Structural feature of graphene-like graphitic carbon nitride nanosheets synthesized via high-energy microwave irradiation
ZOU Jing-ye1, YU Yong-zhi1,2, GU Yong-pan1, YUE Xia-wei1, MENG Jiang1,3, LI Shu-ping3, WANG Ji-gang1,3
1. Jiangsu Key Laboratory of Advanced Metallic Materials, School of Materials Science and Engineering, Southeast University, Nanjing 211189, China;
2. National Engineering Research Center for Domestic & Building Ceramics, Jingdezhen Ceramic Institute, Jingdezhen 333001, Jiangxi, China;
3. Xizang Engineering Laboratory for Water Pollution Control and Ecological Remediation, Xizang Minzu University, Xianyang 712082, Shaanxi, China
Abstract：Microwave synthesis has many advantages covering rapid, high-efficient, environmentally-friendly etc. Herein, graphene-like carbon nitride nanosheets (g-C3N4-NS) were successfully prepared by high-energy microwave heating method using melamine and carbon fibers as precursor and microwave absorber, respectively. The as-synthesized samples were investigated via various analytic techniques including X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and fourier transform infrared spectroscopy (FT-IR). Results show that the g-C3N4-NS sample prepared by microwave heating exhibits the obvious feature of graphene-like ultra-thin nanosheets in comparison with sample synthesized by conventional thermal polycondensation. Meanwhile, compared with graphene-like carbon nitride nanosheets prepared by other approaches including ultrasonic exfoliation and oxidation etching methods, the sample synthesized by microwave heating has smooth, flat and strong rigidity surface.
 LEIBIG J. Uber einige Stickstoff-Verbindungen[J]. Annalen der Pharmacie,1834, 10(1):1-47.
 LIU A Y, COHEN M L. Prediction of new low compressibility solids[J]. Science,1989, 245(4920):841-842.
 TETER D M, HEMLEY R J. Low-compressibility carbon nitrides[J]. Science,1996, 271(5245):53-55.
 WANG Y, WANG X, ANTONIETTI M. Polymeric graphitic carbon nitride as a heterogeneous organocatalyst:from photochemistry to multipurpose catalysis to sustainable chemistry[J]. Angewandte Chemie International Edition,2012, 51(1):68-89.
 YAN S C, LI Z S, ZOU Z G. Photodegradation performance of g-C3N4 fabricated by directly heating melamine[J]. Langmuir,2009, 25(17):10397-10401.
 LU Q, DENG J, HOU Y, et al. One-step electrochemical synthesis of ultrathin graphitic carbon nitride nanosheets and their application to the detection of uric acid[J]. Chemical Communications, 2015, 51(61):12251-12253.
 WANG X, MAEDA K, THOMAS A, et al. A metal-free polymeric photocatalyst for hydrogen production from water under visible light[J]. Nature Materials, 2009, 8(1):76-80.
 HONG J, YIN S, PAN Y, et al. Porous carbon nitride nanosheets for enhanced photocatalytic activities[J]. Nanoscale, 2014, 6(24):14984-14990.
 ZHU K, WANG W, MENG A, et al. Mechanically exfoliated g-C3N4 thin nanosheets by ball milling as high performance photocatalysts[J]. RSC Advances,2015, 5(69):56239-56243.
 HUANG Z, LI F, CHEN B, et al. Nanoporous photocatalysts developed through heat-driven stacking of graphitic carbon nitride nanosheets[J]. RSC Advances, 2015, 5(18):14027-14033.
 XU J, ZHANG L, SHI R, et al. Chemical exfoliation of graphitic carbon nitride for efficient heterogeneous photocatalysis[J]. Journal of Materials Chemistry A, 2013, 1(46):14766-14772.
 WANG W, CHAKRABARTI S, CHEN Z, et al. A novel bottom-up solvothermal synthesis of carbon nanosheets[J]. Journal of Materials Chemistry A,2014, 2(7):2390-2396.
 CHENG N, JIANG P, LIU Q, et al. Graphitic carbon nitride nanosheets:one-step, high-yield synthesis and application for Cu2+ detection[J]. The Analyst,2014, 139(20):5065-5068.
 PATETE J M, PENG X, KOENIGSMANN C, et al. Viable methodologies for the synthesis of high-quality nanostructures[J]. Green Chemistry, 2011, 13(3):482-519.
 高军. 微纳结构g-C3N4的制备与性能研究[D]. 南京:南京大学, 2012. GAO J. Research on synthesis of micro-nano structured g-C3N4 and their properties[D]. Nanjing:Nanjing University, 2012.
 裴昭君. 微波辅助制备石墨相碳化氮可见光催化降解罗丹明B的试验研究[D]. 成都:成都理工大学, 2014. PEI Z J. Study on photocatalytic degradation of rhodamine B with graphite carbon nitrogen under visible light[D]. Chengdu:Chengdu University of Technology, 2014.
