Boehmite lattice hydroxyl-mediated selective hydrogenation of cinnamaldehyde via water as hydrogen source

doi:10.1016/S1872-2067(26)65103-0

Abstract

Abstract:

Selective hydrogenation of cinnamaldehyde (CAL) to cinnamyl alcohol (COL) using water as the hydrogen source offers a promising route to eliminate traditional H₂ preparation. However, this approach faces a trade-off between concurrently crating abundant active hydroxyls for hydrogenation and readily removing residual oxygen under mild conditions, restricting current development. Here, we report a naturally abundant lattice hydroxyl-mediated selective hydrogenation process over a boehmite-supported gold catalyst (Au/AlOOH), using H₂O as the hydrogen source and CO as the oxygen acceptor. This process achieves 79% CAL conversion and 84% COL selectivity at 90 °C, doubling the efficiency of H₂-based hydrogenation counterpart. In contrast, the OH-free Au/Al₂O₃ shows no activity. Mechanistic studies indicate that the Au/AlOOH boundary provides unsaturated Al³⁺ sites for selective C=O adsorption and lattice hydroxyls for hydrogenation, which are continuously replenished from water. CO adsorbed on Au facilitates oxygen removal, regenerating Al³⁺ sites. This work presents a practical hydrogen transfer strategy that leverages the unique lattice hydroxyls of boehmite to efficiently extract hydrogen from water.

Key words: Selective hydrogenation, α,β-Unsaturated aldehydes, Boehmite, Gold catalyst, Water as a hydrogen source

Wenxin He, Yuanhong Lu, Chenxi Guan, Xiaohui Hou, Rui Huang, Dehui Deng. Boehmite lattice hydroxyl-mediated selective hydrogenation of cinnamaldehyde via water as hydrogen source[J]. Chinese Journal of Catalysis, 2026, 87: 386-395.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65103-0

https://www.cjcatal.com/EN/Y2026/V87/I8/386

Figures/Tables 5

Fig. 1. The screening of catalyst and hydrogen source for CAL hydrogenation. (a) Schematic illustration for the hydrogenation of CAL with CO/H2O over Au/AlOOH and with H2 over Au/Al2O3. (b) Conversion (X) and selectivity (S) comparison on the different catalysts. Reaction conditions: 70 mg catalyst, 55 mg CAL, 3 MPa CO, 8 mL H2O/1,4-dioxane (V/V, 4/4), 90 °C, 5 h. Error bars denote the standard deviation from three independent experiments. The reaction conditions are constant unless noted. (c) Stability test of Au/AlOOH and Au/MgO catalysts were performed using double CAL (110 mg). (d) Temperature effect on the catalytic performance of Au/AlOOH (H2O/1,4-dioxane = 4:4). (e) The specific molar rate and STY of Au/AlOOH with different Au content (H2O/1,4-dioxane = 4:4). (f) The hydrogenation of COL and HCAL (0.4 mmol) as substrate on Au/AlOOH. (g) Comparisons of CAL conversion and product selectivity over Au/AlOOH and Au/Al2O3 catalysts using different hydrogen source (H2O/1,4-dioxane = 4:4, 0:4 for H2).

Fig. 2. Structural characterizations for Au/AlOOH and Au/Al2O3. (a-d) HAADF-STEM images. (e) WT-EXAFS spectra of Au/AlOOH and Au/Al2O3 with Au foil and Au2O3 as references. (f) XRD patterns. (g) Infrared spectra measured in transmission mode using KBr as background. (h) Catalytic performance comparison. The reaction conditions are same with Fig. 1(g).

