Design strategies and structure-performance relationships of heterogeneous catalysts for selective hydrogenation of 1,3-butadiene

doi:10.1016/S1872-2067(21)63942-6

Abstract

Abstract:

Selective hydrogenation of 1,3-butadiene is an essential process in the upgrading of the crude C4 cut from the petroleum chemical sector. Catalyst design is crucial to achieve a virtually alkadiene-free product while avoiding over-hydrogenating valuable olefins. In addition to the great industrial relevance, this demanding selectivity pattern renders 1,3-butadiene hydrogenation a widely used model reaction to discriminate selective hydrogenation catalysts in academia. Nonetheless, critical reviews on the catalyst development are extremely lacking in literature. In this review, we aim to provide the reader an in-depth overview of different catalyst families, particularly the precious metal-based monometallic catalysts (Pd, Pt, and Au), developed in the last half century. The emphasis is placed on the development of new strategies to design high-performance architectures, the establishment of structure-performance relationships, and the reaction and deactivation mechanisms. Thrilling directions for future optimization of catalyst formulations and engineering aspect are also provided.

Key words: 1,3-Butadiene, Catalyst design, Selective hydrogenation, Structure-performance relationship, Reaction and deactivation mechanism

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.

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Figures/Tables 25

Fig. 1. Technologies for the utilization of C4 cuts from steaming cracking and fluidized catalytic cracking. Data in the pies taken from Ref. [1].

Fig. 3. Chronological catalyst development for the selective hydrogenation of 1,3-butadiene.

Fig. 4. Correlation of 1-butene yield with Pauling electronegativity for the elements of the first (black symbols), the second (blue symbols) and the third transition series (red symbols). Adapted with permission from Ref. [47]. Copyright 2002, Elsevier.

Table 1 A summary of catalytic performance of representative catalysts in 1,3-butadiene hydrogenation.

