Solar energy-driven C-H activation of methanol for direct C-C coupling to ethylene glycol with high stability by nitrogen doped tantalum oxide

doi:10.1016/S1872-2067(21)63797-X

Abstract

Abstract:

Direct photocatalytic coupling of methanol to ethylene glycol (EG) is highly attractive. The reported photocatalysts for this reaction are all metal sulfide semiconductors, which may suffer from photocorrosion and have low stability. Thus, the development of non-sulﬁde photocatalysts for efficient photocatalytic coupling of methanol to EG and H₂ with high stability is urgent but extremely challenging. Herein, the first metal oxide photocatalyst, tantalum-based semiconductor, is reported for preferential activation of C-H bond within methanol to form hydroxymethyl radical (•CH₂OH) and subsequent C-C coupling to EG. Compared with other metal oxide photocatalysts, such as TiO₂, ZnO, WO₃, Nb₂O₅, tantalum oxide (Ta₂O₅) is unique in that it can realize the selective photocatalytic coupling of methanol to EG. The co-catalyst free nitrogen doped tantalum oxide (2%N-Ta₂O₅) shows an EG formation rate as high as 4.0 mmol g_cat^-1 h^-1, about 9 times higher than that of Ta₂O₅, with a selectivity higher than 70%. The high charge separation ability of nitrogen doped tantalum oxide plays a key role in its high activity for EG production. This catalyst also shows excellent stability longer than 160 h, which has not been achieved over the reported metal sulfide photocatalysts. Tantalum-based photocatalyst is an environmentally friendly and highly stable candidate for photocatalytic coupling of methanol to EG.

Key words: Methanol, C-H activation, C-C coupling, Ethylene glycol, Tantalum-based photocatalyst

Limei Wang, Daxue Du, Biao Zhang, Shunji Xie, Qinghong Zhang, Haiyan Wang, Ye Wang. Solar energy-driven C-H activation of methanol for direct C-C coupling to ethylene glycol with high stability by nitrogen doped tantalum oxide[J]. Chinese Journal of Catalysis, 2021, 42(9): 1459-1467.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63797-X

https://www.cjcatal.com/EN/Y2021/V42/I9/1459

Figures/Tables 8

Fig. 1. (a) Schematic illustration for the synthesis of N-Ta2O5. SEM images of Ta2O5 (b), 0.6%N-Ta2O5 (c), 2%N-Ta2O5 (d), and 7%N-Ta2O5 (e); (f) EDX mapping and element distributions of 2%N-Ta2O5.

Fig. 2. XRD patterns (a) and Raman spectra (b) of Ta2O5 and N-Ta2O5; N 1s (c), and (d) Ta 4f XPS spectra of Ta2O5 and N-Ta2O5.

Fig. 3. (a) UV-Vis diffuse reflectance spectra of Ta2O5 and N-Ta2O5; (b) The corresponding plots of modified Kubelka-Munk function versus the energy of exciting light of Ta2O5 and N-Ta2O5; (c) Energy levels of several related redox couples and band-edge positions of Ta2O5 and N-Ta2O5.

Table 1 Photocatalytic performances of Ta2O5, N-Ta2O5 and some typical metal oxide photocatalysts for the MTEG reaction.

Catalyst	Formation rate (mmol g_cat^-1 h^-1)						e^-/h^{+ a}	Selectivity ^b (%)
Catalyst	EG	HCHO	HCOOH	CO	CO₂	H₂	e^-/h^{+ a}	EG	HCHO	HCOOH
Ta₂O₅	0.43	0.26	0	0	0	0.58	1.09	73	27	0
0.6%N-Ta₂O₅	2.0	2.4	0.01	0	0	4.3	0.96	62	37	1
2%N-Ta₂O₅	4.0	3.2	0.10	0	0	8.7	1.06	71	28	1
7%N-Ta₂O₅	0.2	0.13	0	0	0	0.27	0.93	76	24	0
TiO₂	0	1.6	0.11	0.16	0.042	2.0	0.91	0	84	5.6
ZnO	0	3.0	0.038	0.23	0.028	3.1	0.90	0	91	1.2
WO₃	0	0.48	0.051	0	0	0.23	0.94	0	99	1
Nb₂O₅	0	1.4	0.071	0	0	0.8	1.1	0	99	1

Fig. 4. (a) Time course process of 2%N-Ta2O5 in MTEG reaction within 12 h. (b) The product formation rate of 2%N-Ta2O5 in repeated use within 14 cycles (12 h for each cycle). (c) Quantum yields of EG at different wavelengths and UV-Vis diffuse reflectance spectrum of 2%N-Ta2O5. (d) Photocatalytic performances of 2%N-Ta2O5 in 60 h. Reaction conditions: catalyst, 10 mg; solution, 4.0 mL CH3OH (76 wt%) + 1.0 mL H2O (24 wt%), 5.0 mL; N2 atmosphere; 300 W Xe lamp as light source.

Fig. 5. (a) Transient photocurrent responses of Ta2O5 and N-Ta2O5; (b) SPV spectra of Ta2O5 and N-Ta2O5.

Fig. 6. (a) Electron density differences of the top view for Ta2O5 (left) and N-Ta2O5 (right) models. Iso-surface value is 0.004 e?-3. Yellow and blue contours represent electron accumulation and depletion, respectively. (b) Calculated TDOS for Ta2O5 and N-Ta2O5 models.

Fig. 7. (a) In situ ESR spectra of systems containing Ta2O5 and N-Ta2O5 catalysts in aqueous methanol solutions in the presence of DMPO (a spin-trapping agent) without or with light irradiation; (b) Illustration of the photocatalytic coupling of methanol to EG over N-Ta2O5 catalyst.

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