Tổng hợp và nghiên cứu khả năng ứng dụng của hạt nano vàng phân bố trên vật liệu polyme carbon nitride = sythesis and application of polymeric carbon nitride decorated with gold nanoparticles

HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY MASTER THESIS Synthesis and Application of PolymericCarbon Nitride decorated with Gold Nanoparticles GIAP VAN HUNG Hung.GV202683M@sis.hust.edu.vn Master of Science in Chemistry Supervisor 1: Dr Nguyen Thi Tuyet Mai Institute: Chemical Engineering Institute Supervisor 2: Dr Norbert Steinfeldt Institute: Leibniz Institute for Catalysis (LIKAT) HANOI, OCTOBER 2022 Signature Signature DECLARATION OF INDEPENDENCE I hereby declare that I have prepared this thesis independently and under the guidance of my supervisor, without using any support and resources other than the RoHan Project funded by the German Academic Exchange Service (DAAD, No 57315854) and the Federal Ministry for Economic Cooperation and Development (BMZ) inside the framework "SDG Bilateral Graduate school programme Hung Giap Van ACKNOWLEDGEMENTS First, I would like to express my deepest gratitude to my co-supervisors Dr Norbert Steinfeldt (LIKAT) and Dr Nguyen Thi Tuyet Mai (HUST), for his help and support throughout my thesis work Without them supervision, I would not have been able to complete my thesis Special thanks to the Department of Physical Chemistry, Institute of Chemical Engineering, Hanoi University of Science and Technology together with the research group of Prof Jennifer Stunk at Leibniz Institute of Catalysis (LIKAT Rostock) created favorable conditions for me to study, research and completed this thesis Finally, I would like to thank my family, friends, and relatives has always accompanied, encouraged, and shared with me They are a great source of motivation for me to continue my research path ABSTRACT Photocatalytic hydrogen generation is increasingly perceived as a potential alternative to traditional hydrogen production method [1] Polymeric carbon nitride (p-C3N4) has been considered as a promising photocatalyst candidate due to its low cost, chemical stability, and visible light reactivity However, the performance of pure p-C3N4 is limited due to the rapid recombination of photoinduced electron-hole pairs Therefore, a lot of methods were explored to improve the activity of p-C3N4 In this work, p-C3N4 was prepared in different atmospheres, treated with H2O2 or ultrasound, and then investigated with Au deposition to optimize its photocatalytic performance Before testing in hydrogen evolution reaction (HER) with triethanolamine (TEOA) as sacrificial agent, the materials were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (FTIR), UV-vis diffuse reflectance spectroscopy (DRS), thermal gravity analysis (TGA), elemental analysis (EA), and photoluminescence spectroscopy (PL) The synthesized materials showed improved charge separation efficiency and H2 evolution performance The highly-improved performance is ascribed to the efficient transfer of photo-generated electrons among molecule pC3N4 and Au, which is supported by photoluminescence spectra and transient photocurrent responses TABLE OF CONTENTS ACKNOWLEDGEMENTS ABSTRACT TABLE OF CONTENTS LIST OF TABLES LIST OF FIGURES LIST OF ABBREVIATIONS 10 CHAPTER INTRODUCTION 11 1.1 Background 11 1.2 Objectives and outline of the thesis 11 1.2.1 Thesis outline 11 1.2.2 Thesis Objectives 12 CHAPTER LITERATURE REVIEW 13 2.1 Introduction 13 2.2 Graphitic Carbon Nitride (p-C3N4) 14 2.2.1 History 14 2.2.2 Synthesis of p-C3N4 15 2.2.3 Physical and Chemistry properties 21 2.2.4 Modifications 22 2.2.5 p-C3N4 based nanocomposites 25 2.2.6 Trends of photocatalytic development of p-C3N4 27 2.3 Plasmonic Photocatalysis 28 2.3.1 Fundamentals 29 2.3.2 Surface plasmon benefits for photocatalysis 30 2.3.3 Metal nanoparticle/semiconductor junction 32 2.3.4 Gold nanoparticles based on p-C3N4 33 CHAPTER p-C3N4 - SYNTHESIS, CHARACTERIZATION, AND APPLICATION 34 3.1 Experimental 34 3.1.1 Preparation of p-C3N4 34 3.1.2 Post-treatment of p-C3N4 35 3.1.3 Material characterization 36 3.1.4 Photocatalytic -HER reaction 37 3.1.5 Electrochemical characterization 38 3.2 Results and Discussion 38 3.2.1 Structural and thermal properties 38 3.2.2 Optical and electrochemical properties 47 3.2.3 Evaluation of photocatalytic activity toward H evolution under white light irradiation 50 CHAPTER Au/p-C3N4 COMPOSITES – SYNTHESIS, CHARACTERIZATION, AND APPLICATION 52 4.1 Experimental 52 4.1.2 Material characterization 54 4.1.3 Photocatalytic and electrochemical measurement 54 4.2 Results and Discussion 55 4.2.1 Effect of the p-C3N4 support 55 4.2.2 Effect of Au loading 61 4.2.3 Effect of Au deposition method 66 4.2.4 Possible photocatalytic mechanism 71 CHAPTER GENERAL CONCLUSIONS AND OUTLOOK 73 5.1 General conclusions 73 5.2 Outlook 73 REFERENCES 75 LIST OF TABLES Table Position of the (002) reflection of p-C3N4 support 39 Table Summary of characteristic parameters determined based on N2 adsorptiondesorption isotherms of different p-C3N4 samples 42 Table Near surface composition of various p-C3N4 heterostructures 45 Table Atomic ratio of C, H, N of various p-C3N4 obtained by elemental analysis 46 Table Band gap values of various p-C3N4 calculated from Tauc's method 48 Table Position of p-C3N4 (002) reflection and crystallite size of Au nanoparticles of wt.