Enhanced dehydrochlorination of 1,1,2,2-tetrachloroethane by graphene-based nanomaterials.
Graphene oxide (GO) and reduced graphene oxide (RGO) materials contain a variety of surface O-functional groups that are chemically reactive. When released into the environment these materials may significantly affect the abiotic transformation of organic contaminants, and therefore, may alter their fate and risks. We found that two GO and five RGO materials that varied in C/O ratio, hydrophobicity, and type/distribution of surface O-functionality all had catalytic effects on the dehydrochlorination of 1,1,2,2-tetrachloroethane (TeCA). Even though the catalytic effects of the materials originated from their deprotonated surface O-functional groups, which served as conjugated bases to catalyze the reaction, the catalytic efficiencies of the materials did not correlate strongly with their surface O contents. The spectroscopic evidence (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy), surface charge data, and adsorption experiments demonstrated that the catalytic efficiencies of the GO/RGO materials were controlled by a complex interplay of the type and distribution of surface O-functionality, as well as adsorption affinity of the materials. Both Ca(2+) and Mg(2+) inhibited the catalytic efficiency of the materials by binding to the surface O-functional groups, and consequently, decreasing the basicity of the functional groups. At an environmentally relevant concentration of 10 mg/L, Suwannee River humic acid (used as a model dissolved organic matter) alone had little effect on the dehydrochlorination of TeCA. However, it could inhibit the catalytic efficiency of the GO/RGO materials by coating on their surface and thus, decreasing the adsorption affinity of these materials for TeCA. The findings further underline the potentially important impacts of nanomaterials on contaminant fate and effects in the environment.
College of Environmental Science and Engineering, Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Key Laboratory of Environmental Remediation and Pollution Control, Nankai University, Wei Jin Road 94, Tianjin, 300071, China.
Xuguang
X
Li
College of Environmental Science and Engineering, Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Key Laboratory of Environmental Remediation and Pollution Control, Nankai University, Wei Jin Road 94, Tianjin, 300071, China.
Weifeng
W
Chen
College of Environmental Science and Engineering, Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Key Laboratory of Environmental Remediation and Pollution Control, Nankai University, Wei Jin Road 94, Tianjin, 300071, China.
Chengdong
C
Zhang
College of Environmental Science and Engineering, Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Key Laboratory of Environmental Remediation and Pollution Control, Nankai University, Wei Jin Road 94, Tianjin, 300071, China.
Yao
Y
Li
College of Environmental Science and Engineering, Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Key Laboratory of Environmental Remediation and Pollution Control, Nankai University, Wei Jin Road 94, Tianjin, 300071, China.
Fanfan
F
Wang
College of Environmental Science and Engineering, Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Key Laboratory of Environmental Remediation and Pollution Control, Nankai University, Wei Jin Road 94, Tianjin, 300071, China. Electronic address: chenwei@nankai.edu.cn.
Wei
W
Chen
D000327:Adsorption; D002384:Catalysis; D004980:Ethane / Q000031:analogs & derivatives* / Q000737:chemistry; D006108:Graphite / Q000737:chemistry; D054879:Halogenation; D006812:Humic Substances; D006843:Hydrocarbons, Chlorinated / Q000737:chemistry*; D057927:Hydrophobic and Hydrophilic Interactions; D049329:Nanostructures / Q000737:chemistry*; D010087:Oxides / Q000737:chemistry; D045483:Rivers
D006812:Humic Substances; D006843:Hydrocarbons, Chlorinated; D010087:Oxides; C015530:1,1,2,2-tetrachloroethane; D006108:Graphite; D004980:Ethane
Base-catalyzed reaction; Dehydrochlorination; Graphene oxide; Reduced graphene oxide; Tetrachloroethane