Catalyst	Synthesis method	Conditions			Performance			Ref.
Catalyst	Synthesis method	T /K	H₂:BD /(mol:mol^‒1)	GHSV /(cm³g^‒1h^‒1)	X /%	S_butenes/%	Stability (h)	Ref.
Pd/Al₂O₃	Impregnation, 0.54 wt% Pd	293	6.6	2000000	20	~77	18	[13]
Pd/Al₂O₃	Reverse micelle method, 1 wt% Pd	298	5	22500	98	10	5	[48]
Pd/θ-/α-Al₂O₃	Impregnation, 0.5 wt% Pd	343	1	120000	~74	~96	—	[49]
Pd/SiO₂	Ion exchange	323	2	375000	91	92	—	[50]
Pd₁/graphene	ALD method, 0.25 wt% Pd	323	2.5	33333	95	100	50	[24]
CNT-Pd CLW ^a	Colloid grafting, 0.51 wt% Pd	300	49	2506	94	98	6	[51]
Pd/ZnO-b	Incipient wetness impregnation	313	5	—	96	90	—	[52]
Pd/ZnO-n	Incipient wetness impregnation	313	5	—	97	80	—	[52]
Pd/ZnO-t	Incipient wetness impregnation	313	5	—	100	48	—	[52]
Pd/pollen-TiO₂	Rape pollen-templated synthesis, 0.3 wt% Pd	323	2	36000	95	99	—	[53]
Pd-BMI·BF₄ ^b	Reduction of Pd²⁺in ionic liquids	313	—	—	99	97	—	[54]
Pt/m-Al₂O₃	Surfactant-assisted impregnation, 0.2 wt% Pt	473	8	5000	48	100	25	[55]
Pt@ZSBA ^c	Mercaptosilane-assisted method, 0.16 wt% Pt	298	78	490800	30	~80	6	[56]
Pt/SiO₂	Impregnation, 1 wt% Pt	440	15	—	100	~80	—	[57]
Au/Al₂O₃	Deposition-precipitation, 1 wt% Au	458	49	8000	100	100	—	[30]
Au/TiO₂	Gas-phase grafting, 1 wt% Au	458	49	8000	100	99.7	—	[30]
Au/Al₂O₃	Deposition-precipitation, 0.9 wt% Au	443	67	30000	100	100	—	[58]
Au/ZrO₂	Deposition-precipitation, 0.08 wt% Au, KCN leached	393	46	8100	90	100	6	[31]
Au/SiO₂	Deposition-precipitation, 3.7 wt% Au	393	49	6000	~85	100	9	[15]
Au/γ-Al₂O₃	Deposition-precipitation	473	49	23832	85	100	—	[59]
Au/ZnO	Deposition-precipitation, 1 wt% Au	453	67	30000	100	100	—	[60]
Au/TiO₂	Deposition-precipitation, 1 wt% Au	498	67	30000	100	100	—	[37]
Au/SBA-15	Deposition, 1 wt% Au	473	67	17550	98	100	21	[61]
Au/CeO₂-CN	Deposition precipitation, 0.08 wt% Au, NaCN leached	393	39	24000	45	100	12	[62]
Au/CNTs-i ^d	Deposition precipitation, 1.62 wt% Au	423	71.6	81000	56	100	6	[63]
Dimeric Rh/MgO	Grafting impregnation, 0.4 wt% Rh	313	49	9000	99	97	5	[38]
Ni₆₅-BMI·BF₄	Physical mixing and calcination, 7 wt% Ni	313	2	—	99	>95	—	[64]
Ni₆₅-[P₄₄₄₁][MeSO₄] ^e	Physical mixing and calcination, 6.2 wt% Ni	418	2	—	99	>99	50	[39]
Co-BTC-500 ^f	Carbonization og MOF precursor	348	60	178800	92	~80	6	[65]
Cu/SiO₂	Impregnation, 5.7 wt% Cu	413	66	35000	100	100	60	[66]
Au@Pd@SiO₂	Colloid synthesis, Au:Pd = 2.13, 0.2 wt% Au + Pd	318	67	150000	98	80	—	[67]
Pd-Au/ZnO-t	Wet impregnation, Au:Pd = 0.53, 1 wt% Au	313	5	—	99	100	—	[22]
Pd-Au/Al₂O₃	Deposition precipitation, Au:Pd = 20, 0.87 wt% Au	393	67	30000	100	100	—	[34]
Pd-Au/Al₂O₃	Colloid deposition, Au:Pd = 20, 0.9 wt% Au	333	67	30000	100	99.2	—	[33]
Pd-Ti/SiO₂	Ion exchange and impregnation, Ti:Pd = 1	323	2	375000	89	>95	—	[50]
Pd-Sn/θ-/α-Al₂O₃	Impregnation, 0.5 wt% Pd, 0.2 wt% Sn	343	1	120000	~80	99	—	[49]
KBr-Pd/γ-Al₂O₃	Microwave-assisted synthesis, 0.4 wt% Pd	308	2	36000	100	80	24	[68]
Fe-Pd/-Al₂O₃	ALD coating, 30 cycles	310	2.5	3000	99	95	—	[69]
Al-Pd/Al₂O₃	ALD coating, 0.25 wt% Pd	373	2.5	3000	99	99	62	[70]
Ag-Pd/γ-Al₂O₃	Sol immobilization, 0.5 wt% metal, Ag:Pd = 3	308	2	16200	>90	~90	50	[71]
Cu-Pd/Mn₂O₃	Sol immobilization, 1 wt% Pd, 0.9 wt% Cu	300	2	36000	99	92	10	[72]
Au-Pt/UiO-67	Impregnation-reduction, 1.89 wt% Pt, Au:Pt = 1:1.7	373	50	111000	40	80	6	[36]
Pt-Cu/Al₂O₃	Galvanic replacement method, 0.11 wt% Pt, 13.7 wt% Cu	418-433	8	1200 ^g	100	>95	25	[73]
Au-Ni/TiO₂	Co-deposition precipitation, Au:Ni = 1:0.08, 1 wt% Au	393	67	30000	100	100	—	[37]
Au-Ag/SBA-15	Deposition, 1 wt% Au, Au:Ag = 3	473	67	17550	79	100	21	[61]

Table 1 A summary of catalytic performance of representative catalysts in 1,3-butadiene hydrogenation.

