Liquid-Phase Heterogeneous Catalytic Reactions by Metal-Free Graphene-Based Catalysts

doi:10.3866/PKU.WHXB201512153

Acta Phys. -Chim. Sin.

2016, Vol. 32

Issue (1): 75-84 DOI: 10.3866/PKU.WHXB201512153

REVIEW

Liquid-Phase Heterogeneous Catalytic Reactions by Metal-Free Graphene-Based Catalysts

Jing-He YANG¹,Duo YANG¹,Pei TANG²,Ding MA^2,*(

)

¹ Department of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, Henan Province, P. R. China
² Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China

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Abstract

Metal-free carbon catalysts have been receiving increasing attention in the fields of nanomaterials and catalysis. Compared with conventional metal catalysts, there are many advantages for metal-free carbon catalysts, such as simple synthesis, stable structure, large surface area, and diverse applications. Graphene is one layer of carbon atoms and has a periodic structure of aromatic carbon atoms. Graphene oxide is a highly oxidized form of graphene. As a new carbon material, its application in catalysis has emerged over the past 5 years. Graphene-based materials can efficiently catalyze hydrocarbon conversion, organic synthesis, energy conversion, and other heterogeneous catalytic processes. This review highlights the recent progress in the development of metal-free graphene-based catalysts (graphene oxide and graphene) and associated catalytic reactions.

Key words： Graphitic oxide Graphene Catalysis Metal-free Carbon

Received: 30 October 2015 Published: 15 December 2015

MSC2000:

O643.32+2

Fund: the National Natural Science Foundation of China(21403053);Joint Funds of the National Natural ScienceFoundation of China(U1404503)

Corresponding Authors: Ding MA E-mail: dma@pku.edu.cn

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Cite this article:

Jing-He YANG,Duo YANG,Pei TANG,Ding MA. Liquid-Phase Heterogeneous Catalytic Reactions by Metal-Free Graphene-Based Catalysts. Acta Phys. -Chim. Sin., 2016, 32(1): 75-84.

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http://www.whxb.pku.edu.cn/10.3866/PKU.WHXB201512153 OR http://www.whxb.pku.edu.cn/Y2016/V32/I1/75

Fig 1 Schematic diagrams of graphene and related materials

Fig 2 Schematic diagram for preparation of reduced graphene oxide

Catalyst	Reaction	Reaction conditions	Remarks
KOH/G²⁰	aerobic oxidation of 9H-fluorenes to 9-fluorenones	catalyst (7 mg), substratre (5 mmol), KOH (5 mmol), DMF (15 mL), room temperature, 16 h	5 cycles
N doped G²¹	aerobic oxidation of benzylic alcohols	catalyst (30 mg), alcohol (0.1 mmol), H₂O (80 mL), O₂ (1.01 × 10⁵ Pa), 70℃, 10 h	the doping of N atoms being the active sites
(B, N) doped G⁹	aerobic oxidation of benzylic hydrocarbons, cyclooctane and styrene	catalyst (5 mg), tetralin (1 mL), O₂ 120 ℃	synergism of B and N doping; 2 cycles
rGO²³	oxidation of benzene to phenol by H₂O_2.	catalyst (20 mg), substrate (130 mg), oxidant (2.4 mL, 30%), acetonitrile (1.2 mL), 60 ℃, 16 h	metal impurities study; 7 cycles
N doped G²⁴	oxidation of benzylic positions by tert-buthylhydroperoxide	catalyst (10 mg), substrate (1.0 mmol), TBHP (3.0 mmol, 65%(w) in water), H₂O (10 mL), 80 ℃, 24 h	N doping; 5 cycles
meso-G²⁶	acrobic oxidation of cyclohexane	catalyst (30 mg), substrate (14.0 g), cyclohexanone as initiator (0.39 g), acetone (9.6 g), O₂ (1.5 MPa), 125 ℃, 8 h	Metal impurities do not promote catalytic activity; 4 cycles
rGO³⁰	hydrogenation of nitrobenzene	reagent hydrogen or hydrazine hydrate	rGO shows better catalytic capabilities than activated carbon and Pt/SiO₂
rGO or (N)rGO^{27, 28}	4-nitrophenol reduction to 4-aminophenol by NaBH₄	–	evidence of adsorption of nitrophenol on graphene no leaching; 8 cycles
rGO²⁹	synthesis of dipyrromethane and calix [4] pyrrole	–	active sites are assumed to be the acidic sites
GO²⁷	aerobic oxidation of alcohols (i.e., benzyl alcohol) and unsaturated hydrocarbons (i.e., cis-stilbene)	catalyst (100 mg; 5%–200%(w) respect substrate), atmospheric pressure, 25–150 ℃, 3–144 h	metal impurities are not responsible of the catalytic activity, 10 cycles
GO²⁸	aerobic oxidation of benzyl alcohol to benzaldehyde	density functional theory study	active sites of GO are regeneratedby molecular O₂
GO²⁹	aerobic oxidation of amines to imines	catalyst (5%(w), amine (1 g), 90 ℃, open air conditions, 12 h	metal impurities are excluded as active sites; 6 cycles
GO²⁷	hydration of alkynes	catalyst (100 mg, 200%(w), substrate (50 mg), 100 ℃, 24 h	98%–27% conversions
GO³⁴	Michael addition	catalyst (0.5 mg$ { { \cdot } } $mL^–1, 0.5 mL) t-β-nitrostyrene (0.1676 mmol), 2, 4-pentanedione (1.5 equiv), base (1.1 equiv), 18-crown-6 ether (1.1 equiv), room temperature	specially epoxy and hydroxyl groups promoting the reaction
GO³⁵	aza-Michael addition of amines to alkenes	catalyst (0.5 mL of 0.05 mg$ { { \cdot } } $mL^–1), amine (1 mmol), α, β-unsaturated compounds (1.2 mmol), room temperature, < 30 min	oxygen groups are responsible for the catalytic activities; 9 cycles
GO³⁶	dehydrative etherification of benzyl alcohol	substrate to catalyst ratio 20 mL$ { { \cdot } } $g^–1, 150 ℃, 24 h	85.4% yield to dibenzyl ether

Table 1 Catalytic reaction using graphitic oxide (GO), graphene (G) or reduced graphene oxide (rGO) as catalysts⁷

Fig 3 Aerobic oxidation of benzyl alcohol and 1-phenylethanol catalyzed by N-doped graphene as catalyst²¹

Table 2 Direct oxidation of benzene to phenol under various conditions²³

Fig 4 Relation between yield towards phenol and reaction barriers and proposed mechanism for oxidation of benzene²³

Table 3 Catalytic activity of N-graphene materials for the oxidation of ethylbenzene²⁴

Table 4 Catalytic performances of carbon materials in the aerobic cyclohexane oxidation promoted by initiator²⁶

Fig 5 Oxidation of benzyl alcohol and cis-stilbene using graphene oxide²⁷

Fig 6 Graphitic oxide of alkali reduction and acidic proton treatment²⁹

Table 5 Hydrogenation of nitrobenzene over different carbon catalysts³⁰

Table 6 Reduction of chloronitrobenzene over carbon black with different Mn content³⁰

Fig 7 Model of interaction between nitrobenzene and graphene sheets³⁰

Fig 8 Base synthesis of dipyrromethane and calix[4]pyrrole catalyzed by GO³³

Fig 9 Michael addition catalyzed by GO as phase transfer catalyst³⁵

Fig 10 Catalytic alkylation of arenes via GO³⁷

Fig 11 Mechanism for the GO catalyzed alkylation of arenes³⁷

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