Fig. 3. Electronic properties of catalysts. (a) XANES spectra at the Au L3-edge of Au/AlOOH and Au/Al2O3 with Au foil and Au2O3 as references. (b) Fourier transforms of k3-weighted R-space EXAFS spectra of of Au/AlOOH and Au/Al2O3 with Au foil and Au2O3 as references. Au 4f (c) and Al 2p (d) XPS spectra of Au/AlOOH and Au/Al2O3. (e) O 1s XPS spectra of Au/AlOOH and Au/Al2O3. (f) EPR spectra of Au/AlOOH and Au/Al2O3. (g) NH3-TPD profiles of Au/AlOOH and Au/Al2O3. (h) CO2-TPD profiles of Au/AlOOH and Au/Al2O3. (i) CO-TPD profiles of Au/AlOOH and Au/Al2O3.

Table 1 EXAFS fitting parameters at the Au L3-edge for various samples.

Sample	Shell	CN ^a	R^b (Å)	σ^{2 c} (Å²)	ΔE₀ ^d (eV)	R factor
Au/AlOOH-used	Au-O	0.077±0.125	1.95	0.009±0.002	5.117±1.13	0.0127
Au/AlOOH-used	Au-Au	9.68±1.69	2.85	0.015±0.010	5.117±1.13	0.0127
Au/Al₂O₃-used	Au-Au	13.24±2.95	2.85	0.014±0.003	5.373±1.52	0.0203

Fig. 4. In-situ spectroscopic measurements. In-situ DRIFT spectra of CAL hydrogenation over Au/AlOOH (a) and Au/Al2O3 (b) catalysts during reaction. Condition: 100 °C, 1 MPa feed gas. (c,d) Proposed mechanism for CAL hydrogenation by water on both catalysts.