Catalyst	Synthesis method	Conditions			Performance			Ref.
Catalyst	Synthesis method	T /K	H₂:BD /(mol:mol^‒1)	GHSV /(cm³g^‒1h^‒1)	X /%	S_butenes/%	Stability (h)	Ref.
Pd/Al₂O₃	Impregnation, 0.54 wt% Pd	293	6.6	2000000	20	~77	18	[13]
Pd/Al₂O₃	Reverse micelle method, 1 wt% Pd	298	5	22500	98	10	5	[48]
Pd/θ-/α-Al₂O₃	Impregnation, 0.5 wt% Pd	343	1	120000	~74	~96	—	[49]
Pd/SiO₂	Ion exchange	323	2	375000	91	92	—	[50]
Pd₁/graphene	ALD method, 0.25 wt% Pd	323	2.5	33333	95	100	50	[24]
CNT-Pd CLW ^a	Colloid grafting, 0.51 wt% Pd	300	49	2506	94	98	6	[51]
Pd/ZnO-b	Incipient wetness impregnation	313	5	—	96	90	—	[52]
Pd/ZnO-n	Incipient wetness impregnation	313	5	—	97	80	—	[52]
Pd/ZnO-t	Incipient wetness impregnation	313	5	—	100	48	—	[52]
Pd/pollen-TiO₂	Rape pollen-templated synthesis, 0.3 wt% Pd	323	2	36000	95	99	—	[53]
Pd-BMI·BF₄ ^b	Reduction of Pd²⁺in ionic liquids	313	—	—	99	97	—	[54]
Pt/m-Al₂O₃	Surfactant-assisted impregnation, 0.2 wt% Pt	473	8	5000	48	100	25	[55]
Pt@ZSBA ^c	Mercaptosilane-assisted method, 0.16 wt% Pt	298	78	490800	30	~80	6	[56]
Pt/SiO₂	Impregnation, 1 wt% Pt	440	15	—	100	~80	—	[57]
Au/Al₂O₃	Deposition-precipitation, 1 wt% Au	458	49	8000	100	100	—	[30]
Au/TiO₂	Gas-phase grafting, 1 wt% Au	458	49	8000	100	99.7	—	[30]
Au/Al₂O₃	Deposition-precipitation, 0.9 wt% Au	443	67	30000	100	100	—	[58]
Au/ZrO₂	Deposition-precipitation, 0.08 wt% Au, KCN leached	393	46	8100	90	100	6	[31]
Au/SiO₂	Deposition-precipitation, 3.7 wt% Au	393	49	6000	~85	100	9	[15]
Au/γ-Al₂O₃	Deposition-precipitation	473	49	23832	85	100	—	[59]
Au/ZnO	Deposition-precipitation, 1 wt% Au	453	67	30000	100	100	—	[60]
Au/TiO₂	Deposition-precipitation, 1 wt% Au	498	67	30000	100	100	—	[37]
Au/SBA-15	Deposition, 1 wt% Au	473	67	17550	98	100	21	[61]
Au/CeO₂-CN	Deposition precipitation, 0.08 wt% Au, NaCN leached	393	39	24000	45	100	12	[62]
Au/CNTs-i ^d	Deposition precipitation, 1.62 wt% Au	423	71.6	81000	56	100	6	[63]
Dimeric Rh/MgO	Grafting impregnation, 0.4 wt% Rh	313	49	9000	99	97	5	[38]
Ni₆₅-BMI·BF₄	Physical mixing and calcination, 7 wt% Ni	313	2	—	99	>95	—	[64]
Ni₆₅-[P₄₄₄₁][MeSO₄] ^e	Physical mixing and calcination, 6.2 wt% Ni	418	2	—	99	>99	50	[39]
Co-BTC-500 ^f	Carbonization og MOF precursor	348	60	178800	92	~80	6	[65]
Cu/SiO₂	Impregnation, 5.7 wt% Cu	413	66	35000	100	100	60	[66]
Au@Pd@SiO₂	Colloid synthesis, Au:Pd = 2.13, 0.2 wt% Au + Pd	318	67	150000	98	80	—	[67]
Pd-Au/ZnO-t	Wet impregnation, Au:Pd = 0.53, 1 wt% Au	313	5	—	99	100	—	[22]
Pd-Au/Al₂O₃	Deposition precipitation, Au:Pd = 20, 0.87 wt% Au	393	67	30000	100	100	—	[34]
Pd-Au/Al₂O₃	Colloid deposition, Au:Pd = 20, 0.9 wt% Au	333	67	30000	100	99.2	—	[33]
Pd-Ti/SiO₂	Ion exchange and impregnation, Ti:Pd = 1	323	2	375000	89	>95	—	[50]
Pd-Sn/θ-/α-Al₂O₃	Impregnation, 0.5 wt% Pd, 0.2 wt% Sn	343	1	120000	~80	99	—	[49]
KBr-Pd/γ-Al₂O₃	Microwave-assisted synthesis, 0.4 wt% Pd	308	2	36000	100	80	24	[68]
Fe-Pd/-Al₂O₃	ALD coating, 30 cycles	310	2.5	3000	99	95	—	[69]
Al-Pd/Al₂O₃	ALD coating, 0.25 wt% Pd	373	2.5	3000	99	99	62	[70]
Ag-Pd/γ-Al₂O₃	Sol immobilization, 0.5 wt% metal, Ag:Pd = 3	308	2	16200	>90	~90	50	[71]
Cu-Pd/Mn₂O₃	Sol immobilization, 1 wt% Pd, 0.9 wt% Cu	300	2	36000	99	92	10	[72]
Au-Pt/UiO-67	Impregnation-reduction, 1.89 wt% Pt, Au:Pt = 1:1.7	373	50	111000	40	80	6	[36]
Pt-Cu/Al₂O₃	Galvanic replacement method, 0.11 wt% Pt, 13.7 wt% Cu	418-433	8	1200 ^g	100	>95	25	[73]
Au-Ni/TiO₂	Co-deposition precipitation, Au:Ni = 1:0.08, 1 wt% Au	393	67	30000	100	100	—	[37]
Au-Ag/SBA-15	Deposition, 1 wt% Au, Au:Ag = 3	473	67	17550	79	100	21	[61]