 YUAN Y, YIN L, CAO S, et al. Microwave-assisted heating synthesis:a general and rapid strategy for large-scale production of highly crystalline g-C3N4 with enhanced photocatalytic H2 production[J]. Green Chemistry, 2014, 16:4663-4668.
 WANG J G, LIU S, DING T, et al. Synthesis, characterization, and photoluminescence properties of bulk-quantity β-SiC/SiOx coaxial nanowires[J]. Materials Chemistry and Physics, 2012, 135:1005-1011.
 LIU S, WANG J G. Ultra-violet emission from one dimensional and micro-sized SiC obtained via microwave heating[J]. Materials Science in Semiconductor Processing, 2017, 72:60-66.
 YU Y Z, WANG J G. Direct microwave synthesis of graphitic C3N4 with improved visible-light photocatalytic activity[J]. Ceramics International,2016, 42(3):4063-4071.
 YU Y Z, ZHOU Q, WANG J. The ultra-rapid synthesis of 2D graphitic carbon nitride nanosheets via direct microwave heating for field emission[J]. Chemical Communications, 2016, 52(16):3396-3399.
 YU Y Z, WANG C, LUO L, et al. An environment-friendly route to synthesize pyramid-like g-C3N4 arrays for efficient degradation of rhodamine B under visible-light irradiation[J]. Chemical Engineering Journal,2018, 334:1869-1877.
 梁庆华. 石墨相氮化碳的结构调控及增强光催化性能研究[D]. 北京:清华大学, 2016. LIANG Q H. Structural tuning of graphitic carbon nitrides with highly improved photocatalytic performance[D]. Beijing:Tsinghua University, 2016.
 吴星瞳. 石墨相氮化碳微纳米材料的制备及光催化性能研究[D]. 长春:吉林大学, 2015. WU X T. Studies on synthesis characterization and photocatal-ytic properties of graphitic carbon nitride and its composites[D]. Changchun:Jilin University, 2015.
 NIU P, ZHANG L, LIU G, et al. Graphene-like carbon nitride nanosheets for improved photocatalytic activities[J]. Advanced Functional Materials,2012, 22(22):4763-4770.
 MENENDEZ J A, JUAREZ-PEREZ E J, RUISANCHEZ E, et al. Ball lightning plasma and plasma arc formation during the microwave heating of carbons[J]. Carbon, 2011, 49(1):346-349.
 WANG J G, LIU S, HUANG S, et al. EBSD characterization the growth mechanism of SiC synthesized via direct microwave heating[J]. Materials Characterization, 2016, 114(3):54-61.
 KROKE E, SCHWARZ M, HORATH-BORDON E, et al. Tri-s-triazine derivatives part I from trichloro-tri-s-triazine to graphitic C3N4 structures[J]. New Journal of Chemistry, 2002, 26(5):508-512.
 黄珊,王继刚,刘松,等. 高能微波辐照条件下SiC晶粒的生长过程分析[J]. 无机材料学报, 2014,29(2):149-154. HUANG S, WANG J G, LIU S, et al. Growth process of SiC grains prepared by high-energy microwave irradiation[J]. Journal of Inorganic Materials, 2014,29(2):149-154.
 THOMAS A, FISCHER A, GOETTMANN F, et al. Graphitic carbon nitride materials:variation of structure and morphology and their use as metal-free catalysts[J]. Journal of Materials Chemistry, 2008, 18(41):4893-4908.
 LI X, ZHANG J, CHEN X, et al. Condensed graphitic carbon nitride nanorods by nanoconfinement:Promotion of crystallinity on photocatalytic conversion[J]. Chemistry of Materials, 2011, 23(19):4344-4348.
 SONH X, YANG Q, JIANG X, et al. Porous graphitic carbon nitride nanosheets prepared under self-producing atmosphere for highly improved photocatalytic activity[J]. Applied Catalysis B:Environmental, 2017, 217:322-330.
 HONG Y, LI C, FANG Z, et al. Rational synthesis of ultrathin graphitic carbon nitride nanosheets for efficient photocatalytic hydrogen evolution[J]. Carbon, 2017, 121:463-471.
 BOJDYS M J, MULLER J, ANTONIETTI M, et al. Ionothermal synthesis of crystalline, condensed, graphitic carbon nitride[J]. Chemistry-A European Journal, 2008, 14(27):8177-8182.
 YAN J, ZHOU C, LI P, et al. Nitrogen-rich graphitic carbon nitride:controllable nanosheet-like morphology, enhanced visible light absorption and superior photocatalytic performance[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2016, 508:257-264.
 MING L, YUE H, XU L, et al. Hydrothermal synthesis of oxidized g-C3N4 and its regulation of photocatalytic activity[J]. Journal of Materials Chemistry A,2014, 2(45):19145-19149.
 YANG S, GONG Y, ZHANG J, et al. Exfoliated graphitic carbon nitride nanosheets as efficient catalysts for hydrogen evolution under visible light[J]. Advanced Materials, 2013, 25(17):2452-2456.