Promotional role of Ag1 on Pd1 in dual-site configurations from atomic dispersion of alloy nanoparticles for alkyne dialkoxycarbonylation

doi:10.1016/S1872-2067(23)64631-5

Abstract

Abstract:

Heterogeneous single-metal-site catalysts frequently encounter issues related to the poor stability of their coordination structures, hindering their industrial applications. Synthesizing bimetallic single-metal-site catalysts with two closely connected single sites may realize the full potential of single-site catalysts. Herein, we present a “top-down” dispersion process to prepare bimetallic single-metal-site catalysts from Pd-Ag alloy nanoparticles induced by CO and CH₃I mixture, with the unique binuclear complex structure of Pd₁-Ag₁ established as PdI₂(CO)-I₂-AgI by combined characterization. The Pd₁-Ag₁/activated carbon (AC) catalyst showed a three times increase in conversion for acetylene dialkoxycarbonylation compared to Pd₁/AC, owing to the promotive effect of the single-Ag-site via the binuclear complex configuration. Moreover, Pd₁-Ag₁/AC showed 98% selectivity for 1,4-unsaturated dicarboxylic acid esters over ten cycles without apparent decay, with the activated adsorption amount of acetylene doubled and the reduction of active Pd₁^δ⁺ species partially inhibited. According to density functional theory calculations, the Pd₁-Ag₁/AC catalyst exhibited a substantially lower reaction energy barrier of 0.45 eV for the rate-determining step compared with that of the Pd₁/AC catalyst (1.06 eV). This study provides insight into the preparation and synergetic catalysis of bimetallic single-metal-site catalysts.

Key words: Promotive effect, Bimetallic single-metal-sites catalysts, Atomic dispersion, Alloy nanoparticles, Alkyne dialkoxycarbonylation, Durability

Xingju Li, Zheng Li, Siquan Feng, Xiangen Song, Li Yan, Jiali Mu, Qiao Yuan, Lili Ning, Weimiao Chen, Zhongkang Han, Yunjie Ding. Promotional role of Ag₁ on Pd₁ in dual-site configurations from atomic dispersion of alloy nanoparticles for alkyne dialkoxycarbonylation[J]. Chinese Journal of Catalysis, 2024, 59: 282-292.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64631-5

https://www.cjcatal.com/EN/Y2024/V59/I4/282

Figures/Tables 7

Fig. 1. (a) Schematic illustration for the synthesis of Pd1-Ag1/AC. (b) XRD patterns of Pd-Ag/AC treated with CO/CH3I at 513 K after reaction times of 0, 2, 5, 15, and 60 min. (c) HRTEM image of fresh Pd-Ag/AC. (d,e) HAADF-STEM images of samples treated with CO/CH3I for 2 min. (f) Corresponding EDS mapping to (e), the yellow dots represent I atoms, the pink dots represent Pd atoms and the red dots represent Ag atoms, 5 min (g), and 15 min (h). (i,j) Pd and Ag 3d XPS of Pd-Ag/AC treated with CO/CH3I at 513 K for 0, 2, 5, and 60 min.

Fig. 2. HRTEM (a) and HAADF-STEM (b) images of Pd1-Ag1/AC. (c,d) The R space EXAFS fitting curves of Pd-Ag/AC and Pd1-Ag1/AC. (e,f) Wavelet transform contour of Pd-Ag/AC and Pd1-Ag1/AC.

Table 1 The EXAFS fitting result of standard samples of Pd foil, Ag foil, Pd-Ag/AC and Pd1-Ag1/AC samples.

Sample	Shell	N	R (Å)	σ² (10^-3 Å²)	R-factor
Pd foil	Pd-Pd	12.0	2.74	5.3	0.004
Ag foil	Ag-Ag	12.0	2.87	9.4	0.008
Pd Pd-Ag/AC	Pd-O	0.7	2.00	3.0	0.011
Pd Pd-Ag/AC	Pd-Ag	7.8	2.78	9.0	0.011
Ag Pd-Ag/AC	Ag-O	1.2	2.04	9.5	0.015
Ag Pd-Ag/AC	Ag-Pd	8.0	2.80	7.3	0.015
Pd Pd₁-Ag₁/AC	Pd-CO	1.0	1.83	2.8	0.014
	Pd-(O=AC)	1.0	2.06	3.0
	Pd-I	3.8	2.60	3.3
Ag Pd₁-Ag₁/AC	Ag-(O=AC)	1.0	2.52	3.0	0.012
Ag Pd₁-Ag₁/AC	Ag-I	3.1	2.88	3.5	0.012

Fig. 3. (a) Activity comparison of different catalysts for acetylene dialkoxycarbonylation. Reaction conditions: catalyst (0.3 g Pd1/AC, 0.3 g Ag1/AC, 0.3 g Pd1-Ag1/AC, 0.3 g Pd-Ag/AC, 0.3 g Pd1/AC+0.3 g Ag1/AC; 0.8 wt% Pd, 1.7 wt% Ag), acetylene (8.0 mmol), CH3OH (12 mL), PCO = 2.6 MPa, Pair = 2.5 MPa, 333 K, 3.0 h. The Conv.% is the acetylene conversion and the Sel.% is the selectivity of alkyne dialkoxycarbonylation, including DMSu, DMM and DMF. (b) The reaction stability test of Pd1-Ag1/AC catalyst for acetylene dialkoxycarbonylation. Reaction conditions: catalyst (0.6 g Pd1-Ag1/AC, 0.8 wt% Pd, 1.7 wt% Ag), acetylene (8.0 mmol), CH3OH (12 mL), Pair = 2.5 MPa, PCO = 2.6 MPa, 333 K, 1.0 h. The Conv.% is the acetylene conversion and the Sel.% is the selectivity of alkyne dialkoxycarbonylation, including DMSu, DMM and DMF. (c) Pd 3d XPS of spent Pd1-Ag1/AC and spent Pd1/AC. (d) Arrhenius plots of the Pd1/AC and Pd1-Ag1/AC catalysts for C2H2 dialkoxycarbonylation.

Fig. 4. Differential heat of C2H2 adsorption over Pd1-Ag1/AC, Pd1/AC, and Ag1/AC (a), Pd-Ag/AC, Pd/AC, and Ag/AC (b).

Fig. 5. Proposed reaction mechanism comparison of acetylene dialkoxycarbonylation on Pd1-Ag1/AC (a) and Pd1/AC (b). (c) Energy diagram of the proposed catalytic cycle on Pd1-Ag1/AC and Pd1/AC and the side view of the corresponding structures. Yellow, gray, purple, red, green, and brown spheres indicate the Pd, Ag, I, O, H and C atoms, respectively.

Fig. 6. The PDOS (projected density of states) of Pd1/AC (a) and Pd1-Ag1/AC (b). Red, yellow, blue, and purple represent the d orbits of Pd, the d orbits of Ag, the p orbits of I and the s orbits of I, respectively. The black dotted line represents the center of the d-band of Pd.

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Promotional role of Ag₁ on Pd₁ in dual-site configurations from atomic dispersion of alloy nanoparticles for alkyne dialkoxycarbonylation

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