% Au/p-C3N4 samples .56 Table Table of band gap energy of wt.% Au/p-C3N4 calculated from Tauc's method .58 Table Crystallite size, nano size of different wt.% Au based on p-C3N4 (air) 62 Table Crystallite size and band gap of Au/p-C3N4 synthesized by chemical reduction method .68 LIST OF FIGURES Figure Schematic diagram of the synthesis of p-C3N4 from the thermal polymerization of melamine, cyanamide, dicyandiamide, urea and thiourea [46] 16 Figure 2 Postulated Condensation of Melamine [63] 17 Figure Schematic of self-modification to promote oriented vacancies [78] 19 Figure Using NH3 atmosphere in the synthesis of p-C3N4 [79] 20 Figure a) The pyrolysis time-layer thickness of p-C3N4 [84] b) Synthesis pathway of structurally distorted p-C3N4 nanosheets [87] .21 Figure Scheme of monolayer (a) crystalline and (b) amorphous monolayer of graphite carbon nitride [89] 22 Figure a) The “hard” template approach combines the sol-gel/thermal condensation method [112] b) Different morphologies can be obtained by the “Soft” and “Hard” slide approaches based on p-C3N4 [97] 24 Figure Schematic representation of the charge pairs in p-C3N4 is shown with decay lines, where A represents the electron acceptor while D is the donor[46] 27 Figure Typical bandgap energy values of semiconductor photocatalysts and redox potentials of processes including H 2O separation, CO2 reduction and pollutant decomposition (reaction carried out with pH = 7) [46] 28 Figure 10 Schematic diagram of plasmon oscillations after application of an electric field, and electron cloud formation [145] 30 Figure 11 Scheme of the electromagnetic field intensification on M NP [146] 31 Figure 12 Mechanism of hot electron injection from metal/plasmonic nanoparticles into the semiconductor conduction band [146] 32 Figure Schematic overview about process synthesis of pure p-C3N4 34 Figure The crucible used in the synthesis of p-C3N4 34 Figure 3 Experimental system treatment p-C3N4 by H2O2 solution (left), the pC3N4 mixture after treatment by H2O2 (right) .35 Figure Treatment p-C3N4 using the BANDELIN SONOPULS HD 2070 ultrasonic transducer system 36 Figure Scheme of the experimental set-up used for study of HER reaction with p-C3N4 catalysts under irradiation with white light .37 Figure XRD patterns of various p-C3N4 samples 39 Figure ATR-IR spectra of all various p-C3N4 .40 Figure N2 adsorption-desorption isotherms and corresponding pore size distribution curves (inset) of various p-C3N4 heterostructures .41 Figure The fully survey spectra of XPS spectra for various p-C3N4 heterostructures 42 Figure 10 XPS spectra of C1s, N1s, O1s of all samples 44 Figure 11 TGA-DSC analysis of p-C3N4 support 46 Figure 12 UV-vis DRS spectrum of various p-C3N4 samples 47 Figure 13 PL spectra of various p-C3N4 49 Figure 14.a) Transient photocurrent responses and b) EIS of various p-C3N4 under visible light irradiation 50 Figure 15 Temporal H2 evolution of p-C3N4 samples synthesized under (a) air (300 W Xenon lamp) or (b) Ar atmosphere (1000 W Xenon lamp) after in-situ Au deposition at irradiation with white light (Au amount wt.% ) 51 Figure Schematic illustration of synthetic Au/p-C3N4 by photodeposition method .52 Figure Schematic synthesis of Au/p-C3N4 synthesis by chemical reduction method, using NaBH4 reducing agent 53 Figure Schematic synthesis of Au/p-C3N4 synthesis by chemical reduction method, using NaBH4 reducing agent with surfactant: sodium citrate, PVP 54 Figure 4 LED arrays irradiating visible light (24 V, 1.12 A, 24 W) 55 Figure XRD patterns of synthesized Au/p-C3N4 composites .56 Figure (a) ATR-IR spectra and (b) UV-vis DRS spectra of the different 2wt.% Au/p-C3N4 57 Figure PL spectra of wt.% Au/p-C3N4 59 Figure Transient photocurrent (a) and EIS (b) of Au/p-C3N4 under visible light irradiation .60 Figure Time course of H evolution of Au/p-C3N4 (a) under white and (b) visible light irradiation 60 Figure 10 XRD patterns of Au/p-C3N4 (air) with different wt.% Au 62 Figure 11 SEM images of (a) 2wt.% Au and (b) wt % Au based on p-C3N4 (air) 63 Figure 12 ATR-IR spectra of with different wt.% Au based on p-C3N4 (air) 64 Figure 13 (a) UV-vis spectra and (b) PL spectra of different wt.% Au based on p-C3N4 (air) 65 Figure 14 Time course of H2 evolution of Au/p-C3N4 (air) with different wt.