Fig. 5. Structure sensitivity of Pd catalysts in the hydrogenation of 1,3-butadiene. (a) Relative variation of turnover number with respect to Pd dispersion for the hydrogenation of 1,3-butadiene. Adapted with permission from Ref. [76]. Copyright 1983, Elsevier. (b) Turnover frequency as a function of mean particle size over supported Pd catalysts at 293 K. Adapted with permission from Ref. [21]. Copyright 1991, Elsevier. (c) Turnover frequency as a function of particle size over Pd/Al2O3, normalized by the total number of Pd surface atoms (left), and Pd surface atoms within incomplete (111) facets (right). Adapted with permission from Ref. [77]. Copyright 2006, Elsevier. TOFs of Pd single crystals in (b) and (c) were indicated by the arrows.

Fig. 6. Shape effect of Pd catalysts in the hydrogenation of 1,3-butadiene. (a,c) TEM images of Pd catalysts with different shapes: I, prism; II and V, icosahedra; III and VI, cubes, IV, nanowires; (b) the TOFs as a function of Pd(111) concentration; (d) comparison of TOFs of shape-controlled Pd nanostructures on different supports. (a,b) Adapted with permission from Ref. [80]. Copyright 2008 Royal Society of Chemistry. (c,d) Adapted with permission from Ref. [51]. Copyright 2012, Wiley-VCH.

Table 2 Kinetic data of 1,3-butadiene hydrogenation on platinum surfaces.

