甲烷/甲醇光催化转化研究进展

doi:10.3866/PKU.WHXB201810002

Abstract

Abstract:

With the increasing energy demands and the limited petroleum reserves, it is highly desirable to produce fuels and chemicals from non-petroleum feedstocks, such as coal, natural gas and biomass. Catalytic conversion of C₁ resources (CO, CO₂, CH₃OH, CH₄, etc.) affords various products and attracts increasing attention from both academia and industries. Methane and methanol are important C₁ feedstocks in the production of fuels and chemicals. In order to obtain high selectivity for the target product, it is necessary to control the activation of C―H bonds in methane and methanol. However, this remains a great challenge. Although the traditional thermal catalytic conversion of methane and methanol has been developed over decades, there are still some disadvantages associated with the catalytic process, such as harsh reaction conditions, high energy consumption, and low selectivity. Photocatalysis, which is driven by photoenergy, can compensate for the Gibbs free energy. In the photocatalytic reactions, semiconductor photocatalysts absorb photons and generate electrons and holes in their conduction and valence bands, respectively, to accelerate the reaction rate. The position of the conduction band determines the oxidation capacity, and the bandgap determines the light absorption property. Normally, the oxidation capacity of photocatalysts is regulated by choosing semiconductors with a suitable bandgap or anions/cations doping. Fabrication of heterojunction and loading metalsare recognized as effective methods to promote the separation of electron-hole pairs and improve the photocatalytic efficiency. In contrast to thermal catalysis, photocatalysis can be carried out under mild reaction conditions with low energy consumption. Recently, photocatalysis has been considered an attractive route for the efficient conversion of methane and methanol to fuels and chemicals. Partial oxidation of methane, which is necessary to avoid the formation of byproducts, can be achieved by adjusting the wavelength and intensity of the light and the oxidation capacity of the photocatalysts. In addition, light-induced plasmon resonance improves the efficiency of methane conversion by forming an intrinsic high-energy magnetic field that can polarize methane. In methanol conversion, the C―H bond can be selectively activated, instead of the O―H bond, by light irradiation. Therefore, C―C coupling can be realized for the production of various value-added chemicals from methanol. This review summarizes the recent advances in the photocatalytic conversion of methane and methanol including the reactions of reforming, oxidation, and coupling. Perspectives and challenges for further research on the photocatalytic conversion of methane and methanol are also discussed.

Key words: Activation of C―H bond, C₁ chemistry, Methane, Methanol, Photocatalysis

Shuyi ZHANG,Jingxian BAO,Bo WU,Liangshu ZHONG,Yuhan SUN. Research Progress on the Photocatalytic Conversion of Methane and Methanol[J]. Acta Physico-Chimica Sinica 2019, 35(9), 923-939. doi: 10.3866/PKU.WHXB201810002

Figures/Tables 22

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Entry	Catalyst	Reaction	Reaction conditions				Catalytic performance			Ref.
Entry	Catalyst	Reaction	T/℃	P/MPa	Light source	I/(mW∙cm^-2)	Reaction rate	Conv./%	Sel./%	Ref.
1	Rh-Au/SBA-15	methane to syngas	500	0.1	LA-251Xe-lamp (HA30 filter)	280	1650–1750 μmol_CH₄·g^-1∙s^-1 2150–2200 μmol_CO₂·g^-1∙s^-1	NA	~100	28
2	Pt/black-TiO₂	methane to syngas	650	0.1	sunlight	100	129 mmol_H₂·g^-1∙h^-1 103 mmol_CO·g^-1∙h^-1	NA	NA	29
3	Ni/SiO₂-Im	methane to syngas	550	0.1	LA-251Xe-lamp (HA30 filter)	1070	1270 μmol_H₂·g^-1 Ni∙min^-1 1270 μmol_H₂·g-1 Ni∙min^-1	NA	~100	30
4	Pt-Si-CeO₂	methane to syngas	600	0.1	solar simulator	3000	90 mmol_H₂·g^-1∙h^-1 154 mmol_CO·g^-1∙h^-1	25	NA	31
5	Ni/Al₂O₃	methane to syngas	550	0.1	LA-251Xe-lamp (HA30 filter)	1070	132 μmol_H₂·g^-1∙h^-1 130 μmol_CO·g^-1∙h^-1	NA	~100	32
6	Bi-V/BETA	methane to methanol	70	0.1	Hg lamp	NA	10.7 μmol_CH₃_OH·g^-1∙h^-1	NA	NA	33
7	Beta zeolite	methane to methanol	RT	0.5	deep-UV (185 nm)	NA	NA	6.3	5.4	34
8	V-MCM-41	methane to methanol	300	0.1	Hg lamp UV (> 270 nm)	NA	9.6 μmol_CH₃_OH·g^-1∙h^-1	7.1	88	35
9	n-GaN NWs	methane to benzene	5	0.1	Xe lamp UV (290–380 nm)	7.5	11.39 ×10 μmol_CH₄·g^-1∙h^-1 1.77 × 10^-2 μmol_C₆_H₆·g^-1∙h^-1	NA	96	36
10	Au/ZnO	methane to ethane	RT	0.1	Xe lamp (300–800 nm)	600	11.25 μmol_C₂_H₆·g^-1∙h^-1 10 μmol_H₂·g^-1∙h^-1	NA	NA	37
11	(Zn⁺, Zn²⁺)/ZSM-5	methane to ethane	RT	0.1	Hg lamp (< 270 nm)	100	9.8 mmol_CH₄·g^-1∙h^-1 4.9 mmol_H₂·g^-1∙h^-1	24	99	38
12	Ga³⁺-EST-10	methane to ethane	RT	0.1	Hg lamp (< 370 nm)	100	29.8 μmol_CH₄·g^-1∙h^-1	14.9	NA	39