% Au under white light 66 Figure 15 Characterizations (a) XRD, (b) ATR-IR, (c) PL and (d) UV-vis DRS of different methods of Au/p-C3N4 synthesis 67 Figure 16 SEM images of Au/p-C3N4 synthesized by chemical reduction using (a) NaBH4 in dark, (b) NaBH4 + Sodium citrate and (c) NaBH4 + PVP .69 Figure 17 XPS spectra of various p-C3N4 and Au/p-C3N4: (a) Fully scanned spectra of various p-C3N4 compare with Au/p-C3N4, (b) C 1s, (c) N 1s, (d) O 1s and (e) Au 4f .70 Figure 18 Time course of H evolution of Au/p-C3N4 synthesized samples (by different methods) under white light .71 Figure 19 Schematic illustration of the mechanism H evolution reaction by Au/p-C3N4 composite from water in the presence of TEOA 72 LIST OF ABBREVIATIONS Abbreviations Meaningful AuNPs Gold nanoparticles CB Conductive Band CVD Chemical vapor deposition EIS Electrochemical impedance spectroscopy GC Gas chromatography HAuCl4 Chloroauric acid HER Hydrogen Evolution Reaction LSPR Localized surface plasmon resonance M Metal M NP Metal Nano Particles MOFs Metal Organic Frameworks NaBH4 Sodium borohydride p-C3N4 Graphitic carbon Nitride PVD Physical vapor deposition PVP Polyvinylpyrrolidone SC Semiconductor TEOA Triethanolamine VB Valence band 10 [97] Z Yang, Y J Zhang, and Z Schnepp, "Soft and hard templating of graphitic carbon nitride," , J Mater Chem A, vol 3, no 27, pp 1408114092, 2015, doi: 10.1039/c5ta02156a [98] Y Wang, J S Zhang, X C Wang, M Antonietti, and H R Li, "Boronand Fluorine-Containing Mesoporous Carbon Nitride Polymers: Metal-Free Catalysts for Cyclohexane Oxidation," , Angew Chem Int Edit, vol 49, no 19, pp 3356-3359, 2010, doi: 10.1002/anie.201000120 [99] J S Zhang et al., "Synthesis of a Carbon Nitride Structure for Visible-Light Catalysis by Copolymerization," , Angew Chem Int Edit, vol 49, no 2, pp 441-444, 2010, doi: 10.1002/anie.200903886 [100] Q J Fan, J J Liu, Y C Yu, and S L Zuo, "A template induced method to synthesize nanoporous graphitic carbon nitride with enhanced photocatalytic activity under visible light," , Rsc Adv, vol 4, no 106, pp 61877-61883, 2014, doi: 10.1039/c4ra12033g [101] W Z Shen, L W Ren, H Zhou, S C Zhang, and W B Fan, "Facile onepot synthesis of bimodal mesoporous carbon nitride and its function as a lipase immobilization support," , J Mater Chem, vol 21, no 11, pp 38903894, 2011, doi: 10.1039/c0jm03666h [102] F He, G Chen, Y G Yu, Y S Zhou, Y Zheng, and S Hao, "The sulfurbubble template-mediated synthesis of uniform porous g-C3N4 with superior photocatalytic performance," , Chem Commun, vol 51, no 2, pp 425-427, 2015, doi: 10.1039/c4cc07106a [103] F He, G Chen, Y S Zhou, Y G Yu, Y Zheng, and S Hao, "The facile synthesis of mesoporous g-C3N4 with highly enhanced photocatalytic H-2 evolution performance," , Chem Commun, vol 51, no 90, pp 1624416246, 2015, doi: 10.1039/c5cc06713h [104] J Liu and M Antonietti, "Bio-inspired NADH regeneration by carbon nitride photocatalysis using diatom templates," , Energ Environ Sci, vol 6, no 5, pp 1486-1493, May 2013, doi: 10.1039/c3ee40696b [105] M Shalom, S Inal, C Fettkenhauer, D Neher, and M Antonietti, "Improving Carbon Nitride Photocatalysis by Supramolecular Preorganization of Monomers," , J Am Chem Soc, vol 135, no 19, pp 7118-7121, May 15 2013, doi: 10.1021/ja402521s 86 [106] T Jordan, N Fechler, J S Xu, T J K Brenner, M Antonietti, and M Shalom, ""Caffeine Doping" of Carbon/Nitrogen-Based Organic Catalysts: Caffeine as a Supramolecular Edge Modifier for the Synthesis of Photoactive Carbon Nitride Tubes," , Chemcatchem, vol 7, no 18, pp 2826-2830, Sep 14 2015, doi: 10.1002/cctc.201500343 [107] Y S Jun, J Park, S U Lee, A Thomas, W H Hong, and G D Stucky, "Three-Dimensional Macroscopic Assemblies of Low-Dimensional Carbon Nitrides for Enhanced Hydrogen Evolution," , Angew Chem Int Edit, vol 52, no 42, pp 11083-11087, Oct 11 2013, doi: 10.1002/anie.201304034 [108] Y J Cui, Z X Ding, X Z Fu, and X C Wang, "Construction of Conjugated Carbon Nitride Nanoarchitectures in Solution at Low Temperatures for Photoredox Catalysis," , Angew Chem Int Edit, vol 51, no 47, pp 11814-11818, 2012, doi: 10.1002/anie.201206534 [109] Z J Huang, F B Li, B F Chen, and G Q Yuan, "Hydrogen from Water over Openly-Structured Graphitic Carbon Nitride Polymer through Photocatalysis," , Chemsuschem, vol 9, no 5, pp 478-484, Mar 2016, doi: 10.1002/cssc.201501520 [110] Y G Xu et al., "High yield synthesis of nano-size g-C3N4 derivatives by a dissolve-regrowth method with enhanced photocatalytic ability," , Rsc Adv, vol 5, no 33, pp 26281-26290, 2015, doi: 10.1039/c5ra01206f [111] Q Gu, Y S Liao, L S Yin, J L Long, X X Wang, and C Xue, "Template-free synthesis of porous graphitic carbon nitride microspheres for enhanced photocatalytic hydrogen generation with high stability," , Appl Catal B-Environ, vol 165, pp 503-510, Apr 2015, doi: 10.1016/j.apcatb.2014.10.045 [112] K Kailasam, J D Epping, A Thomas, S Losse, and H Junge, "Mesoporous carbon nitride-silica composites by a combined solgel/thermal condensation approach and their application as photocatalysts," , Energ Environ Sci, vol 4, no 11, pp 4668-4674, Nov 2011, doi: 10.1039/c1ee02165f [113] J S Zhang, M W Zhang, R Q Sun, and X C Wang, "A Facile Band Alignment of Polymeric Carbon Nitride Semiconductors to Construct Isotype Heterojunctions," , Angew Chem Int Edit, vol 51, no 40, pp 10145-10149, 2012, doi: 10.1002/anie.201205333 87 [114] J Q Zhang et al., "Engineering monomer structure of carbon nitride for the effective and mild photooxidation reaction," , Carbon, vol 100, pp 450455, Apr 2016, doi: 10.1016/j.carbon.2016.01.027 [115] X J Ye, Y J Cui, and X C Wang, "Ferrocene-Modified Carbon Nitride for Direct Oxidation of Benzene to Phenol with Visible