Pt surface	TON (TOF)	E_a/(kJ mol^‒1)	a(C₄H₆)	a(H₂)
Pt(111) ^a	80	38	0	1
Pt(100) ^a	110	33	0	0.5
Pt(110) ^a	280	39	0	1
Pt foil ^b	(0.90)	41	-0.1	1.16
Pt(111) ^b	(0.85)	39	—	—
Pt(100) ^b	(0.27)	53	—	—
Pt(755) ^b	(0.71)	41	-0.13	1.12

Fig. 7. Structure sensitivity of Pt catalysts in the selective hydrogenation of 1,3-butadiene. (a) The apparent activation energy and reaction orders as a function of the particle size of Pt. The TOFs as a function of Pt dispersion over different catalysts: (b) Pt/Al2O3; (c) Ptm^Au/SiO2 and Pt/SiO2-SEA. Product distribution over different catalysts: (d) Pt/SiO2; (e) naked Pt nanoparticles; (f) Ptm^Au/SiO2. (a) Adapted with permission from Ref. [84]. Copyright 2017, Royal Society of Chemistry. (b) Adapted with permission from Ref. [83]. Copyright 1995, Elsevier. (c) Adapted with permission from Ref. [25]. Copyright 2018, American Chemical Society. (d) Adapted with permission from Ref. [85]. Copyright 2017, Royal Society of Chemistry. (e) Adapted with permission from Ref. [86]. Copyright 2013, American Chemical Society. Data in (f) taken from Ref. [25].

Fig. 8. Structure sensitivity of Au catalysts in the selective hydrogenation of 1,3-butadiene. (a) Evolution of the activity and TOF of supported gold catalysts in the hydrogenation of 1,3-butadiene in the presence of an excess of propylene at 333 K as a function of the average gold particle size [87]. Black and red symbols, chloride-free catalysts; blue symbols, chloride-containing catalysts. (b) The HD formation rate and TOFs over Au/TiO2(110) as a function of the gold particle size. H2-D2 exchange was performed in batch mode using a mixture of 6 Torr H2 and 6 Torr D2 at 425 K. (c) Arrhenius plots of the rate constants of HD formation over 1MLE (monolayer equivalent) Au/TiO2(110) surface with different gold particle sizes. (b,c) Adapted with permission from Ref. [88]. Copyright 2009, Wiley-VCH. (d) Reproduced with permission from Ref. [15]. Copyright 2010, American Chemical Society.

Fig. 9. (a) Catalytic performance of Pd catalysts over different carriers. Data taken from Ref. [48]. (b) BD conversion as a function of the PdH concentration over Pd/SiO2. (c) Arrhenius plots of the TOFs in 1,3-butadiene hydrogenation over different oxide-supported Pd-Ni catalysts. (c) Adapted with permission from Ref. [92]. Copyright 2015, Elsevier.

Fig. 10. (a) The TONs as a function of reaction time over different carriers supported Pt catalysts; (b) Shp (butenes/butenes+butane) as a function of reaction time over different carrier supported Pt catalysts; (c) BD conversion as a function of reaction time over different zeolite-supported Pt catalysts; (d) Performance of TiO2-supported Pd catalysts with different phases and porosities. (a,b) Adapted with permission from Ref. [95]. Copyright 1990, Elsevier. (c) Adapted with permission from Ref. [56]. Copyright 2015, Royal Society of Chemistry. (d) Adapted with permission from Ref. [53]. Copyright 2018, American Chemical Society.

Fig. 11. (a) The TONs and butene selectivity as a function of reaction time over Pt/SiO2-Al2O3-B with (blue symbols) and without (black symbols) ammonia pre-treatments. Performance of Pt/Al2O3 after different treatments: (b) vacuum treatment; vacuum treatment followed by H2O (c), and ethylenediamine (d) adsorption. (e) Time course of 1,3-butadiene conversion over as-prepared Au/ZrO2-CP-1073-673 (circle), and the water-treated counterpart (triangle). With the addition of ca. 0.0021% moisture in the feed after 6 h (square), and cut of the moisture in the feed with drying for additional 2 h at 473 K (diamond). (a) Adapted with permission from Ref. [95]. Copyright 1990, Elsevier. (b?d) Adapted with permission from Ref. [83]. Copyright 1995, Elsevier. (e) Adapted with permission from Ref. [100]. Copyright 2011, Elsevier.

