Highly selective catalysts for the hydrogenation of alkynols: A review

doi:10.1016/S1872-2067(20)63773-1

Abstract

Abstract:

The semi-hydrogenation of alkynols to enols is a crucial process in the production of pharmaceuticals, agrochemicals, fragrances, and flavors that involves a complex set of parallel and consecutive isomerization and hydrogenation reactions and proceeds via several key intermediates. In view of the industrial importance of large-scale enol production through alkynol hydrogenation, various noble and non-noble metal (e.g., Ni and Pd)-based catalysts promoting this transformation have been developed. This paper reviews the design of highly selective catalysts for the semi-hydrogenation of alkynols, focusing on the role of additives, second metals, catalyst supports, and reaction conditions and combining catalytic reaction kinetics with theoretical calculations to establish the reaction mechanism and the decisive factors for boosting selectivity. Finally, a strategy for designing highly efficient and selective catalysts based on the characteristics of aqueous-phase alkynol hydrogenation is proposed.

Key words: Alkynol, Enol, Selective hydrogenation, Metal-based catalyst, Catalyst design

Xiao Chen, Chuang Shi, Changhai Liang. Highly selective catalysts for the hydrogenation of alkynols: A review[J]. Chinese Journal of Catalysis, 2021, 42(12): 2105-2121.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63773-1

https://www.cjcatal.com/EN/Y2021/V42/I12/2105

Figures/Tables 27

Table 1 Schematic alkynol hydrogenation pathways.

No.	Alkynol	Schematic hydrogenation pathway
1	3-Hexyn-1-ol
2	3-Phenyl-2-propyn-1-ol
3	2-Butyne-1,4-diol
4	2-Methyl-3-butyne-2-ol
5	1,1-Diphenyl-2-propyn-1-ol
6	Dehydroisophytol

Scheme 1 General mechanism of alkyne hydrogenation.

Table 2 Performance of previously reported Pd-based catalysts for the selective hydrogenation of alkynols.