Light," , Chemsuschem, vol 7, no 3, pp 738-742, Mar 2014, doi: 10.1002/cssc.201301128 [116] X Q Fan et al., "Construction of Graphitic C3N4-Based Intramolecular Donor - Acceptor Conjugated Copolymers for Photocatalytic Hydrogen Evolution," , Acs Catal, vol 5, no 9, pp 5008-5015, Sep 2015, doi: 10.1021/acscatal.5b01155 [117] S Chu et al., "Band Structure Engineering of Carbon Nitride: In Search of a Polymer Photocatalyst with High Photooxidation Property," , Acs Catal, vol 3, no 5, pp 912-919, May 2013, doi: 10.1021/cs4000624 [118] A K Geim and K S Novoselov, "The rise of graphene," , Nat Mater, vol 6, no 3, pp 183-191, Mar 2007, doi: DOI 10.1038/nmat1849 [119] M Xiao et al., "Understanding the roles of carbon in carbon/g-C3N4 based photocatalysts for H-2 evolution," , Nano Res, Oct 15 2021, doi: 10.1007/s12274-021-3897-7 [120] B Chai, X Liao, F K Song, and H Zhou, "Fullerene modified C3N4 composites with enhanced photocatalytic activity under visible light irradiation," , Dalton T, vol 43, no 3, pp 982-989, 2014, doi: 10.1039/c3dt52454j [121] Z Guo et al., "High activity of g-C3N4/multiwall carbon nanotube in catalytic ozonation promotes electro-peroxone process," , Chemosphere, vol 201, pp 206-213, Jun 2018, doi: 10.1016/j.chemosphere.2018.02.176 [122] H Gu, T S Zhou, and G Y Shi, "Synthesis of graphene supported graphene-like C3N4 metal-free layered nanosheets for enhanced electrochemical performance and their biosensing for biomolecules," , Talanta, vol 132, pp 871-876, Jan 15 2015, doi: 10.1016/j.talanta.2014.09.042 [123] S F Duan et al., "Phosphorus-doped Isotype g-C3N4/g-C3N4: An Efficient Charge Transfer System for Photoelectrochemical Water 88 Oxidation," , Chemcatchem, vol 11, no 2, pp 729-736, Jan 23 2019, doi: 10.1002/cctc.201801581 [124] H L Zhu, D M Chen, D Yue, Z H Wang, and H Ding, "In-situ synthesis of g-C3N4-P25 TiO2 composite with enhanced visible light photoactivity," , J Nanopart Res, vol 16, no 10, Sep 19 2014, doi: 10.1007/s11051-0142632-7 [125] M J Munoz-Batista, A Kubacka, and M Fernandez-Garcia, "Effect of gC3N4 loading on TiO2-based photocatalysts: UV and visible degradation of toluene," , Catal Sci Technol, vol 4, no 7, pp 2006-2015, 2014, doi: 10.1039/c4cy00226a [126] D M Chen, K W Wang, D G Xiang, R L Zong, W Q Yao, and Y F Zhu, "Significantly enhancement of photocatalytic performances via coreshell structure of ZnO@mpg-C3N4," , Appl Catal B-Environ, vol 147, pp 554-561, Apr 2014, doi: 10.1016/j.apcatb.2013.09.039 [127] W L Yu, J X Chen, T T Shang, L F Chen, L Gu, and T Y Peng, "Direct Z-scheme g-C3N4/WO3 photocatalyst with atomically defined junction for H-2 production," , Appl Catal B-Environ, vol 219, pp 693704, Dec 15 2017, doi: 10.1016/j.apcatb.2017.08.018 [128] K Katsumata, R Motoyoshi, N Matsushita, and K Okada, "Preparation of graphitic carbon nitride (g-C3N4)/WO3 composites and enhanced visiblelight-driven photodegradation of acetaldehyde gas," , J Hazard Mater, vol 260, pp 475-482, Sep 15 2013, doi: 10.1016/j.jhazmat.2013.05.058 [129] I Aslam et al., "The synergistic effect between WO3 and g-C3N4 towards efficient visible-light-driven photocatalytic performance," , New J Chem, vol 38, no 11, pp 5462-5469, 2014, doi: 10.1039/c4nj01370k [130] J Chen et al., "In-situ reduction synthesis of nano-sized Cu2O particles modifying g-C3N4 for enhanced photocatalytic hydrogen production," , Appl Catal B-Environ, vol 152, pp 335-341, Jun 25 2014, doi: 10.1016/j.apcatb.2014.01.047 [131] S Ye, L G Qiu, Y P Yuan, Y J Zhu, J Xia, and J F Zhu, "Facile fabrication of magnetically separable graphitic carbon nitride photocatalysts with enhanced photocatalytic activity under visible light," , J Mater Chem A, vol 1, no 9, pp 3008-3015, 2013, doi: 10.1039/c2ta01069k 89 [132] K C Christoforidis, T Montini, E Bontempi, S Zafeiratos, J J D Jaen, and P Fornasiero, "Synthesis and photocatalytic application of visible-light active beta-Fe2O3/g-C3N4 hybrid nanocomposites," , Appl Catal BEnviron, vol 187, pp 171-180, Jun 15 2016, doi: 10.1016/j.apcatb.2016.01.013 [133] Y J Wang, R Shi, J Lin, and Y F Zhu, "Enhancement of photocurrent and photocatalytic activity of ZnO hybridized with graphite-like C3N4," , Energ Environ Sci, vol 4, no 8, pp 2922-2929, Aug 2011, doi: 10.1039/c0ee00825g [134] A Dhakshinamoorthy, A M Asiri, and H Garcia, "Metal-Organic Framework (MOF) Compounds: Photocatalysts for Redox Reactions and Solar Fuel Production," , Angew Chem Int Edit, vol 55, no 18, pp 54145445, Apr 25 2016, doi: 10.1002/anie.201505581 [135] S B Wang, J L Lin, and X C Wang, "Semiconductor-redox catalysis promoted by metal-organic frameworks for CO2 reduction," , Phys Chem Chem Phys, vol 16, no 28, pp 14656-14660, 2014, doi: 10.1039/c4cp02173h [136] J D Hong, C P Chen, F E Bedoya, G H Kelsall, D O'Hare, and C Petit, "Carbon nitride nanosheet/metal-organic framework nanocomposites with synergistic photocatalytic activities," , Catal Sci Technol, vol 6, no 13, pp 5042-5051, 2016, doi: 10.1039/c5cy01857a [137] H Wang et al., "Synthesis and applications of novel graphitic carbon nitride/metal-organic frameworks mesoporous photocatalyst for dyes removal," , Appl