Entry	Catalyst	Reaction	Reaction conditions				Catalytic performance			Ref.
Entry	Catalyst	Reaction	T/℃	P/MPa	Light source	I/(mW∙cm^-2)	Reaction rate	Conv./%	Sel./%	Ref.
1	0.5% Pt/TiO₂	methanol to hydrogen	RT	0.1	LED (365 nm)	3	66.75 mol_H₂∙g^-1∙min^-1	NA	NA	22
2	1% Pt/TiO₂	methanol to hydrogen	30	0.1	iron halogenide mercury arc lamp	1.67 ×10^-7 Einsteins^-1∙cm^-2	18.6 mmol_H₂∙g^-1∙h^-1 2.88 mmol_CO₂∙g^-1∙h^-1	NA	CO₂: 46.4	64
3	MgO	methanol to formaldehyde	RT	0.1	mercury lamp UV	388	~55 μmol_H₂∙g^-1∙h^-1	NA	no CO_x	65
4	AgNPs/g-C₃N₄ aerogel	methanol to formaldehyde	RT	0.1	Xe lamp (350–780 nm)	NA	152.2 μmol_H₂∙g^-1∙h^-1	NA	no CO_x	66
5	Au/WO₃	methanol to formaldehyde	25	0.1	Xe arc lamp (380–950 nm)	800	120 μmol_MeOH∙g^-1∙min^-1	NA	32–40	67
6	Cu/TiO₂	methanol to methyl formate	15–45	0.1	high pressure mercury lamp UV	18.6	56.4 mmol_MF∙g^-1∙h^-1	65-85	55–65	68
7	CuO/CuZnAl hydrotalcites-ZnO	methanol to methyl formate	26–45	0.1	high pressure mercury lamp UV	25.3	NA	84.5	59.1	69
8	3% Ag/SiO₂	methanol to methyl formate	40	0.1	high pressure mercury lamp UV	NA	23.46 mmol_MF∙g^-1∙h^-1	NA	NA	70
9	Au-Ag alloy/TiO₂	methanol to methyl formate	15–45	0.1	UV	~19	~22 mmol_MF∙g^-1∙h^-1	90	85	71
10	MoS₂ foam/CdS	methanol to ethylene glycol	RT	0.1	300-W Xe lamp (420–780 nm)	NA	11 mmol_EG∙g^-1∙h^-1 12 mmol_H₂∙g^-1∙h^-1	NA	90	20
11	Pt/TiO₂	methanol to ethylene glycol	60	0.1	Xe lamp UV light (320–400 nm)	120	16.8umol_EG∙g^-1∙h^-1	NA	86.4	72
12	Pt/TiO₂	methanol to aliphatic alcohol	60	0.1	Xe lamp irradiation (200–400 nm)	100	TOF of aliphatic alcohol 0.003 h^-1	1.3–8.6	54–87	73


Entry	Substrate	Olefins	Main product	10^-3 TON	10^-3 TOF/h^-1	Selectivity to target product/%	Anti-Markovnikov regioselectivity/%
1				18.0	1.2	87.2	90
2				33.1	2.2	84.0	92
3				34.6	2.3	74.6	93
4				45.3	3.0	62.3	93
5				14.9	1.0	54.4	100
6				59.2	3.9	57.7	100
7				105.2	7.0	77.0	100


Entry	Substrate	Target product	10^-3 TON	10^-3 TOF/h^-1	Selectivity to target product/%	A/(P + A)	Anti-Markovnikov regioselectivity/%
1			45.3	3.0	62.3	0.92	93
2			83.2	5.6	86.8	0.97	100
3			207.9	13.9	79.1	0.93	100
4			282.6	28.3	79.7	0.86	100

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Research Progress on the Photocatalytic Conversion of Methane and Methanol

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