Precise construction of Pt-O-W active sites via atom replacement on CuWOx nanoislands for efficient glycerol hydrogenolysis to 1,3-propanediol

doi:10.1016/S1872-2067(25)64898-4

Abstract

Abstract:

Interfacial engineering is central to heterogeneous catalytic hydrogenation. However, achieving the precise control of bimetallic interfaces in supported bifunctional catalysts remains a critical issue. Herein, we present a strategic atom-replacement approach in which Cu acts as a spatial mediator and anchoring site, enabling Pt to be selectively deposited onto CuWO_x nanoislands, thereby forming well-defined high-density Pt-WO_x active sites for the selective hydrogenolysis of glycerol. The characterization results demonstrate that Cu species modulate the electronic states of the Pt-WO_x centers, while the cooperative interaction between Pt and Cu enhances the hydrogen spillover across the Pt-WO_x interface. This synergy promotes the formation of 1,3-propanediol (1,3-PDO) by optimizing the reaction pathway. Consequently, the Pt-WO_x/γ-Al₂O₃ catalyst achieved 65% selectivity to 1,3-PDO with a space-time yield of 0.302 g_1,3-PDO·g_cat^-1·h^-1 at a high glycerol concentration (30.0 wt%), outperforming all previously reported Al₂O₃-based systems. This work not only provides a new approach for nanoisland synthesis, but also offers valuable insights into interfacial control in heterogeneous catalysis.

Key words: Heterogeneous catalysis, Pt-W catalyst, Glycerol hydrodeoxygenation, Nanoisland, 1,3-Propanediol

Jieqi Zou, Qian He, Lei Liu, Binbin Zhao, Jinxiang Dong. Precise construction of Pt-O-W active sites via atom replacement on CuWO_x nanoislands for efficient glycerol hydrogenolysis to 1,3-propanediol[J]. Chinese Journal of Catalysis, 2026, 84: 347-358.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64898-4

https://www.cjcatal.com/EN/Y2026/V84/I5/347

Figures/Tables 8

Scheme 1. Procedure for the synthesis of homogeneous and highly dispersed “nanoisland” cluster catalysts.

Fig. 1. Structural characterization and electron microscopy images of nanoislands. (a) XRD patterns of different catalysts. (b) FT-IR patterns to determine the structure of CuWOx. (c) UV-vis patterns of the catalysts before and after the addition of Cu. AC-high-angle angular dark-field (HAADF)-STEM and EDS mapping images of CuWOx/γ-Al2O3 (d-f) and Pt-WOx/γ-Al2O3 (g-i). (e1,h1) are the HAADF intensity maps obtained by point-by-point scanning of atoms along the line marked in (e2,h2).

Table 1 Basic parameters of the sample.

Samples	C_Pt^a (wt%)	C_W^a (wt%)	C_Cu^a (wt%)	Cu/W atomic ratio^a	D_Pt^b (%)	H₂^c (mmol·g^-1)	NH₃^d (mmol·g^-1)
CuWO_x/γ-Al₂O₃	—	5.42	0.84	0.45	—	0.24	0.70
WO_x/γ-Al₂O₃	—	5.33	—	—	—	0.17	0.59
Pt-WO_x/γ-Al₂O₃	1.87	5.34	0.16	0.09	61.36	1.23	1.41
Pt/WO_x/γ-Al₂O₃	1.98	5.25	—	—	58.94	0.56	1.07

Fig. 2. In-situ FT-IR and XPS investigations of the electron transfer between Pt and W and the strength of Cu-mediated interactions. (a) In-situ DRIFTS spectra of CO chemisorption on the CuWOx/γ-Al2O3 sample. (b) Corresponding Gaussian fitting of CO-DRIFTS spectra for the Pt-WOx/γ-Al2O3 sample. XPS spectra of Pt-WOx/γ-Al2O3 and Pt/WOx/γ-Al2O3 in the Pt 4f (c), W 4f (d), and O 1s (e) regions. (f) In-situ DRIFTS spectra of CO chemisorption on Pt-WOx/γ-Al2O3 and Pt/WOx/γ-Al2O3 samples.

Fig. 3. Catalyst performance tests. (a) Catalytic performance of various catalysts in the glycerol hydrogenation reaction (150 °C). (b) Impact of different reaction temperatures on the catalytic performance (12 h). (c) Comparison of the 1,3-PDO productivity and Pt efficiency among current aluminum-containing Pt-W catalytic systems for glycerol hydrodeoxygenation. Detailed data are also compiled in Table S4.

Fig. 4. Analysis of the ability of the catalyst to dissociate and activate H2. In-situ H2-DRIFTS of CuWOx/γ-Al2O3 (a) and two Pt-containing catalysts (b,c), together with an enlarged comparison (d). H2-TPD profiles (e) and comparative H2 uptake (f) of the different catalysts.

Fig. 5. Adsorption and hydrogenolysis of glycerol. (a) Adsorption configuration of glycerol on Pt-WOx nanoislands. Liquid FT-IR spectra of glycerol, 1,3-PDO, 1,2-PDO (b) compared with the FT-IR spectra of glycerol (c) adsorbed on γ-Al2O3. (d) FT-IR spectra of glycerol adsorption on CuWOx/γ-Al2O3 with temperature adsorption and desorption. In-situ FT-IR spectra of glycerol on Pt-WOx/γ-Al2O3 (e) and Pt/WOx/γ-Al2O3 (f) under Ar-H2 atmosphere switching. (g) Desorption plots of the intensity ratio of primary to secondary hydroxyl groups with increasing temperature on γ-Al2O3 and CuWOx/γ-Al2O3. (h) Comparison of magnified plots of the changes in the intensity of primary and secondary hydroxyl groups after switching H2 in Fig. (e). (i) H2-TPR spectra of different sample surfaces.

Fig. 6. Catalyst surface acidity and mechanism. NH3-TPD spectra of different catalysts (a) and results of Gaussian peak fitting in the highly acidic region of Pt-containing samples (b). (c) Pyridine adsorption FT-IR spectra of Pt-containing samples collected at 150 °C. Real-time H2 adsorption IR spectra of NH3 adsorption on Pt-WOx/γ-Al2O3 (d), Pt/WOx/γ-Al2O3 (e), and CuWOx/γ-Al2O3 (f) after Ar blowdown and 1 h of NH3 adsorption collected at 100 °C. Glycerol adsorption hydrogenolysis mechanism diagram over Pt-containing catalysts prepared by atom replacement (g) and impregnation (h) methods.

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