Catal B-Environ, vol 174, pp 445-454, Sep 2015, doi: 10.1016/j.apcatb.2015.03.037 [138] C L Tan, X Huang, and H Zhang, "Synthesis and applications of graphene-based noble metal nanostructures," , Mater Today, vol 16, no 12, pp 29-36, Jan-Feb 2013, doi: 10.1016/j.mattod.2013.01.021 [139] X M Zhang, Y L Chen, R S Liu, and D P Tsai, "Plasmonic photocatalysis," , Rep Prog Phys, vol 76, no 4, Apr 2013, doi: 10.1088/0034-4885/76/4/046401 [140] X D Li, T P Chen, Y Liu, and K C Leong, "Influence of localized surface plasmon resonance and free electrons on the optical properties of 90 ultrathin Au films: a study of the aggregation effect," , Opt Express, vol 22, no 5, pp 5124-5132, Mar 10 2014, doi: 10.1364/Oe.22.005124 [141] P Drude, "Zur Elektronentheorie der Metalle," Phys Rev Lett., vol 306, pp 556-613, 1990 [142] P Drude, "Zur Elektronentheorie der Metalle; II Teil Galvanomagnetische und thermomagnetische Effecte," Phys Rev Lett., vol 308, pp 369-402, 1990 [143] S A C M Rahm, D Schurig, J.B Pendry, D.R Smith, "Optical design of reflectionless complex media by finite embedded coordinate transformations," Phys Rev Lett., vol 100, 063903, 2008 [144] C W Keliang Hou, Xiang Liu, "Study on Backward Scattering Characteristics of Submicron Particles," Optics and Photonics Journal, vol 10, 5, 2000 [145] K L Kelly, E Coronado, L L Zhao, and G C Schatz, "The optical properties of metal nanoparticles: The influence of size, shape, and dielectric environment," , J Phys Chem B, vol 107, no 3, pp 668-677, Jan 23 2003, doi: 10.1021/jp026731y [146] P Jiménez-Calvo, "Synthesis, characterization, and performance of gC3N4 based materials decorated with Au nanoparticles for (photo) catalytic applications," Thesis for: Ph.D in Chemical-Physics of Materials, 2019 [147] B Oregan and M Gratzel, "A Low-Cost, High-Efficiency Solar-Cell Based on Dye-Sensitized Colloidal Tio2 Films," , Nature, vol 353, no 6346, pp 737-740, Oct 24 1991, doi: DOI 10.1038/353737a0 [148] S Linic, P Christopher, and D B Ingram, "Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy," , Nat Mater, vol 10, no 12, pp 911-921, Dec 2011, doi: 10.1038/Nmat3151 [149] E C Le Ru, E Blackie, M Meyer, and P G Etchegoin, "Surface enhanced Raman scattering enhancement factors: a comprehensive study," , J Phys Chem C, vol 111, no 37, pp 13794-13803, Sep 20 2007, doi: 10.1021/jp0687908 [150] B N J Persson and A Baratoff, "Theory of Photon-Emission in ElectronTunneling to Metallic Particles," , Phys Rev Lett, vol 68, no 21, pp 32243227, May 25 1992, doi: DOI 10.1103/PhysRevLett.68.3224 91 [151] Y Shiraishi et al., "Quantum tunneling injection of hot electrons in Au/TiO2 plasmonic photocatalysts," , Nanoscale, vol 9, no 24, pp 83498361, Jun 28 2017, doi: 10.1039/c7nr02310c [152] A Furube, L Du, K Hara, R Katoh, and M Tachiya, "Ultrafast plasmoninduced electron transfer from gold nanodots into TiO2 nanoparticles," , J Am Chem Soc, vol 129, no 48, pp 14852-+, Dec 2007, doi: 10.1021/ja076134v [153] S K Cushing and N Wu, "Progress and Perspectives of Plasmon-Enhanced Solar Energy Conversion," J Phys Chem Lett, vol 7, no 4, pp 666-75, Feb 18 2016, doi: 10.1021/acs.jpclett.5b02393 [154] A Kahn, "Fermi level, work function and vacuum level," , Mater Horiz, vol 3, no 1, pp 7-10, Jan 2016, doi: 10.1039/c5mh00160a [155] S S Kocha, J A Turner, and A J Nozik, "Study of the Schottky-Barrier and Determination of the Energetic Positions of Band Edges at the N-Type and P-Type Gallium Indium-Phosphide Electrode-Electrolyte Interface," , J Electroanal Chem, vol 367, no 1-2, pp 27-30, Apr 1994, doi: Doi 10.1016/0022-0728(93)03020-P [156] V Subramanian, E Wolf, and P V Kamat, "Semiconductor-metal composite nanostructures To what extent metal nanoparticles improve the photocatalytic activity of TiO2 films?," , J Phys Chem B, vol 105, no 46, pp 11439-11446, Nov 22 2001, doi: 10.1021/jp011118k [157] M Haruta, "Catalysis - Gold rush," , Nature, vol 437, no 7062, pp 10981099, Oct 20 2005, doi: 10.1038/4371098a [158] J S Qiguang Yang, Wan-Joong Kim, SungSoo Jung, Bagher Tabibi, Justin Vazquez, Jasmine Austin, Doyle Temple, "Optical properties of morphology-controlled gold nanoparticles," SPIE Conference Proceedings, vol 7226, 727617, 2009 [159] M Rycenga et al., "Controlling the Synthesis and Assembly of Silver Nanostructures for Plasmonic Applications," , Chem Rev, vol 111, no 6, pp 3669-3712, Jun 2011, doi: 10.1021/cr100275d [160] W D Callister, "Materials Science and Engineering: An Introduction," Book p 722, 2007 [161] P Wang, B B Huang, Y Dai, and M H Whangbo, "Plasmonic photocatalysts: harvesting visible light with noble metal nanoparticles," , 92 Phys Chem Chem Phys, vol 14, no 28, pp 9813-9825, 2012, doi: 10.1039/c2cp40823f [162] S Sarina, E R Waclawik, and H Y Zhu, "Photocatalysis on supported gold and silver nanoparticles under ultraviolet and visible light irradiation," , Green Chem, vol 15, no 7, pp 1814-1833, 2013, doi: 10.1039/c3gc40450a [163] S Patnaik, S Martha, G Madras, and K Parida, "The effect of sulfate pretreatment to improve the deposition of Au-nanoparticles in a gold-modified sulfated g-C3N4 plasmonic photocatalyst towards