M/C3N4/AC (M = Au, Pt, Ru)-catalyzed acetylene coupling with ethylene dichloride: How effective are the bifunctionalities?

doi:10.1016/S1872-2067(21)63913-X

Abstract

Abstract:

Acetylene coupling with ethylene dichloride, which uses both coal and oil resources, is attractive for sustainable PVC manufacturing. Herein, highly active and stable carbon nitride-based catalysts were developed by a novel pre-oxidation-pyrolysis process, affording unprecedented dehydrochlorination activity with good durability. The best-performing system was further modified with different precious metals (Au, Pt, and Ru) to promote the hydrochlorination chemistry between the in-situ formed hydrogen chloride and acetylene co-feed. The presence of metal centers intensifies the hydrochlorination activity but weakens the dehydrochlorination ability due to competitive adsorption between the two reactants at the metal sites. Superior coupling performance was achieved over C₃N₄/AC and single-atom Au/C₃N₄/AC catalysts in cascade reactors. Our results strongly suggest that dehydrochlorination is an essential step in the coupling reaction, and the activation of acetylene and ethylene dichloride molecules requires different active sites that should be engineered in future work.

Key words: Acetylene hydrochlorination, Bi-functional catalyst, Dehydrochlorination, Ethylene dichloride, Vinyl chloride

Qing Yu, Shiyi Wang, Mengru Wang, Xiaoling Mou, Ronghe Lin, Yunjie Ding. M/C₃N₄/AC (M = Au, Pt, Ru)-catalyzed acetylene coupling with ethylene dichloride: How effective are the bifunctionalities?[J]. Chinese Journal of Catalysis, 2022, 43(3): 820-831.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63913-X

https://www.cjcatal.com/EN/Y2022/V43/I3/820

Figures/Tables 6

Fig. 1. Characterizations of the bulk and supported carbon nitride catalysts. (a) XRD; (b) TEM; (c) N 1s XPS. (d) The distribution of different functionalities: (1) C=N-C; (2) N-(C)3 or H-N-(C)2; (3) quaternary N; and (4) π-excitations.

Table 1 Characterization data of the selected catalysts.

Sample ^a	V_total^b/(cm³ g^‒1)	V_micro^c/(cm³ g^‒1)	A_meso^c/(m² g^‒1)	A_BET^d/(m² g^‒1)	M ^e/(wt%)	C ^f/(at%)	N ^f/(at%)	O ^f/(at%)
C₃N₄	0.02	0.00	5	6	—	42.1	55.9	2.0
AC	0.52	0.22	467	979	—	—	—	—
C₃N₄-D/AC	0.33	0.15	285	634	—	88.2	8.1	3.7
C₃N₄-D/AC-523	0.33	0.14	296	621	—	87.7	8.0	4.3
C₃N₄-D/AC-573	0.38	0.15	334	689	—	86.5	8.7	4.8
C₃N₄-D/AC-623	0.43	0.17	385	786	—	88.3	8.0	3.7
C₃N₄-U/AC	0.54	0.21	477	979	—	94.2	2.3	3.5
C₃N₄-U/AC-523	0.46	0.21	402	889	—	—	—	—
C₃N₄-U/AC-573	0.98	0.21	407	894	—	94.0	3.1	2.9
C₃N₄-U/AC-623	0.98	0.22	439	939	—	—	—	—
C₃N₄-D/AC-623-100h ^g	0.17	0.01	202	225	—	—	—	—
C₃N₄-U/AC-573-100h ^g	0.43	0.15	412	754	—	—	—	—
Au/AC	0.52	0.23	425	968	1.01	—	—	—
Au/C₃N₄	0.10	0.00	26	26	1.00	—	—	—
Au/C₃N₄-U/AC-573	0.49	0.21	422	905	0.99	90.5	2.8	5.7
Pt/C₃N₄-U/AC-573	0.48	0.19	427	893	1.02	—	—	—
Ru/C₃N₄-U/AC-573	0.44	0.22	336	858	1.01	—	—	—
BaCl₂/AC	0.44	0.19	339	788	10.63	—	—	—
Au/C₃N₄-U/AC-573-50h ^h	0.34	0.13	314	628	—	—	—	—

Fig. 2. Characterization of the fresh Au/C3N4-U/AC-573 catalyst. (a) HAADF-STEM images at different magnifications, XPS spectra of Au 4f (b) and Cl 2p (c); (d) Normalized XANES spectra; (e) FT-EXAFS of Au L3 edge of the Au/C3N4-U/AC-573 catalyst and the reference samples.

Fig. 3. (a) Catalytic performance of different catalysts in the dehydrochlorination of ethylene dichloride; (b) Effect of pre-oxidation treatment on the catalytic performance of supported carbon nitride catalysts with different precursors; (c) Comparison of the performance of the developed catalysts with those of previously reported results; (d) Time-on-stream performance of the best-performing catalysts in this work. Reaction conditions: (a,b) GHSVEDC = 144 h-1, FT = 100 cm3 min-1, Tbed = 573 K, PEDC = 2.4%, Wcat. = 0.5 g; (c,d) PEDC = 4.8 %, FT = 50 cm3 min-1, Tbed = 573 K, Wcat .= 1 g (100 TOS) or 0.25 g (50 h TOS). Reference catalysts: DAR-3-700 [12], C4444P+Cl- [16], N-AC [17], TPPC/AC [18], g-C3N4/AC [19], N-AC [21], and 30Pyrrole/AC [22].

Fig. 4. Characterizations of the fresh catalysts and those after 100 h on-stream tests in the dehydrochlorination of ethylene dichloride. (a) N2 sorption; (b) TG (top) and DTG (bottom) analysis.

Fig. 5. (a) Comparison of the performance of different catalysts in single-bed reactor for dehydrochlorination of ethylene dichloride, reaction conditions: GHSVEDC = 144 h-1, FT = 50 cm3 min-1, Tbed = 573 K, PEDC = 4.8 %, Wcat = 0.5 g, and acetylene coupling with ethylene dichloride, reaction conditions: GHSVEDC = 144 h-1, nEDC/nC2H2 = 1.2, Tbed = 573 K, Wcat = 0.5 g; performance of bifunctional catalysts in dual-bed reactor for acetylene coupling with ethylene dichloride (b) accompanied with time-on-stream performance of the best-developed dual-bed system (e). Reaction conditions: GHSVEDC = 72 h-1, nEDC/nC2H2 = 1.2, Tbed = 573 K, Cat.-T: C3N4-U/AC-573, Wcat. = 0.5 g, Cat.-B: M/C3N4-U/AC-573, Wcat. = 0.5 g. Au/C3N4-U/AC-573* was packed at the top. Schematic illustrations of the reaction pathways over the single- (c) and dual-bed (d) systems. The formation of HCl was facilitated (solid purple arrow) on the dual-bed system while it was inhibited (dashed purple arrow) in the single-bed reactor.

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M/C₃N₄/AC (M = Au, Pt, Ru)-catalyzed acetylene coupling with ethylene dichloride: How effective are the bifunctionalities?

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