References

[1]	M. Luneau, J. S. Lim, D. A. Patel, E. C. H. Sykes, C. M. Friend, P. Sautet, Chem. Rev., 2020, 120, 12834-12872.
[2]	X. Lan, T. Wang, ACS Catal., 2020, 10, 2764-2790.
[3]	X. Wang, X. Liang, P. Geng, Q. Li, ACS Catal., 2020, 10, 2395-2412.
[4]	M. Zahid, A. Ismail, M. F. Khan, N. Ali, S. H. Bakhtiar, A. El Jery, B. Al Alwan, R. Ullah, F. Raziq, W. He, K. H. L. Zhang, J. Yi, X. Wu, S. Ali, L. Qiao, Coord. Chem. Rev., 2025, 525, 216295.
[5]	R. Huang, M. Xia, Y. Zhang, C. Guan, Y. Wei, Z. Jiang, M. Li, B. Zhao, X. Hou, Y. Wei, Q. Chen, J. Hu, X. Cui, L. Yu, D. Deng, Nat. Catal., 2023, 6, 1005-1015.
[6]	Y. Wei, S. Wang, Y. Zhang, M. Li, J. Hu, Y. Liu, J. Li, L. Yu, R. Huang, D. Deng, ACS Catal., 2023, 13, 15824-15832.
[7]	L. He, F.-J. Yu, X.-B. Lou, Y. Cao, H.-Y. He, K.-N. Fan, Chem. Commun., 2010, 46, 1553-1555.
[8]	Y. Lu, Q. Chen, Y. Zhang, Y. Wei, X. Hou, R. Huang, D. Deng, ACS Catal., 2024, 14, 10113-10121.
[9]	L. Lin, S. Yao, R. Gao, X. Liang, Q. Yu, Y. Deng, J. Liu, M. Peng, Z. Jiang, S. Li, Y.-W. Li, X.-D. Wen, W. Zhou, D. Ma, Nat. Nanotechnol., 2019, 14, 354-361.
[10]	L. He, L.-C. Wang, H. Sun, J. Ni, Y. Cao, H.-Y. He, K.-N. Fan, Angew. Chem. Int. Ed., 2009, 48, 9538-9541.
[11]	B. Peng, K. Zhang, Y. Sun, B. Han, M. He, J. Am. Chem. Soc., 2025, 147, 13083-13100.
[12]	Y. Zhai, D. Pierre, R. Si, W. Deng, P. Ferrin, A. U. Nilekar, G. Peng, J. A. Herron, D. C. Bell, H. Saltsburg, M. Mavrikakis, M. Flytzani-Stephanopoulos, Science, 2010, 329, 1633-1636.
[13]	M. Yang, S. Li, Y. Wang, J. A. Herron, Y. Xu, L. F. Allard, S. Lee, J. Huang, M. Mavrikakis, M. Flytzani-Stephanopoulos, Science, 2014, 346, 1498-1501.
[14]	S. Hilaire, X. Wang, T. Luo, R. J. Gorte, J. Wagner, Appl. Catal. A, 2001, 215, 271-278.
[15]	J. H. Kwak, J. Hu, D. Mei, C.-W. Yi, D. H. Kim, C. H. F. Peden, L. F. Allard, J. Szanyi, Science, 2009, 325, 1670-1673.
[16]	L. Liu, J. Lu, Y. Yang, W. Ruettinger, X. Gao, M. Wang, H. Lou, Z. Wang, Y. Liu, X. Tao, L. Li, Y. Wang, H. Li, H. Zhou, C. Wang, Q. Luo, H. Wu, K. Zhang, J. Ma, X. Cao, L. Wang, F.-S. Xiao, Science, 2024, 383, 94-101.
[17]	X. Xu, H. Liu, J. Wang, T. Chen, X. Ding, H. Chen, Surf. Interfaces, 2021, 25, 101272.
[18]	H. T. Le, R. Lazzari, J. Goniakowski, R. Cavallotti, S. Chenot, C. Noguera, J. Jupille, A. Koltsov, J.-M. Mataigne, J. Phys. Chem. C, 2017, 121, 11464-11471.
[19]	Y. Fan, R. Li, B. Wang, X. Feng, X. Du, C. Liu, F. Wang, C. Liu, C. Dong, Y. Ning, R. Mu, Q. Fu, Nat. Commun., 2024, 15, 3046.
[20]	D. Wang, R. Li, X. Sun, L. Lin, K. Li, R. Zhang, R. Mu, Q. Fu, ACS Catal., 2024, 14, 5147-5155.
[21]	B. L. Moroz, P. A. Pyrjaev, V. I. Zaikovskii, V. I. Bukhtiyarov, Catal. Today, 2009, 144, 292-305.
[22]	Z. Zhang, Y. Zhu, H. Asakura, B. Zhang, J. Zhang, M. Zhou, Y. Han, T. Tanaka, A. Wang, T. Zhang, N. Yan, Nat. Commun., 2017, 8, 16100.
[23]	S. Liu, M. Dong, Y. Wu, S. Luan, Y. Xin, J. Du, S. Li, H. Liu, B. Han, Nat. Commun., 2022, 13, 2320.
[24]	A. P. Amrute, Z. Łodziana, H. Schreyer, C. Weidenthaler, F. Schüth, Science, 2019, 366, 485-489.
