan M,. Ruitenbeek K. P. de Jong, ACS Catal., 2016, 6, 4017-4024.
[38]	R. Wang, Y. Chen, X. Shang, B. Liang, X. Zhang, H. Zhuo, H. Duan, X. Li, X. Yang, X. Su, Y. Huang, T. Zhang, ACS Catal., 2024, 14, 11121-11130.
[39]	Y. Xiang, N. Kruse, Nat. Commun., 2016, 7, 13058.
[40]	T. Ishida, T. Yanagihara, X. Liu, H. Ohashi, A. Hamasaki, T. Honma, H. Oji, T. Yokoyama, M. Tokunaga, Appl. Catal. A, 2013, 458, 145-154.
[41]	G. Kresse, J. Furthmüller, Comput. Mater. Sci., 1996, 6, 15-50.
[42]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[43]	G. Kresse, J. Hafner, Phys. Rev. B, 1994, 49, 14251-14269.
[44]	R. Zhang, G. Wen, H. Adidharma, A. G. Russell, B. Wang, M. Radosz, M. Fan, ACS Catal., 2017, 7, 8285-8295.
[45]	N. Tien-Thao, M. H. Zahedi-Niaki, H. Alamdari, S. Kaliaguine, Appl. Catal. A, 2007, 326, 152-163.
[46]	Y. Zhang, S. Xu, Y. Wang, Z. Liu, Int. J. Hydrogen Energy, 2023, 48, 16267-16278.
[47]	Y. Yang, H. Zhang, H. Ma, W. Qian, Q. Sun, W. Ying, Fuel, 2022, 326, 125090.
[48]	Z. Wang, J. J. Spivey, Appl. Catal. A, 2015, 507, 75-81.
[49]	N. Tien-Thao, M. H. Zahedi-Niaki, H. Alamdari, S. Kaliaguine, J. Catal., 2007, 245, 348-357.

Direct synthesis of long-chain primary alcohols from syngas over Na-driven Co₂C-Co catalyst

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 9

References

Related Articles 15

Recommended Articles

Metrics

[1]	Syeda Sidra Bibi, Sheraz Ahmed, Heuntae Jo, Jaehoon Kim. Turning methanation into chain growth: Na-induced mechanistic bifurcation on Co-ZrO_x catalyst [J]. Chinese Journal of Catalysis, 2026, 85(6): 394-411.
[2]	Yihan Ye, Yilun Ding, Tao Peng, Cheng Liu, Xinzhe Li, Yongzhi Zhao, Jianping Xiao, Feng Jiao, Xiulian Pan. Role of accumulated carbonaceous species on dynamic confinement in zeolite catalysis [J]. Chinese Journal of Catalysis, 2026, 84(5): 74-79.
[3]	Xuanbei Peng, Mengqi An, Ruishao Mao, Yanliang Zhou, Ming Chen, Dongya Huang, Kailin Su, Shiyong Zhang, Jun Ni, Xiuyun Wang, Lilong Jiang. Scheelite-type alkali metal perrhenates supported Co-based catalysts for highly efficient ammonia synthesis [J]. Chinese Journal of Catalysis, 2026, 83(4): 432-443.
[4]	Xueqing Zhang, Wusha Jiye, Yuhua Zhang, Jinlin Li, Li Wang. Advances in iron-based Fischer-Tropsch synthesis with high carbon efficiency [J]. Chinese Journal of Catalysis, 2025, 74(7): 4-21.
[5]	Haodi Wang, Feng Jiao, Jingyao Feng, Yuting Sun, Guangjin Hou, Xiulian Pan, Xinhe Bao. Role of extra-framework aluminum species within MOR zeolites for syngas conversion via OXZEO catalysis [J]. Chinese Journal of Catalysis, 2024, 67(12): 135-143.
[6]	Peigong Liu, Tiejun Lin, Lei Guo, Xiaozhe Liu, Kun Gong, Taizhen Yao, Yunlei An, Liangshu Zhong. Tuning cobalt carbide wettability environment for Fischer-Tropsch to olefins with high carbon efficiency [J]. Chinese Journal of Catalysis, 2023, 48(5): 150-163.
[7]	Chuncheng Liu, Evgeny A. Uslamin, Sophie H. van Vreeswijk, Irina Yarulina, Swapna Ganapathy, Bert M. Weckhuysen, Freek Kapteijn, Evgeny A. Pidko. An integrated approach to the key parameters in methanol-to-olefins reaction catalyzed by MFI/MEL zeolite materials [J]. Chinese Journal of Catalysis, 2022, 43(7): 1879-1893.
[8]	Mengru Wang, Yi Wang, Xiaoling Mou, Ronghe Lin, Yunjie Ding. Design strategies and structure-performance relationships of heterogeneous catalysts for selective hydrogenation of 1,3-butadiene [J]. Chinese Journal of Catalysis, 2022, 43(4): 1017-1041.
[9]	Xiaoqin Han, Jiachang Zuo, Danlu Wen, Youzhu Yuan. Toluene methylation with syngas to para-xylene by bifunctional ZnZrO_x-HZSM-5 catalysts [J]. Chinese Journal of Catalysis, 2022, 43(4): 1156-1164.
[10]	Kai Guo, Haitao Lei, Xialiang Li, Zongyao Zhang, Yabo Wang, Hongbo Guo, Wei Zhang, Rui Cao. Alkali metal cation effects on electrocatalytic CO₂ reduction with iron porphyrins [J]. Chinese Journal of Catalysis, 2021, 42(9): 1439-1444.
[11]	Xuemei Li, Junying Tian, Hailong Liu, Congkui Tang, Chungu Xia, Jing Chen, Zhiwei Huang. Effective synthesis of 5-amino-1-pentanol by reductive amination of biomass-derived 2-hydroxytetrahydropyran over supported Ni catalysts [J]. Chinese Journal of Catalysis, 2020, 41(4): 631-641.
[12]	Zheng-Qing Huang, Teng-Hao Li, Bolun Yang, Chun-Ran Chang. Role of surface frustrated Lewis pairs on reduced CeO₂(110) in direct conversion of syngas [J]. Chinese Journal of Catalysis, 2020, 41(12): 1906-1915.
[13]	HUANG Weixin, FU Qiang. Surface and Interface Chemistry of Model Catalysts [J]. Chinese Journal of Catalysis, 2019, 40(s1): 165-168.
[14]	Zhibiao Shi, Haiyan Yang, Peng Gao, Xinqing Chen, Hongjiang Liu, Liangshu Zhong, Hui Wang, Wei Wei, Yuhan Sun. Effect of alkali metals on the performance of CoCu/TiO₂ catalysts for CO₂ hydrogenation to long-chain hydrocarbons [J]. Chinese Journal of Catalysis, 2018, 39(8): 1294-1302.
[15]	Yinwen Li, Xin Zhang, Min Wei. New development in Fe/Co catalysts: Structure modulation and performance optimization for syngas conversion [J]. Chinese Journal of Catalysis, 2018, 39(8): 1329-1346.