Fig. 12. Selective hydrogenation of 1,3-butadiene over single-atom Pd catalysts. (a) Butene selectivity as a function of BD conversion; (b) product distribution at 95% BD conversion. (c) XPS Pd 3d spectra of Pd1/graphene and Pd1/C3N4; (d) BD conversion as a function of reaction temperature in 1,3-butadiene hydrogenation over Pd1/graphene and Pd1/C3N4. (a,b) Reproduced with permission from Ref. [24]. Copyright 2015, American Chemical Society. (c,d) Adapted with permission from Ref. [93]. Copyright 2019, American Chemical Society.

Fig. 13. Selective hydrogenation of 1,3-butadiene over single-atom Pt catalysts. (a) Schematic illustration of the 0.2Pt/m-Al2O3-H2 synthesis process. Aluminum isopropoxide, P123, and H2PtCl6 mixture ethanolic solution self-assembled into a gel after ethanol evaporation at 333 K. The gel was calcined at 673 K and reduced in 5% H2/N2 at 673 K, forming the single atom catalyst 0.2Pt/m-Al2O3-H2 [55]. Comparison on the performance of different Pt catalysts in 1,3-butadiene hydrogenation: (b) The selectivity of butenes and conversion of propene at 303 and 323 K [55], and (c) the selectivity of butenes and the conversion of 1,3-butadieneat 473 K for 24 h [55]. (d?g) HAADF-STEM images with (f) colored intensity map from selected region [73]. (h) EXAFS k3-weighted Fourier transforms [73]. (i) Conversion and butene selectivity as a function of temperature over Cu15/Al2O3, Pt0.1Cu14/Al2O3 and Pt0.2Cu12/Al2O3 NPs (1,3-butadiene(1.25%), H2 (20%) and He (balance), GHSV = 1200 h?1) [73]. (j) Total rate of BD hydrogenation as a function of temperature over the Pt and Cu sites of the Pt/Cu(111) single-atom catalyst where the surface concentration of the single Pt site is 0.02 ML (monolayer) and that of the Cu site is 0.98 ML. The pressure is fixed at 1 bar. Adapted with permission from Ref. [26]. Copyright 2018, American Chemical Society.

Fig. 14. (a) Conversion of 1,3-butadiene at 393 K over Au/ZrO2 catalysts containing different gold contents: 0 (triangle), 0.01 (circle), 0.05 (pentagon), 0.08 (hexagon), 0.23 (square), and 0.76 (diamond). Adapted with permission from Ref. [31]. Copyright 2005, Wiley-VCH. (b) The TOFs of Au/ZrO2 as a function of average particle size of gold. Data taken from Ref. [31].

Fig. 15. Selectivity plots as a function of conversion over different catalysts in the selective hydrogenation of 1,3-butadiene: (a) MgO-supported Rh(C2H4)2 complexes; (b) zeolite-supported Rh(C2H4)2 complexes; (c) zeolite-supported Rh(CO)2 complexes; (d) zeolite-supported Rh(C2H4)2 complexes after treatment at 353 K in H2 for 1 h; (e) MgO-supported Rh(C2H4)2 complexes after treatment at 353 K in H2 for 1 h; (f) MgO-supported Rh(C2H4)2 complexes after treatment at 353 K in H2 for 1 h and then treated with a pulse of CO. Selectivity plots for MgO-supported rhodium dimers in the absence (g) and in the presence (h) of CO ligands in the hydrogenation of 1,3-butadiene. Conditions: feed composition: 2 vol% 1,3-butadiene, balanced with H2; total pressure = 1 bar. 1-butene (circle), trans-2-butene (diamond), cis-2-butene (square), butane (triangle). Reproduced with permission from Ref. [38]. Copyright 2012, American Chemical Society.