[25]	Z. Tian, L. Wang, T. Shen, P. Yin, W. Da, Z. Qian, X. Zhao, G. Wang, Y. Yang, M. Wei, Chem. Eng. J., 2023, 472, 144876.
[26]	P. Liu, X. Zou, X.-Y. Meng, C. Peng, X. Li, Y. Wang, F. Zhao, Y.-X. Pan, AlChE J., 2023, 69, e18016.
[27]	Y. Choi, G. Kim, J. Kim, S. Lee, J.-C. Kim, R. Ryoo, H. Lee, Appl. Catal. B, 2023, 325, 122325.
[28]	Y. Fan, F. Wang, R. Li, C. Liu, Q. Fu, ACS Catal., 2023, 13, 2277-2285.
[29]	R. Wei, Z. Gao, W. Huang, Mol. Catal., 2023, 548, 113457.
[30]	D. R. Aireddy, K. Ding, ACS Catal., 2022, 12, 4707-4723.
[31]	M. Shekhar, J. Wang, W.-S. Lee, W. D. Williams, S. M. Kim, E. A. Stach, J. T. Miller, W. N. Delgass, F. H. Ribeiro, J. Am. Chem. Soc., 2012, 134, 4700-4708.
[32]	H. Funke, A. C. Scheinost, M. Chukalina, Phys. Rev. B, 2005, 71, 094110.
[33]	Z. Liu, D. Jiang, L. Yang, J. Yu, X. Li, X. Liu, L. Zhao, X.-L. Zhang, F. Han, W. Zhou, H. Liu, Nano Energy, 2021, 88, 106302.
[34]	S. Yao, X. Zhang, W. Zhou, R. Gao, W. Xu, Y. Ye, L. Lin, X. Wen, P. Liu, B. Chen, E. Crumlin, J. Guo, Z. Zuo, W. Li, J. Xie, L. Lu, C. J. Kiely, L. Gu, C. Shi, J. A. Rodriguez, D. Ma, Science, 2017, 357, 389-393.
[35]	C. López-Cartes, T. C. Rojas, R. Litr n, D. Martínez-Martínez, J. M. de la Fuente, S. Penadés, A. Fern ndez, J. Phys. Chem. B, 2005, 109, 8761-8766.
[36]	W. Shangguan, G. Li, S. Gui, X. Zhang, S. Meng, S. Chen, Y. Li, Adv. Funct. Mater., 2025, 35, 2501285.
[37]	P. Wang, Y. Sheng, F. Wang, H. Yu, Appl. Catal. B, 2018, 220, 561-569.
[38]	Q. Fu, H. Saltsburg, M. Flytzani-Stephanopoulos, Science, 2003, 301, 935-938.
[39]	J. Dong, Q. Fu, Z. Jiang, B. Mei, X. Bao, J. Am. Chem. Soc., 2018, 140, 13808-13816.
[40]	X. Zhang, M. Zhang, Y. Deng, M. Xu, L. Artiglia, W. Wen, R. Gao, B. Chen, S. Yao, X. Zhang, M. Peng, J. Yan, A. Li, Z. Jiang, X. Gao, S. Cao, C. Yang, A. J. Kropf, J. Shi, J. Xie, M. Bi, J. A. van Bokhoven, Y.-W. Li, X. Wen, M. Flytzani-Stephanopoulos, C. Shi, W. Zhou, D. Ma, Nature, 2021, 589, 396-401.
[41]	P. Liu, Y. Zhao, R. Qin, S. Mo, G. Chen, L. Gu, D. M. Chevrier, P. Zhang, Q. Guo, D. Zang, B. Wu, G. Fu, N. Zheng, Science, 2016, 352, 797-800.
[42]	Y. Liang, Z. Zhang, X. Su, X. Feng, S. Xing, W. Liu, R. Huang, Y. Liu, Angew. Chem. Int. Ed., 2023, 62, e202309030.
[43]	G. Vilé, D. Albani, M. Nachtegaal, Z. Chen, D. Dontsova, M. Antonietti, N. López, J. Pérez-Ramírez, Angew. Chem. Int. Ed., 2015, 54, 11265-11269.
[44]	K.-I. Shimizu, Y. Miyamoto, T. Kawasaki, T. Tanji, Y. Tai, A. Satsuma, J. Phys. Chem. C, 2009, 113, 17803-17810.
[45]	C. Costentin, H. Dridi, J. M. Savéant, J. Am. Chem. Soc., 2014, 136, 13727-13734.
[46]	Y. Bonita, V. Jain, F. Geng, T. P. O’Connell, N. X. Ramos, N. Rai, J. C. Hicks, Appl. Catal. B, 2020, 277, 119272.
[47]	X. Lan, K. Xue, T. Wang, J. Catal., 2019, 372, 49-60.
[48]	Y. Liang, Q. Tang, L. Liu, D. Wang, J. Dong, Appl. Catal. B, 2023, 333, 122783.
[49]	V. Ponec, Appl. Catal. A, 1997, 149, 27-48.
[50]	S. Nishiyama, T. Hara, S. Tsuruya, M. Masai, J. Phys. Chem. B, 1999, 103, 4431-4439.