No.	Catalyst	Substrate	T (°C)	P (MPa)	Alkynol conversion (%)	Enol selectivity (%)	Ref.
1	PVP-Pd	2-Butyne-1,4-diol	50	2	100	96	[29]
2	Pd/CaCO₃	2-Butyne-1,4-diol	50	2.1	—	99.5	[10]
3	Pd/CaCO₃-NH₃	2-Butyne-1,4-diol	50	2.4	—	100	[11]
4	Pd/CaCO₃	3-Hexyn-1-ol	-10	0.1	100	95.3	[30]
5	PdPb/CaCO₃	2-Methyl-3-butyn-2-ol	80	0.1	99	95	[15]
6	Pd/ACF	2-Butyne-1,4-diol	30	0.6	80	97	[34]
7	Pd/C	2-Butyne-1,4-diol	65	0.3	65	73	[35]
8	Pd/C	2-Butyne-1,4-diol	50	2.1	—	99.2	[10]
9	c-Pd/C	2-Methyl-3-butyn-2-ol	20	0.1	24-35	100	[12]
10	Pd NCs@NCM	3-Phenyl-2-propyn-1-ol	45	H₂ balloon	93.1	97.7	[36]
11	c-Pd/TiS	3-Hexyn-1-ol	30	0.3	97	99	[32]
12	c-Pd/TiS	2-Methyl-3-butyn-2-ol	30	0.3	97	95	[32]
13	Pd/SiO₂	3-Hexyn-1-ol	RT	0.1-0.2	85	80	[38]
14	Pd/GPMHS40	3-Hexyn-1-ol	40	—	100	>90	[39]
15	Pd@MonoSil-ArSO₃	3-Hexyn-1-ol	RT	0.115	94 ± 1	94 ± 1	[40]
16	Pd/SiO₂-Schiff	2-Butyne-1,4-diol	50	2	95.2	100	[41]
17	Pd/Al₂O₃	2-Butyne-1,4-diol	60	0.45	90.8	95.3	[42]
18	Pd/γ-Al₂O₃	2-Butyne-1,4-diol	50	0.6	100	94	[43]
19	Pd/Mg(Al)O	2-Butyne-1,4-diol	50	0.6	90	88	[46]
20	Pd@TiO₂	3-Hexyn-1-ol	RT	—	61.4	63	[47]
21	Pd/TiO₂	3-Hexyn-1-ol	40	0.2	100	60-87	[48]
22	Pd/ZnO	2-Methyl-3-butyn-2-ol	130	1	10	96	[50]
23	Pd@Cu₂O	3-Phenyl-2-propyn-1-ol	20	0.1	96.1	91.0	[36]
24	Pd/ZPGly20	2-Butyne-1,4-diol	RT	0.1	98.3	97.3	[52]
		2-Methyl-3-butyn-2-ol	RT	0.1	75.3	94.9
		3-Hexyn-1-ol	RT	0.1	99.6	90.6
		3-Phenyl-2-propyn-1-ol	RT	0.1	95	93.7
25	Pd/FCN resin	2-Butyne-1,4-diol	22	—	90	94.7	[53]
26	Pd/OFP resin	2-Butyne-1,4-diol	22	0.1	90	85	[54]
27	D/Pd	3-Hexyn-1-ol	—	0.1	75	80	[55]
28	Pd@borate	2-Butyne-1,4-diol	RT	0.176	93.3	75.5	[56]
		2-Methyl-3-butyn-2-ol	RT	0.14	92	93.9
		3-Hexyn-1-ol	RT	0.126	99.5	94.5
		3-Phenyl-2-propyn-1-ol	RT	0.15	96.2	79
29	Pd/MOF-5	2-Butyne-1,4-diol	20	0.1	95	95	[57]
30	Pd/MIL-101(Cr)	2-Butyne-1,4-diol	50	0.5	100	94	[58]
31	PVP-Pd/ZIF-8	2-Butyne-1,4-diol	50	2	99.7	97.5	[59]
32	PdCu/CaCO₃	3-Hexyn-1-ol	-10	0.1	100	95.7	[30]
33	PdAu/SiO₂	3-Hexyn-1-ol	20	2	15	100	[38]
34	PdCu/ZnO	Dehydroisophytol	80	0.4	99	95-97	[60]
35	PdAg/ZnO	Dehydroisophytol	80	0.4	99	97-98	[60]
36	PdAu	2-Methyl-3-butyn-2-ol	30	—	98.2	98.9	[62]
37	PdBi/SiO₂	2-Methyl-3-butyn-2-ol	50	0.1	100	94-96	[63]
38	PdZn/Al₂O₃	2-Methyl-3-butyn-2-ol	100	0.1	25	90	[66]
39	PdZn/TiO₂	2-Methyl-3-butyn-2-ol	60	0.5	95	81.5-88.9	[68]
40	Pd/ZnO/SMF	2-Butyne-1,4-diol	80	1.5	99	99	[69]
41	Pd/ZnO/SMF	2-Methyl-3-butyn-2-ol	35	0.5	99.9	94.5	[69]
42	PdIn/In₂O₃	2-Methyl-3-butyn-2-ol	80	0.1	99	95	[15]

Table 2 Performance of previously reported Pd-based catalysts for the selective hydrogenation of alkynols.

