Zinc Loss Inhibition in Phosphorus-Doped Zinc-Based Core-Shell Catalysts for Vinyl Acetate Synthesis

DOI: https://doi.org/10.62517/jiem.202503105

Author(s)

Yilei Feng, Peng Ren, Dashun Lu, Hao Jiang, Ruyue Tan, Xugen Wang*, Bin Dai*

Affiliation(s)

School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, Xinjiang, China *Corresponding Author.

Abstract

A phosphorus-incorporated, zinc-based core-shell catalyst was synthesized via an in situ method for selective coating. The catalyst showed excellent activity and stability for the vinyl acetate synthesis. Results indicated that the optimal activity (53%) was achieved when adding 5% of HEDP (Etidronic acid) to the RF solution during the core-shell preparation, followed by calcination at 650℃. Characterization showed that the addition of HEDP decreased the electron cloud density around Zn, enhancing the adsorption of acetic acid and reducing the adsorption of acetylene, which facilitated the reaction and improved the conversion rate of acetic acid. A stability test over 550 h showed that the activity decreased by about 3%; the Zn loss rate was 6.29% (0.011%/h). The loss rate for the catalysts without a phosphorous source and with HEDP was 0.031%/h and 0.025%/h, respectively. This indicates that the addition of HEDP effectively mitigates the Zn loss rate.

Keywords

Origin of Generation; HEDP; Zn Loss; Core-shell Catalyst

References

[1] TAZEHABADI M J M, ANSARI M, SABZEVARI A. Controlled synthesis of poly (vinyl alcohol)-poly (acrylic acid) copolymers via cobalt mediated radical polymerization of vinyl acetate initiated by V-70. Journal of Molecular Structure, 2025, 1331: 141637-141637. [2] ZHANG Y, LI Q, ZHANG Y, et al. Construction of efficient hydrogen evolution catalyst and analysis of the influence of complexing agent type. International Journal of Hydrogen Energy, 2023, 49(PC): 676-688. [3] MILITZER C, BUCHSBAUM J, DZHAGAN V, et al. Atomic Layer Deposition of Titanium Phosphate from Titanium Tetrachloride and Triethyl Phosphate onto Carbon Fibers. Advanced Materials Interfaces, 2018, 5(16): n/a-n/a. [4] HUANG J, WANG W, LI H. Water–Medium Organic Reactions Catalyzed by Active and Reusable Pd/Y Heterobimetal–Organic Framework. ACS Catalysis, 2013, 3(7): 1526-1536. [5] XIANGYU J, BO J, MANRUI M, et al. Complex Core–Shell Architectures through Spatially Organized Nano-Assemblies. ACS Nano, 2025, 3(7): 1526-1536. [6] YIRAN B, YUNJIAN W, YIBING Y, et al. Unveiling the role of heteroatom doping and strain in Core-Shell catalysts for CO2RR. Chemical Engineering Journal, 2025, 507: 160155. [7] CHEN Z, ZHAO F, ZHANG H, et al. Effects of trifluoromethanesulfonic acid ligand on the Zinc-based catalysts for the acetylene hydration. Chinese Chemical Letters, 2022, 34(6): 107963. [8] ZHANG H, XIAO R, LI R, et al. Enhanced aqueous Cr (VI) removal using chitosan-modified magnetic biochars derived from bamboo residues. Chemosphere, 2020, 261: 127694. [9] QIAN H-S, HAN F-M, ZHANG B, et al. Non-catalytic CVD preparation of carbon spheres with a specific size. Carbon, 2004, 42(4): 761-766. [10] KRISHNAMOORTHY N, SIVASANKARAPILLAI V S, NATARAJAN V K, et al. Biocidal activity of ZnO NPs against pathogens and antioxidant activity - a greener approach by Citrus hystrix leaf extract as bio-reductant. Biochemical Engineering Journal, 2023, 192: 108818. [11] YU Y-B, ZHANG Q, WU L-Y, et al. Reaction mechanism of N-(4-hydroxyphenyl) ethanamide electrodegradation via phosphorus-graphene prepared from triphenylphosphine: Generation and destruction of the reactive species. Chemical Engineering Journal, 2020, 403: 126322. [12] JIANG H, YAN L, ZHANG S, et al. Electrochemical Surface Restructuring of Phosphorus-Doped Carbon@MoP Electrocatalysts for Hydrogen Evolution. Nano-Micro Letters, 2021, 13: 215. [13] YANG J, GUO D, ZHAO S, et al. Cobalt Phosphides Nanocrystals Encapsulated by P‐Doped Carbon and Married with P‐Doped Graphene for Overall Water Splitting. Small, 2019, 15(10): n/a-n/a. [14] GHAFFARIZADEH S A, ZANDAVI S H, WARD C A. Specific Surface Area from Nitrogen Adsorption Data at 77 K Using the Zeta Adsorption Isotherm. The Journal of Physical Chemistry C, 2017, 21(41), 23011-23016. [15] LI M, XU Z, CHEN Y, et al. MOFs-Derived Zn-Based Catalysts in Acetylene Acetoxylation. Nanomaterials, 2021, 12(1): 98.