visible light induced water reduction reaction," , Phys Chem Chem Phys, vol 18, no 41, pp 28502-28514, Nov 2016, doi: 10.1039/c6cp04262g [164] R C Pawar, S Kang, S H Ahn, and C S Lee, "Gold nanoparticle modified graphitic carbon nitride/multi-walled carbon nanotube (gC3N4/CNTs/Au) hybrid photocatalysts for effective water splitting and degradation," , Rsc Adv, vol 5, no 31, pp 24281-24292, 2015, doi: 10.1039/c4ra15560b [165] L Zhang, F X Mao, L R Zheng, H F Wang, X H Yang, and H G Yang, "Tuning Metal Catalyst with Metal-C3N4 Interaction for Efficient CO2 Electroreduction," , Acs Catal, vol 8, no 12, pp 11035-11041, Dec 2018, doi: 10.1021/acscatal.8b03789 [166] S Q Chang, A Y Xie, S Chen, and J Xiang, "Enhanced photoelectrocatalytic oxidation of small organic molecules by gold nanoparticles supported on carbon nitride," , J Electroanal Chem, vol 719, pp 86-91, Apr 2014, doi: 10.1016/j.jelechem.2014.01.026 [167] Q Z Zhang, J J Deng, Z H Xu, M Chaker, and D L Ma, "HighEfficiency Broadband C3N4 Photocatalysts: Synergistic Effects from Upconversion and Plasmons," , Acs Catal, vol 7, no 9, pp 6225-6234, Sep 2017, doi: 10.1021/acscatal.7b02013 [168] M A Gondal et al., "Facile synthesis, characterization and photocatalytic performance of Au-Ag alloy nanoparticles dispersed on graphitic carbon nitride under visible light irradiations," , J Mol Catal a-Chem, vol 423, pp 114-125, Nov 2016, doi: 10.1016/j.molcata.2016.06.013 [169] G Darabdhara and M R Das, "Bimetallic Au-Pd nanoparticles on 2D supported graphitic carbon nitride and reduced graphene oxide sheets: A 93 comparative photocatalytic degradation study of organic pollutants in water," , Chemosphere, vol 197, pp 817-829, Apr 2018, doi: 10.1016/j.chemosphere.2018.01.073 [170] Y Z Guo et al., "Understanding the roles of plasmonic Au nanocrystal size, shape, aspect ratio and loading amount in Au/g-C3N4 hybrid nanostructures for photocatalytic hydrogen generation," , Phys Chem Chem Phys, vol 20, no 34, pp 22296-22307, Sep 14 2018, doi: 10.1039/c8cp04241a [171] Z H Xu et al., "Towards enhancing photocatalytic hydrogen generation: Which is more important, alloy synergistic effect or plasmonic effect?," , Appl Catal B-Environ, vol 221, pp 77-85, Feb 2018, doi: 10.1016/j.apcatb.2017.08.085 [172] L Ge, C C Han, and J Liu, "In situ synthesis and enhanced visible light photocatalytic activities of novel PANI-g-C3N4 composite photocatalysts," , J Mater Chem, vol 22, no 23, pp 11843-11850, 2012, doi: 10.1039/c2jm16241e [173] R Kumar, M A Barakat, and F A Alseroury, "Oxidized gC3N4/polyaniline nanofiber composite for the selective removal of hexavalent chromium," , Sci Rep-Uk, vol 7, Oct 2017, doi: 10.1038/s41598-017-12850-1 [174] J H Li, B A Shen, Z H Hong, B Z Lin, B F Gao, and Y L Chen, "A facile approach to synthesize novel oxygen-doped g-C3N4 with superior visible-light photoreactivity," , Chem Commun, vol 48, no 98, pp 1201712019, 2012, doi: 10.1039/c2cc35862j [175] G H Dong, Z H Ai, and L Z Zhang, "Efficient anoxic pollutant removal with oxygen functionalized graphitic carbon nitride under visible light," , Rsc Adv, vol 4, no 11, pp 5553-5560, 2014, doi: 10.1039/c3ra46068a [176] P X Qiu et al., "Fabrication of an exfoliated graphitic carbon nitride as a highly active visible light photocatalyst," , J Mater Chem A, vol 3, no 48, pp 24237-24244, 2015, doi: 10.1039/c5ta08406g [177] J C Tong, L Zhang, F Li, K Wang, L F Han, and S K Cao, "Rapid and high-yield production of g-C3N4 nanosheets via chemical exfoliation for photocatalytic H-2 evolution," , Rsc Adv, vol 5, no 107, pp 88149-88153, 2015, doi: 10.1039/c5ra16988g 94 [178] P K Chuang, K H Wu, T F Yeh, and H S Teng, "Extending the piConjugation of g-C3N4 by Incorporating Aromatic Carbon for Photocatalytic H-2 Evolution from Aqueous Solution," , Acs Sustain Chem Eng, vol 4, no 11, pp 5989-5997, Nov 2016, doi: 10.1021/acssuschemeng.6b01266 [179] Z J Huang, F B Li, B F Chen, and G Q Yuan, "Porous and low-defected graphitic carbon nitride nanotubes for efficient hydrogen evolution under visible light irradiation," , Rsc Adv, vol 5, no 124, pp 102700-102706, 2015, doi: 10.1039/c5ra23419k [180] B C Zhu, P F Xia, W K Ho, and J G Yu, "Isoelectric point and adsorption activity of porous g-C3N4," , Appl Surf Sci, vol 344, pp 188195, Jul 30 2015, doi: 10.1016/j.apsusc.2015.03.086 [181] F R Pomilla et al., "An Investigation into the Stability of Graphitic C3N4 as a Photocatalyst for CO2 Reduction," , J Phys Chem C, vol 122, no 50, pp 28727-28738, Dec 20 2018, doi: 10.1021/acs.jpcc.8b09237 [182] H W Guo, M Q Chen, Q Zhong, Y A Wang, W H Ma, and J Ding, "Synthesis of Z-scheme alpha-Fe2O3/g-C3N4 composite with enhanced visible-light photocatalytic reduction of CO2 to CH3OH," , J Co2 Util, vol 33, pp 233-241, Oct 2019, doi: 10.1016/j.jcou.2019.05.016 [183] F Chang, C L Li, J R Luo, Y C Xie, B Q Deng, and X F Hu, "Enhanced visible-light-driven photocatalytic performance of porous graphitic carbon nitride," , Appl Surf Sci, vol 358, pp 270-277, Dec 15 2015, doi: 10.1016/j.apsusc.2015.08.124 [184] Y Zheng, Z S Zhang, and C H Li, "A comparison of graphitic carbon nitrides