No.	Catalyst	Substrate	T (°C)	P (MPa)	Alkynol conversion (%)	Enol selectivity (%)	Ref.
1	PVP-Pd	2-Butyne-1,4-diol	50	2	100	96	[29]
2	Pd/CaCO₃	2-Butyne-1,4-diol	50	2.1	—	99.5	[10]
3	Pd/CaCO₃-NH₃	2-Butyne-1,4-diol	50	2.4	—	100	[11]
4	Pd/CaCO₃	3-Hexyn-1-ol	-10	0.1	100	95.3	[30]
5	PdPb/CaCO₃	2-Methyl-3-butyn-2-ol	80	0.1	99	95	[15]
6	Pd/ACF	2-Butyne-1,4-diol	30	0.6	80	97	[34]
7	Pd/C	2-Butyne-1,4-diol	65	0.3	65	73	[35]
8	Pd/C	2-Butyne-1,4-diol	50	2.1	—	99.2	[10]
9	c-Pd/C	2-Methyl-3-butyn-2-ol	20	0.1	24-35	100	[12]
10	Pd NCs@NCM	3-Phenyl-2-propyn-1-ol	45	H₂ balloon	93.1	97.7	[36]
11	c-Pd/TiS	3-Hexyn-1-ol	30	0.3	97	99	[32]
12	c-Pd/TiS	2-Methyl-3-butyn-2-ol	30	0.3	97	95	[32]
13	Pd/SiO₂	3-Hexyn-1-ol	RT	0.1-0.2	85	80	[38]
14	Pd/GPMHS40	3-Hexyn-1-ol	40	—	100	>90	[39]
15	Pd@MonoSil-ArSO₃	3-Hexyn-1-ol	RT	0.115	94 ± 1	94 ± 1	[40]
16	Pd/SiO₂-Schiff	2-Butyne-1,4-diol	50	2	95.2	100	[41]
17	Pd/Al₂O₃	2-Butyne-1,4-diol	60	0.45	90.8	95.3	[42]
18	Pd/γ-Al₂O₃	2-Butyne-1,4-diol	50	0.6	100	94	[43]
19	Pd/Mg(Al)O	2-Butyne-1,4-diol	50	0.6	90	88	[46]
20	Pd@TiO₂	3-Hexyn-1-ol	RT	—	61.4	63	[47]
21	Pd/TiO₂	3-Hexyn-1-ol	40	0.2	100	60-87	[48]
22	Pd/ZnO	2-Methyl-3-butyn-2-ol	130	1	10	96	[50]
23	Pd@Cu₂O	3-Phenyl-2-propyn-1-ol	20	0.1	96.1	91.0	[36]
24	Pd/ZPGly20	2-Butyne-1,4-diol	RT	0.1	98.3	97.3	[52]
		2-Methyl-3-butyn-2-ol	RT	0.1	75.3	94.9
		3-Hexyn-1-ol	RT	0.1	99.6	90.6
		3-Phenyl-2-propyn-1-ol	RT	0.1	95	93.7
25	Pd/FCN resin	2-Butyne-1,4-diol	22	—	90	94.7	[53]
26	Pd/OFP resin	2-Butyne-1,4-diol	22	0.1	90	85	[54]
27	D/Pd	3-Hexyn-1-ol	—	0.1	75	80	[55]
28	Pd@borate	2-Butyne-1,4-diol	RT	0.176	93.3	75.5	[56]
		2-Methyl-3-butyn-2-ol	RT	0.14	92	93.9
		3-Hexyn-1-ol	RT	0.126	99.5	94.5
		3-Phenyl-2-propyn-1-ol	RT	0.15	96.2	79
29	Pd/MOF-5	2-Butyne-1,4-diol	20	0.1	95	95	[57]
30	Pd/MIL-101(Cr)	2-Butyne-1,4-diol	50	0.5	100	94	[58]
31	PVP-Pd/ZIF-8	2-Butyne-1,4-diol	50	2	99.7	97.5	[59]
32	PdCu/CaCO₃	3-Hexyn-1-ol	-10	0.1	100	95.7	[30]
33	PdAu/SiO₂	3-Hexyn-1-ol	20	2	15	100	[38]
34	PdCu/ZnO	Dehydroisophytol	80	0.4	99	95-97	[60]
35	PdAg/ZnO	Dehydroisophytol	80	0.4	99	97-98	[60]
36	PdAu	2-Methyl-3-butyn-2-ol	30	—	98.2	98.9	[62]
37	PdBi/SiO₂	2-Methyl-3-butyn-2-ol	50	0.1	100	94-96	[63]
38	PdZn/Al₂O₃	2-Methyl-3-butyn-2-ol	100	0.1	25	90	[66]
39	PdZn/TiO₂	2-Methyl-3-butyn-2-ol	60	0.5	95	81.5-88.9	[68]
40	Pd/ZnO/SMF	2-Butyne-1,4-diol	80	1.5	99	99	[69]
41	Pd/ZnO/SMF	2-Methyl-3-butyn-2-ol	35	0.5	99.9	94.5	[69]
42	PdIn/In₂O₃	2-Methyl-3-butyn-2-ol	80	0.1	99	95	[15]

