Highly efficient Ag-modified copper phyllosilicate nanotube: Preparation by co-ammonia evaporation hydrothermal method and application in the selective hydrogenation of carbonate

doi:10.1016/j.jmst.2020.02.020

Abstract

Abstract:

Rapidly deactivation of Cu/SiO₂ catalysts at high liquid hour space velocity (LHSV) has been an important obstacle for scale-up application. Herein, silver modified copper phyllosilicate nanotubes were fabricated by different strategies, and implemented to the selective hydrogenation of ethylene carbonate (EC) to methanol and ethylene glycol (EG) as alternative route for the indirect utilization of CO₂. The CuPs Ag-copre catalyst synthesized by the co-ammonia evaporation hydrothermal process achieved 79% methanol and 99% EG yield within various ranges of EC LHSV, which was attributed to the balanced Cu⁺/Cu⁰ ratio and the enhanced H₂ dissociation ability. Inlaid silver species over copper phyllosilicate promoted the interaction between the metal and the support, which substantially regulated the reducibility and dispersion of copper species, meanwhile, increased the stability for long-term running of the catalyst.

Key words: Copper, Silver, Carbonate, Hydrogenation, Methanol, Ethylene glycol

Huabo Li, Yuanyuan Cui, Yixin Liu, Lu Zhang, Quan Zhang, Juhua Zhang, Wei-Lin Dai. Highly efficient Ag-modified copper phyllosilicate nanotube: Preparation by co-ammonia evaporation hydrothermal method and application in the selective hydrogenation of carbonate[J]. J. Mater. Sci. Technol., 2020, 47: 29-37.

Figures/Tables 12

Scheme 1. Methanol production for the CO2 indirect utilization via carbonate process.

Table 1 Catalytic activity over Ag modified CuPs catalysts.

Entry	Catalyst	Conversion (%)	Yield (%)
Entry	Catalyst	Conversion (%)	Methanol	Ethylene glycol
1	CuPs	>99	72	98
2	CuPs Ag-copre	>99	79	99
3	CuPs Ag-post	>99	74	98
4	CuPs Fe-copre	96	31	87
5	CuPs Ni-copre	>99	12	85
6	CuPs Co-copre	92	42	79
7	CuPs Ru-copre	>99	73	99
8	Cu/SiO₂ ^a	47	28	36
9	Ag/SiO₂	11	6	9

Fig. 1. EC conversion and methanol yield as a function of different EC LHSV over Ag modified CuPs catalysts.

Fig. 2. EC hydrogenation over CuPs Ag-copre catalyst as a function of time on stream. Reaction Conditions: LHSV(EC) =0.20 h-1, P(H2) =3.0 MPa, T =453 K, n(H2):n(EC) = 80.

Fig. 3. N2 adsorption-desorption isotherms (a) and pore diameter distribution (b) of the calcined CuPs Ag-copre, CuPs Ag-post, CuPs and Ag/SiO2 samples.

Fig. 4. FT-IR spectra of the calcined Ag modified CuPs catalysts.

Fig. 5. XRD patterns of the Ag modified CuPs catalysts: (a) calcined, (b) reduced.

Table 2 Physicochemical parameters of the Ag modified CuPs catalysts.

Catalyst	^aM loading (%)		S_BET (m²/g)	V_p (cm³/g)	d_p (nm)	^b d_Cu (nm)	^cD_Cu (%)	^c S_Cu⁰ (m²/g_cat)	^d TOF (h^-1)
Catalyst	Cu	Ag	S_BET (m²/g)	V_p (cm³/g)	d_p (nm)	^b d_Cu (nm)	^cD_Cu (%)	^c S_Cu⁰ (m²/g_cat)	^d TOF (h^-1)
CuPs	33.5	-	497	1.05	6.6	6.2	27.8	60.5	9.1
CuPs Ag-copre	35.1	1.6	511	1.21	7.0	7.5	33.1	75.6	12.7
CuPs Ag-post	31.9	2.5	408	0.53	4.2	9.3	26.1	54.3	11.3
Ag/SiO₂	-	1.9	137	0.45	10.3	7.7	-	-	-

Fig. 6. TEM images of CuPs Ag-copre (a,c) and CuPs Ag-post (b,d) catalysts: calcined (a,b) and reduced (c,d); SEM images of the calcined CuPs Ag-copre (e) and CuPs Ag-post (f) samples.

Fig. 7. H2-TPR profiles of the Ag modified CuPs catalysts.

Fig. 8. Cu 2p (a), Ag 3d (b) XPS and Cu LMM (c) XAES spectra of the reduced Ag modified CuPs catalysts.

Fig. 9. Correlation of methanol yield and Cu+ content over Ag modified CuPs catalysts.

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