synthesized from different precursors through pyrolysis," , J Photoch Photobio A, vol 332, pp 32-44, Jan 2017, doi: 10.1016/j.jphotochem.2016.08.005 [185] Y M He, Y Wang, L H Zhang, B T Teng, and M H Fan, "Highefficiency conversion of CO2 to fuel over ZnO/g-C3N4 photocatalyst," , Appl Catal B-Environ, vol 168, pp 1-8, Jun 2015, doi: 10.1016/j.apcatb.2014.12.017 [186] S Z Liu, D G Li, H Q Sun, H M Ang, M O Tade, and S B Wang, "Oxygen functional groups in graphitic carbon nitride for enhanced 95 photocatalysis," , J Colloid Interf Sci, vol 468, pp 176-182, Apr 15 2016, doi: 10.1016/j.jcis.2016.01.051 [187] K Q D.J Martin, S.A Shevlin, A.D Handoko, X Chen, Z Guo, J Tang, "Highly efficient photocatalytic H2 evolution from water using visible light and structure controlled graphitic carbon nitride," Angew Chem Int Ed , vol 53, pp 9240-9245, 2014 [188] H A Bicalho et al., "Facile synthesis of highly dispersed Fe(II)-doped gC3N4 and its application in Fenton-like catalysis," , Mol Catal, vol 435, pp 156-165, Jul 2017, doi: 10.1016/j.mcat.2017.04.003 [189] F Y Wei et al., "Oxygen self-doped g-C3N4 with tunable electronic band structure for unprecedentedly enhanced photocatalytic performance," , Nanoscale, vol 10, no 9, pp 4515-4522, Mar 2018, doi: 10.1039/c7nr09660g [190] J Wang et al., "Simple Synthesis of High Specific Surface Carbon Nitride for Adsorption-Enhanced Photocatalytic Performance," , Nanoscale Res Lett, vol 13, Aug 22 2018, doi: 10.1186/s11671-018-2654-7 [191] Y L Zhu, Y Q Shi, Z Q Huang, L J Duan, Q L Tai, and Y Hu, "Novel graphite-like carbon nitride/organic aluminum diethylhypophosphites nanohybrid: Preparation and enhancement on thermal stability and flame retardancy of polystyrene," , Compos Part a-Appl S, vol 99, pp 149-156, Aug 2017, doi: 10.1016/j.compositesa.2017.03.023 [192] M Wojtoniszak, D Roginska, B Machalinski, M Drozdzik, and E Mijowska, "Graphene oxide functionalized with methylene blue and its performance in singlet oxygen generation," , Mater Res Bull, vol 48, no 7, pp 2636-2639, Jul 2013, doi: 10.1016/j.materresbull.2013.03.040 [193] M Ayan-Varela et al., "Investigating the Dispersion Behavior in Solvents, Biocompatibility, and Use as Support for Highly Efficient Metal Catalysts of Exfoliated Graphitic Carbon Nitride," , Acs Appl Mater Inter, vol 7, no 43, pp 24032-24045, Nov 2015, doi: 10.1021/acsami.5b06974 [194] Y L Liao, S M Zhu, Z X Chen, X H Lou, and D Zhang, "A facile method of activating graphitic carbon nitride for enhanced photocatalytic activity," , Phys Chem Chem Phys, vol 17, no 41, pp 27826-27832, 2015, doi: 10.1039/c5cp05186j 96 [195] R G J Tauc, A Vancu, "Optical Properties and Electronic Structure of Amorphous Germanium," Wiley Online Library, vol 15, no 2, pp 627637, 1966 [196] J Y Qin, J P Huo, P Y Zhang, J Zeng, T T Wang, and H P Zeng, "Improving the photocatalytic hydrogen production of Ag/g-C3N4 nanocomposites by dye-sensitization under visible light irradiation," , Nanoscale, vol 8, no 4, pp 2249-2259, 2016, doi: 10.1039/c5nr06346a [197] X J Bai, L Wang, R L Zong, and Y F Zhu, "Photocatalytic Activity Enhanced via g-C3N4 Nanoplates to Nanorods," , J Phys Chem C, vol 117, no 19, pp 9952-9961, May 16 2013, doi: 10.1021/jp402062d [198] B Liu et al., "Phosphorus-Doped Graphitic Carbon Nitride Nanotubes with Amino-rich Surface for Efficient CO2 Capture, Enhanced Photocatalytic Activity, and Product Selectivity," , Acs Appl Mater Inter, vol 10, no 4, pp 4001-4009, Jan 31 2018, doi: 10.1021/acsami.7b17503 [199] Y J Zhou et al., "Brand new P-doped g-C3N4: enhanced photocatalytic activity for H-2 evolution and Rhodamine B degradation under visible light," , J Mater Chem A, vol 3, no 7, pp 3862-3867, 2015, doi: 10.1039/c4ta05292g [200] J J Ji et al., "Simultaneous Noncovalent Modification and Exfoliation of 2D Carbon Nitride for Enhanced Electrochemiluminescent Biosensing," , J Am Chem Soc, vol 139, no 34, pp 11698-11701, Aug 30 2017, doi: 10.1021/jacs.7b06708 [201] J J Xue, S S Ma, Y M Zhou, Z W Zhang, and M He, "Facile Photochemical Synthesis of Au/Pt/g-C3N4 with Plasmon-Enhanced Photocatalytic Activity for Antibiotic Degradation," , Acs Appl Mater Inter, vol 7, no 18, pp 9630-9637, May 13 2015, doi: 10.1021/acsami.5b01212 [202] Y J Zhang, A Thomas, M Antonietti, and X C Wang, "Activation of Carbon Nitride Solids by Protonation: Morphology Changes, Enhanced Ionic Conductivity, and Photoconduction Experiments," , J Am Chem Soc, vol 131, no 1, pp 50-+, Jan 14 2009, doi: 10.1021/ja808329f [203] L C Liu, T Wei, X Guan, X H Zi, H He, and H X Dai, "Size and Morphology Adjustment of PVP-Stabilized Silver and Gold Nanocrystals 97 Synthesized by Hydrodynamic Assisted Self-Assembly," , J Phys Chem C, vol 113, no 20, pp 8595-8600, May 21 2009, doi: 10.1021/jp810668x [204] L C Chen et al., "Gold Nanoparticle-Graphite-Like C3N4 Nanosheet Nanohybrids Used for Electrochemiluminescent Immunosensor," , Anal Chem, vol 86, no 9, pp 4188-4195, May 2014, doi: 10.1021/ac403635f [205] M R F Ahmad Monshi, Mohammad Reza Monshi, "Modified Scherrer Equation to Estimate More Accurately Nano-Crystallite Size Using XRD," World Journal of