Fig. 2. Pd NPs supported on hierarchically porous silica grafted with polymethylhydrosiloxane for the selective hydrogenation of 3-hexyn-1-ol. Reprinted with permission from Ref. [39]. Copyright © 2017, American Chemical Society.

Fig. 4. Schematic fabrication of Pd/Fe-Co-Ni LDH nanocages and their use as catalysts for MBY hydrogenation. Reprinted with permission from Ref. [49]. Copyright © 2020 Elsevier B.V. All rights reserved.

Fig. 5. Synthesis (top) and images of MonoBor (left), Pd(NO3)2-impregnated MonoBor (center), and Pd@MonoBor (right) monolithic columns (i.d. = 3 mm, length = 25 mm). Reprinted with permission from Ref. [53]. Copyright © 2013 Elsevier Inc. All rights reserved.

Fig. 6. Kinetic data for BYD hydrogenation over (a) 1 wt% PVP-Pd@ZIF-8 and (b) PVP-Pd colloid. Reprinted from Ref. [59] with permission from the Royal Society of Chemistry.

Fig. 10. Catalytic performances of Pd-In/In2O3-250 and PdPb/CaCO3 for the semi-hydrogenation of MBY. (a) Time-conversion and (b) selectivity-conversion profiles. Reprinted with permission from Ref. [15]. Copyright @2019, the Royal Society of Chemistry.

Table 3 Activities of Pt-based catalysts for the selective hydrogenation of BYD.

No.	Catalyst	T (°C)	P (MPa)	Alkynol conversion (%)	Enol selectivity (%)	Ref.
1	Pt/CaCO₃	50	2.4	~95	83	[72]
2	Pt/CaCO₃-NH₃	50	2.4	—	100	[72]
3	Pt-Li/CaCO₃	50	2.4	99.6	83	[73]
4	Pt-Cs/CaCO₃	50	2.4	—	99	[73]
5	PtCu/Cu_xFe_yO@C	120	4	100	96.1	[74]
6	Pt@ZIF-8	120	3	100	94	[75]
7	Pt/SBA-15	120	3	~100	68	[75]
8	Pt nano-sol	120	3	~95	68	[75]
9	Pt/SiC	100	1	96	96	[76]
10	Pt/bovine-bone	55	0.6	~100	83	[77]
11	Pt/PANI	22	0.1	85	75	[78]
12	Pt/P4VP	22	0.1	85	80	[79]
13	Pt/graphite	40	0.5	70	~55	[80]

Fig. 11. One-step synthesis of the Pt@ZIF-8 catalyst for the selective hydrogenation of BYD to BED. Reprinted with permission from Ref. [75]. Copyright © 2016 Dalian Institute of Chemical Physics, Chinese Academy of Sciences.

Fig. 12. Schematic structural evolution of the Pt/SiC catalyst for the selective hydrogenation of BYD to BED. Reprinted from Ref. [76] with permission from the Royal Society of Chemistry.

Fig. 13. (a) MBY and MBE conversions after 1-h hydrogenation over Au@Au6Pd1, Au@Au4Pd1, Au@Au3Pd1, Au@Au2Pd1, Au@Au2Pd3, Au@Au1Pd4, and Au@Au0Pd5 at 30 °C. (b) Semi-hydrogenation selectivity of different nanocubes for MBE at a conversion of ~95%. Time-dependent hydrogenation conversions of MBY and MBE selectivities of Au@Au6Pd1 (c), Au@Au4Pd1 (d), and Au@Au2Pd1 (e) nanocubes. (f) Four-cycle durability test of Au@Au4Pd1 nanocubes. Reprinted with permission from Ref. [62]. Copyright 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Table 4 Activities of previously reported Ni-based catalysts for the selective hydrogenation of BYD.