Fig. 16. Selective hydrogenation of 1,3-butadiene over ionic liquids with different metal nanoparticles. Pd nanoparticles with (a) and without (b) the participant of BMI·BF4 under 313 K and 4 bar. (a,b) Adapted with permission from Ref. [54]. Copyright 2005, Wiley-VCH. (c) Binding energies of 1,3-butadiene and its partial hydrogenation products on Ni6 and Ni6 + IL. Data taken from Ref. [64]. (d) Optimized geometries of the (I) Ni6 cluster and the (II) Ni6 + IL; electrostatic potential maps of (III) Ni6 cluster and the (IV) Ni6 + IL. Red and blue regions in electrostatic potential maps represent the electron rich and deficient regions, respectively. Reproduced with permission from Ref. [64]. Copyright 2017, Elsevier.

Fig. 17. (a) TEM image of SiO2-encapsulated Pd nanocubes; (b) High-resolution TEM image of 30Al/Pd/Al2O3; Butene selectivity as a function of BD conversion over unsupported and SiO2-encapsulated Pd nanocubes, and the reference SiO2-supported catalysts (c), and Pd/Al2O3 with and without ALD alumina overcoats (d). (e) The synthesis of well dispersed Co species incorporated on porous carbon from metal-organic frameworks (Co-BTC-T); (f) catalytic performance of Co-BTC-T in 1,3-butadiene hydrogenation. (g) Energy dispersive X-ray spectroscopic maps showing core-shell (250 °C), partially alloyed (350 °C) and alloyed (450 °C) Au@Pd@SiO2 nanorods with XPd (atomic Pd fraction) = 0.08 and NPd (the number of Pd layer) = 2. (h) Catalytic activity and selectivity of different structure Au@Pd@SiO2 nanorods in the selective hydrogenation of butadiene. For all catalytic tests, 20 mg catalyst with 0.02 wt% metal was used. The reaction mixture consisted of 0.3% butadiene, 30% propene, 20% H2 and an amount of He to balance the flow rate to 50 mL min?1. (i) Au@Pd@SiO2 nanorods with variable Pd content and shell thickness were used: XPd = 0.04, NPd = 1 (red); XPd = 0.08, NPd = 2 (orange); XPd = 0.21, NPd = 5 (green); XPd = 0.32, NPd = 6 (blue); and Au@SiO2 (brown) and Pd@SiO2 (black) reference samples containing spherical 3.0 and 6.1 nm particles, respectively. Activity expressed as TOF (s?1) at 45 °C (left axis) and the selectivity at 98% butadiene conversion (right axis) as a function of the atomic Pd fraction. (a,c) Adapted with permission from Ref. [115]. Copyright 2015, Elsevier. (b,d) Adapted with permission from Ref. [70]. Copyright 2015, American Chemical Society. (e,f) Reproduced with permission from Ref. [65]. Copyright 2019, Elsevier. (g-i) Adapted with permission from Ref. [67]. Copyright 2021, Macmillan Publishers Ltd.: Nature.

Fig. 18. Shape effect of ZnO as the carrier for Pd catalysts in the hydrogenation of 1,3-butadiene. (a) TEM images of different shaped ZnO-supported Pd catalysts; (b) In situ HEXRD during temperature-programmed reduction for different shaped ZnO supported Pd catalysts; (c) The product distribution in BD hydrogenation. I, Pd-TiO2; II, Pd-ZnO-tetrapod; III, Pd-ZnO-brick; IV, Pd-ZnO-needle. (a?c) Adapted with permission from Ref. [52]. Copyright 2017, American Chemical Society.

Fig. 19. Reaction pathway of 1,3-butadiene hydrogenation over Pd1/graphene. Adapted with permission from Ref. [105]. Copyright, 2018 Elsevier.