Nano Science and Engineering, vol 2, pp 154-160, 2012 [206] M F Lu et al., "Au-loaded porous g-C3N4 nanosheets for enhanced photocatalytic IPA degradation under visible-light irradiation," , J Phys D Appl Phys, vol 52, no 9, Feb 27 2019, doi: 10.1088/1361-6463/aaf782 [207] X P Sun, S J Dong, and E Wang, "Large-scale synthesis of micrometerscale single-crystalline Au plates of nanometer thickness by a wet-chemical route," , Angew Chem Int Edit, vol 43, no 46, pp 6360-6363, 2004, doi: 10.1002/anie.200461013 [208] K C Christoforidis et al., "Metal-free dual-phase full organic carbon nanotubes/g-C3N4 heteroarchitectures for photocatalytic hydrogen production," , Nano Energy, vol 50, pp 468-478, Aug 2018, doi: 10.1016/j.nanoen.2018.05.070 [209] J Jiang, J G Yu, and S W Cao, "Au/PtO nanoparticle-modified g-C3N4 for plasmon-enhanced photocatalytic hydrogen evolution under visible light," , J Colloid Interf Sci, vol 461, pp 56-63, Jan 2016, doi: 10.1016/j.jcis.2015.08.076 [210] S Balu, Y L Chen, T C K Yang, N Chen, and S W Chen, "Effect of ultrasound-induced hydroxylation and exfoliation on P90-TiO2/g-C3N4 hybrids with enhanced optoelectronic properties for visible-light photocatalysis and electrochemical sensing," , Ceram Int, vol 46, no 11, pp 18002-18018, Aug 2020, doi: 10.1016/j.ceramint.2020.04.115 [211] C M Li et al., "Z-scheme mesoporous photocatalyst constructed by modification of Sn3O4 nanoclusters on g-C3N4 nanosheets with improved photocatalytic performance and mechanism insight," , Appl Catal BEnviron, vol 238, pp 284-293, Dec 15 2018, doi: 10.1016/j.apcatb.2018.07.049 98 [212] C M Li et al., "Mesoporous ferriferrous oxide nanoreactors modified on graphitic carbon nitride towards improvement of physical, photoelectrochemical properties and photocatalytic performance," , J Colloid Interf Sci, vol 531, pp 331-342, Dec 2018, doi: 10.1016/j.jcis.2018.07.083 [213] J F Wang, J Chen, P F Wang, J Hou, C Wang, and Y H Ao, "Robust photocatalytic hydrogen evolution over amorphous ruthenium phosphide quantum dots modified g-C3N4 nanosheet," , Appl Catal B-Environ, vol 239, pp 578-585, Dec 30 2018, doi: 10.1016/j.apcatb.2018.08.048 [214] X S Zhou et al., "A carbon nitride/TiO2 nanotube array heterojunction visible-light photocatalyst: synthesis, characterization, and photoelectrochemical properties," , J Mater Chem, vol 22, no 34, pp 17900-17905, 2012, doi: 10.1039/c2jm32686h [215] T D Tran, M T T Nguyen, H V Le, D N Nguyen, Q D Truong, and P D Tran, "Gold nanoparticles as an outstanding catalyst for the hydrogen evolution reaction," , Chem Commun, vol 54, no 27, pp 3363-3366, Apr 2018, doi: 10.1039/c8cc00038g [216] Y J Liu, H X Liu, H M Zhou, T D Li, and L N Zhang, "A Z-scheme mechanism of N-ZnO/g-C3N4 for enhanced H-2 evolution and photocatalytic degradation," , Appl Surf Sci, vol 466, pp 133-140, Feb 2019, doi: 10.1016/j.apsusc.2018.10.027 [217] Z W Zhu, Z S Wang, J W Di, Y M Long, and W F Li, "Enhanced visible-light photocatalytic properties of g-C3N4 by coupling with ZnAl2O4," , Catal Commun, vol 86, pp 86-90, Nov 2016, doi: 10.1016/j.catcom.2016.08.017 [218] L H Xie, Z Y Ai, M Zhang, R Z Sun, and W R Zhao, "Enhanced Hydrogen Evolution in the Presence of Plasmonic Au-Photo-Sensitized gC3N4 with an Extended Absorption Spectrum from 460 to 640 nm," , Plos One, vol 11, no 8, Aug 30 2016, doi: 10.1371/journal.pone.0161397 [219] Y H Ling, F J Ren, and J Y Feng, "Reverse bias voltage dependent hydrogen sensing properties on Au-TiO2 nanotubes Schottky barrier diodes," , Int J Hydrogen Energ, vol 41, no 18, pp 7691-7698, May 18 2016, doi: 10.1016/j.ijhydene.2016.02.007 99 [220] S Liu, D Li, H Sun, H.M Ang, M.O Tadé, S Wang, Oxygen functional groups in graphitic carbon nitride for enhanced photocatalysis, J Colloid Interface Sci 468 (2016) 176–182 DOI https://doi.org/10.1016/j.apsusc.2015.09.042 [221] G Dong, Z Ai, L Zhang, Efficient anoxic pollutant removal with oxygen functionalized graphitic carbon nitride under visible light, RSC Adv (2014) 5553–5560 DOI https://doi.org/10.1039/C2CC35862J [222] J Li, B Shen, Z Hong, B Lin, B Gao, Y Chen, A facile approach to synthesize novel oxygen-doped g-C3N4 with superior visible-light photoreactivity, Chem Commun 48 (2012) 12017–12019 DOI https://doi.org/10.1039/C3RA46068A [223] M Ilkaeva, I Krivtsov, E Bartashevich, S Khainakov, J.R García, E Díaz, S Ordóđez, Carbon nitride assisted chemoselective C–H bond photooxidation of alkylphenolethoxylates in water medium, Green Chem 19 (2017) 4299–4304 DOI https://doi.org/10.1039/C7GC01588G 100 ... Department of Physical Chemistry, Institute of Chemical Engineering, Hanoi University of Science and Technology together with the research group of Prof Jennifer Stunk at Leibniz Institute of Catalysis... Table Position of p-C3N4 (002) reflection and crystallite size of Au nanoparticles of wt.% Au/p-C3N4 samples .56 Table Table of band gap energy of wt.% Au/p-C3N4 calculated from Tauc''s... [1] Polymeric carbon nitride (p-C3N4) has been considered as a promising photocatalyst candidate due to its low cost, chemical stability, and visible light reactivity However, the performance of