A Cu-incorporated NASICON catalyst executing one-step conversion of methanol and acetic acid to acrylic acid and its esters

doi:10.1016/S1872-2067(26)65014-0

Abstract

Abstract:

Direct synthesis of acrylic acid (AA) from methanol and acetic acid is promising for the high-value utilization of coal-based chemicals. However, this direct synthesis faces challenges due to limited catalyst functionality or insufficient synergistic effects among multiple active sites. Herein, we constructed a series of bifunctional catalysts (CuO-NSCs) by incorporating Cu into NASICON material for direct synthesis of AA. A total selectivity of 96.0% to AA, methyl acrylate (MA), and methyl acetate was achieved over a 2.5 wt% CuO-NSC catalyst, with the 56.3% selectivity of AA+MA, approximately 23% higher than the one ever reported (33%). Our research revealed that NASICON substrate promoted the formation of more Cu⁺ species, which are crucial redox active sites for methanol dehydrogenation into formaldehyde; furthermore, the appropriate introduction of Cu somewhat regulated surficial acid-base properties, specifically increasing the density of medium-strength acidic and basic sites that are essential for the aldolization of acetic acid and formaldehyde. Apparently, the superior activity of the catalyst was attributed to good synergistic effects between the redox sites and acid-base sites.

Key words: Acrylic acid, Acetic acid, Methanol, Sodium superionic conductor, One-step conversion

Jiahao Wang, Qiliang Gao, Chao Li, Xiujuan Gao, Jian Gong, Faen Song, Junfeng Zhang, Yizhuo Han, Qingde Zhang. A Cu-incorporated NASICON catalyst executing one-step conversion of methanol and acetic acid to acrylic acid and its esters[J]. Chinese Journal of Catalysis, 2026, 85: 356-370.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65014-0

https://www.cjcatal.com/EN/Y2026/V85/I6/356

Figures/Tables 14

Scheme 1. Present synthesis pathways for the production of acrylic acid.

Fig. 1. (a) Catalytic performance for direct AA synthesis over catalysts with different CuO loadings. Reaction conditions: 380 °C, feed ratio = 2:1, LHSV =1.5 mL·g-1·h-1, and the fed air rate =26 mL·min-1. (b) Evaluation results using formaldehyde and HAc as raw material.

Fig. 2. Effects of reaction conditions on the 2.5 wt%CuO-NSC catalyst. (a) Effect of reaction temperature. Reaction conditions: LHSV = 1.5 mL·g-1·h-1, methanol/HAc feed ratio = 2:1, air feed rate = 26 mL·min-1. (b) Effect of LHSV. Reaction conditions: 380 °C, methanol/HAc feed ratio = 2:1, air feed rate = 26 mL·min-1. (c) Effect of feed ratio. Reaction conditions: 380 °C, LHSV = 1 mL·g-1·h-1, air feed rate = 26 mL·min-1. (d) Effect of air feed rate. Reaction conditions: 380 °C, LHSV = 1 mL·g-1·h-1, methanol/HAc feed ratio = 3:1.

Fig. 3. XRD spectra (a) and Raman spectra (b) of the synthesized catalysts. (A) 0 wt%CuO-NSC; (B) 1.0wt %CuO-NSC; (C) 2.5 wt%CuO-NSC; (D) 5.0 wt%CuO-NSC; (E) 7.5 wt%CuO-NSC.

Fig. 4. The 31P (I = ½) MAS-NMR spectrum of the prepared catalysts.

Table 1 The textural properties of the synthesized catalysts.