Fig. 20. (a) Different adsorption modes for 1,3-butadiene on Pt(111) surfaces: I, di-σ; II, di-p-cis; III, di-p trans; IV, 1,2-di-σ-3,4-p; V, 1,4-di-σ-2,3-p; VI, 1,2,3,4-tetra-σ. (b) Energy profiles of 1,3-butadiene hydrogenation over Pt(111) surface via the 1B4R (top) and 2B1R (bottom) intermediates. (c) Hydrogenation of 2-butenyl on Pt(111) surface from the adsorbed h3 (R-h3) or partially decoordinated h1 (R-h1) reactant via a three transition state (TS-3c) or a six-center one (TS-6c), forming 1-butene in a di-σ (1B-di-σ) or p (1B-p) mode, respectively. (d) Potential energy profiles for the formation of butene from 1,3-butadienehydrogenation with the tetra-σ and the di-σ configurations on the Pt(111) surface. (a) Reproduced with permission from Ref. [118]. Copyright 2004, Elsevier. (b) Adapted with permission from Ref. [119]. Copyright 2005, American Chemical Society. (c) Reproduced with permission from Ref. [120]. Copyright 2010, American Chemical Society. (d) Reproduced with permission from Ref. [84]. Copyright 2017, Royal Society of Chemistry.

Fig. 21. (a) In situ SFG vibrational spectra of reaction intermediates produced on different sized Pt nanoparticle catalysts during 1,3-BD hydrogenation (T = 348 K with 10 Torr of 1,3-BD, 100 Torr of H2, and 650 Torr of Ar). Blue dots and red dashed lines represent averages and standard deviations of nine SFG spectra, respectively, while black lines represent optimized model SFG spectra. (b) Normalized SFG for the CH2(a)/CH3(p,up) and CH3(s) vibrational modes as a function of nanoparticle size. (c) The proposed initial reaction pathways over Pt nanoparticles of different sizes. Reproduced with permission from Ref. [86]. Copyright 2013, American Chemical Society.

Fig. 22. (a) Reaction scheme for 1,3-butadiene hydrogenation over Au(111). Insets show the adsorption modes of reactant (R), transition state (TS), and product (P). Reproduced with permission from Ref. [59]. Copyright 2014, Elsevier. (b) Temperature and gas atmosphere profile during the hydrogenation of 1,3-butadiene under operando conditions [123]. (c) The overall energy profiles and reaction snapshots for 1,3-butadiene hydrogenation over AuOH/t-ZrO2 (203) surface. Reproduced with permission from Ref. [110]. Copyright 2006, Wiley-VCH.

Fig. 23. (a) The hydrogenation rate as a function of carbon coverage over Pt(110) surface. The dotted line corresponds to the curve A = A0 × (1 - qc2). (b) Arrhenius plots on the clean Pt(110) surface and the carbon-covered surface. (c) High-angle annular dark-field scanning transmission electron micrographs of supported gold catalysts. The red of smaller than 1 nm. (d) Evolution of the 1,3-butadiene conversion as a function of time-on-stream over the Au/TiO2 to the Au/SiO2-A50 catalysts at 473 K. Conditions: 60 mg catalysts, 0.3% 1,3-butadiene, 30% propene, 20% hydrogen, and He for balance, and flow rate was 50 mL min?1. (e) Evolution of the 1,3-butadiene conversion during the hydrogenation of 1,3-butadiene over Au/TiO2 in time order, after air regeneration (50 mL min?1, at 723 K for 1.5 h), and after consecutive air-regeneration (50 mL min?1, at 723 K for 1.5 h) and reduction (50 mL min?1, at 723 K for 3 h). Reaction conditions were the same as in (d). (f) The conversion of 1,3-butadieneas a function of water vapor over Au/g-Al2O3 catalysts. (g) Optimized adsorption modes for 1,3-butadiene hydrogenation in the presence (left) and absence (right) of water on Au(111). (a,b) Reproduced with permission from Ref. [126]. Copyright 1987, Elsevier. (c?e) Reproduced with permission from Ref. [14]. Copyright 2017, American Chemical Society. (f,g) Adapted with permission from Ref. [59]. Copyright 2014, Elsevier.

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