No.	Catalyst	Reactor	T (°C)	P (MPa)	BYD conversion (%)	Selectivity (%)		Ref.
No.	Catalyst	Reactor	T (°C)	P (MPa)	BYD conversion (%)	BDO	BED	Ref.
1	Raney Ni	batch	70	6.9	100	93	trace	[83]
2	Raney Ni	CSTR	70	6.9	100	98-99	trace	[83]
3	Raney Ni	fixed bed	120	13.8	100	95.3	trace	[84]
4	Raney Ni	batch	40	atmospheric pressure	100	91.6	trace	[85]
5	Raney 350-NiSi_x	fixed bed	90	3	84.8	9.3	80.4	[88]
6	Ni/AlPO₄-P	batch	40	0.3-0.7	10.3 μmol s^-1 g^-1	—	92.5	[89]
7	NiCu/AlPO₄-P	batch	40	0.3-0.7	9.51 μmol s^-1 g^-1	—	97.9	[89]
8	Ni-3Fe/Al₂O₃	slurry-bed	120	4	99.9	0.5	97.3	[90]
9	Ni/Al₂O₃	slurry-bed	120	4	65	62	30	[91]
10	Ni/Al₂O₃-SiO₂	slurry-bed	120	4	93.6	75.2	19.5	[91]
11	9Ni1Cu@SiO₂	batch	50	1	100	90.5	—	[92]

Fig. 14. Hydrogenation of BYD over the Ni33 catalyst in STR mode. Reaction conditions: T = 70 °C, P = 6.89 MPa, catalyst mass = 9.6 g, aqueous BYD volume = 40 mL (3.09 mM/mL), stir rate = 1900 rpm. Reprinted with permission from Ref. [84]. Copyright © 2017, American Chemical Society.

Fig. 15. Effect of contact time on BYD conversion (a) and the selectivities for BED and BDO (b) formation over Raney Ni-Si catalysts at 3 MPa H2 and 90 °C. Reprinted with permission from Ref. [88]. Copyright © 2014, Springer Nature.

Fig. 16. Results of stability testing for Ni/Al2O3 and Ni-3Fe/Al2O3: Effects of run time on (a) BYD conversion and (b) cis-BED selectivity. Reproduced with permission from Ref. [90]. Copyright @2019, the Royal Society of Chemistry.

Fig. 17. Proposed mechanism of BYD hydrogenation over phyllosilicate-derived NiCu@SiO2 catalysts. Reprinted with permission from Ref. [92]. Copyright 2019, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fig. 18. Effect of alkyne conversion on BYD selectivity for four different Pt catalysts with increasing occupation/blockage of defect sites. Reprinted with permission from ref. [80]. Copyright © 2012, American Chemical Society.

Fig. 19. (a) Comparison of metal-based catalysts in terms of their specific activity and selectivity for BED formation during BYD hydrogenation. (b) Detailed view of data enclosed in the red box of (a).

Fig. 20. A: Hydrogenation of BYD over catalyst RN1-32 in STR mode. (H2 Uptake vs. Time.) B: Hydrogenation of BYD over catalyst RN1-32 in STR mode. (Concentration vs. Time.) Reprinted with permission from Ref. [84]. Copyright © 2017, American Chemical Society.

Fig. 21. Natural bond orbital charge (qNBO) (left) and changes in the natural electron configuration (ΔnNEC) before and after BD adsorption on Ni22 (111) (right). The color of atoms in the left panel changes from red (positively charged) to green (negatively charged). Reprinted with permission from Ref. [96]. Copyright © 2012, Elsevier B.V. All rights reserved.

Fig. 22. Mechanisms of hydrogenation on the Pd9(H)2 cluster for BYD as a model reactant. Both reaction paths are representative of all investigated reactants. Upper and lower diagrams illustrate C≡C to C=C and C=C to C-C hydrogenation, respectively. Reprinted with permission from Ref. [97]. Copyright © 2014, American Chemical Society.

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