Catalyst	Surface area (m²⋅g⁻¹)	Pore volume (cm³⋅g⁻¹)	Average pore diameter (nm)
0wt%CuO/NSC	43.5	0.25	16.0
1.0wt%CuO/NSC	39.5	0.28	28.5
2.5wt%CuO/NSC	76.2	0.41	21.2
5.0wt%CuO/NSC	61.2	0.27	17.6
7.5wt%CuO/NSC	43.8	0.29	26.4

Fig. 5. Ti 2p (a) and Cu 2p (c) XPS spectra of the catalysts. (A) 0 wt%CuO-NSC; (B) 1.0 wt%CuO-NSC; (C) 2.5 wt%CuO-NSC; (D) 5.0 wt%CuO-NSC; (E) 7.5 wt%CuO-NSC. Ti 2p (b) and Cu 2p (d) XPS fitting spectra of the catalysts. Normalized Cu K-edge XANES (e), and FT k3 -weighted Cu K-edge EXAFS spectra in R-space (f) of the 2.5 wt%CuO-NSC, 7.5 wt%CuO-NSC, Cu-foil, Cu2O, CuO. WT-EXAFS of Cu K-edge signal of the CuO (g), Cu2O (h), 2.5 wt%CuO-NSC (i), and 7.5 wt%CuO-NSC (j).

Table 2 The distribution of Ti species on the representative catalysts based on Ti 2p XPS spectra.

Catalyst	Ti³⁺ (%)	Ti⁴⁺ (%)	Ti³⁺/Ti⁴⁺
0 wt%CuO/NSC	53.4	46.6	1.14
1.0 wt%CuO/NSC	54.6	45.4	1.20
2.5 wt%CuO/NSC	55.9	44.1	1.26
5.0 wt%CuO/NSC	60.2	39.8	1.51
7.5 wt%CuO/NSC	65.2	34.8	1.87

Fig. 6. XPS spectra of O 1s of representative catalysts. (A) 0 wt% CuO-NSC; (B) 1.0 wt% CuO-NSC; (C) 2.5 wt% CuO-NSC; (D) 5.0 wt% CuO-NSC; (E) 7.5 wt% CuO-NSC. The shaded regions in the figure: α denotes lattice oxygen species, β represents chemically adsorbed oxygen species, and γ corresponds to hydroxyl oxygen species.

Table 3 Calculation of acid-base sites of the presentative catalysts based on NH3/CO2-TPD profiles.

Catalyst	Total acidic sites (μmol⋅g_cat^-1)	Acidic sites density (μmol⋅g_cat^-1)			Total basic sites (μmol⋅g_cat^-1)	Basic sites density (μmol⋅g_cat^-1)		B/L
Catalyst	Total acidic sites (μmol⋅g_cat^-1)	Weak	Medium	Strong	Total basic sites (μmol⋅g_cat^-1)	Weak	Medium	B/L
0 wt%CuO-NSC	143	29	98	16	45	16	29	1.68
1.0 wt%CuO-NSC	148	30	70	48	50	21	29	0.91
2.5 wt%CuO-NSC	149	38	57	54	54	22	32	0.66
5.0 wt%CuO-NSC	121	38	56	27	76	27	49	0.56
7.5 wt%CuO-NSC	115	49	30	36	69	29	40	0.26

Fig. 7. (a) NH3-TPD profiles of selected catalysts. (b) Py-IR adsorption spectra for various catalysts. (c) CO2-TPD profiles of representative catalysts. (A) 0 wt%CuO-NSC; (B) 1.0 wt%CuO-NSC; (C) 2.5 wt%CuO-NSC; (D) 5.0 wt%CuO-NSC; (E) 7.5 wt%CuO-NSC.

Fig. 8. In-situ DRIFTS spectra of HAc (a) and methanol (b,c) over the catalysts as-prepared. (A) 0 wt%CuO-NSC; (B) 1.0 wt%CuO-NSC; (C) 2.5 wt% CuO-NSC; (D) 5.0 wt%CuO-NSC; (E) 7.5 wt%CuO-NSC.

Scheme 2. Reaction routes on bifunctional NASICON catalysts.

Fig. 9. The durability of 2.5 wt%CuO-NSC catalyst in a period of 50 h. Reaction conditions: 380 °C, feed ratio = 3:1, LHSV = 1 mL·g-1·h-1 and the fed air rate = 26 mL·min-1.

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