Insights into photocatalytic CO2 reduction on C3N4: Strategy of simultaneous B, K co-doping and enhancement by N vacancies

Abstract C3N4 is a promising non-metal photocatalyst for CO2 conversion to value-added products, while it shows unsatisfactory performance due to the low CO2 adsorption ability and poor utilization of the photo-excited charge carriers. The deficiency of electron donation sites and unoptimized electronic structure are the primary reasons behind. To address the challenges, herein, we propose a new synthesis strategy of rational co-doping of B, K elements in line with controllable introduction of Nv into C3N4 within one step during synthesis. The synergistic effects of the modification factors resulted in an enhanced C3N4 catalyst with an electron-rich surface and tailored electronic structure, which significantly facilitated the CO2 adsorption and activation in sequence. Moreover, the drawback of single element doping is largely avoided due to the synergistic effects provided by this rational multiple modification strategy. A 5-h photocatalytic production of 5.93 μmol g−1 CH4 and 3.16 μmol g−1 CO respectively were achieved using CO2 and H2O as feedstocks without the presence of any organic hole scavenger, which are 161% and 527% of CH4 and CO produced by pristine C3N4.

[1]  Xi‐Wen Du,et al.  Porous P-doped graphitic carbon nitride nanosheets for synergistically enhanced visible-light photocatalytic H2 production , 2015 .

[2]  Zhengguo Zhang,et al.  Enhanced Photocatalytic Hydrogen Evolution Performance of Mesoporous Graphitic Carbon Nitride Co-doped with Potassium and Iodine , 2018 .

[3]  Yan‐Zhen Zheng,et al.  Heteroatoms binary-doped hierarchical porous g-C3N4 nanobelts for remarkably enhanced visible-light-driven hydrogen evolution , 2018, Applied Catalysis B: Environmental.

[4]  Seng Sing Tan,et al.  Kinetic modelling for photosynthesis of hydrogen and Methane through catalytic reduction of carbon dioxide with water vapour , 2008 .

[5]  Jiaguo Yu,et al.  Mechanistic insight into the enhanced photocatalytic activity of single-atom Pt, Pd or Au-embedded g-C 3 N 4 , 2018 .

[6]  Jiaguo Yu,et al.  Single‐Atom Engineering of Directional Charge Transfer Channels and Active Sites for Photocatalytic Hydrogen Evolution , 2018, Advanced Functional Materials.

[7]  Jiaguo Yu,et al.  First-principle calculation study of tri- s -triazine-based g-C 3 N 4 : A review , 2018 .

[8]  Xi. Wu,et al.  Strong base g-C3N4 with perfect structure for photocatalytically eliminating formaldehyde under visible-light irradiation , 2018, Applied Catalysis B: Environmental.

[9]  Jie Liang,et al.  Phosphorus- and Sulfur-Codoped g-C3N4: Facile Preparation, Mechanism Insight, and Application as Efficient Photocatalyst for Tetracycline and Methyl Orange Degradation under Visible Light Irradiation , 2017 .

[10]  Jianghong Zhao,et al.  Ammonia-induced robust photocatalytic hydrogen evolution of graphitic carbon nitride. , 2015, Nanoscale.

[11]  M. Jaroniec,et al.  Facet effect of Pd cocatalyst on photocatalytic CO 2 reduction over g-C 3 N 4 , 2017 .

[12]  J. Kuhn,et al.  Oxygen vacancy formation characteristics in the bulk and across different surface terminations of La(1−x)SrxFe(1−y)CoyO(3−δ) perovskite oxides for CO2 conversion , 2016 .

[13]  Shaozheng Hu,et al.  Band gap-tunable potassium doped graphitic carbon nitride with enhanced mineralization ability. , 2015, Dalton transactions.

[14]  W. Ho,et al.  Enhanced visible-light-driven photocatalytic removal of NO: Effect on layer distortion on g-C₃N₄ by H₂ heating , 2015 .

[15]  Yunpei Zhu,et al.  Mesoporous Phosphorus-Doped g-C3N4 Nanostructured Flowers with Superior Photocatalytic Hydrogen Evolution Performance. , 2015, ACS applied materials & interfaces.

[16]  Lei Yu,et al.  Novel (Na, O) co-doped g-C3N4 with simultaneously enhanced absorption and narrowed bandgap for highly efficient hydrogen evolution , 2017 .

[17]  Lianjun Liu,et al.  Photocatalytic CO2 Reduction with H2O on TiO2 Nanocrystals: Comparison of Anatase, Rutile, and Brookite Polymorphs and Exploration of Surface Chemistry , 2012 .

[18]  Hui Huang,et al.  Tunable ternary (N, P, B)-doped porous nanocarbons and their catalytic properties for oxygen reduction reaction. , 2014, ACS applied materials & interfaces.

[19]  A. B. Jorge,et al.  H2 and O2 Evolution from Water Half-Splitting Reactions by Graphitic Carbon Nitride Materials , 2013 .

[20]  Wenjun Luo,et al.  A Nanojunction Polymer Photoelectrode for Efficient Charge Transport and Separation , 2017, Angewandte Chemie.

[21]  Zhiyong Zhang,et al.  The Spatially Oriented Charge Flow and Photocatalysis Mechanism on Internal van der Waals Heterostructures Enhanced g-C3N4 , 2018, ACS Catalysis.

[22]  Yihe Zhang,et al.  Chlorine intercalation in graphitic carbon nitride for efficient photocatalysis , 2017 .

[23]  S. Grimme,et al.  A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. , 2010, The Journal of chemical physics.

[24]  Jinhua Ye,et al.  In situ surface alkalinized g-C3N4 toward enhancement of photocatalytic H2 evolution under visible-light irradiation , 2016 .

[25]  Shengwei Liu,et al.  Enhanced photocatalytic conversion of greenhouse gas CO2 into solar fuels over g-C3N4 nanotubes with decorated transparent ZIF-8 nanoclusters , 2017 .

[26]  Jianhua Zhao,et al.  Advances in Energy, Environment and Materials Science , 2016 .

[27]  Jiaguo Yu,et al.  First principle investigation of halogen-doped monolayer g-C3N4 photocatalyst , 2017 .

[28]  Yihe Zhang,et al.  Band structure engineering and efficient charge transport in oxygen substituted g-C3N4 for superior photocatalytic hydrogen evolution , 2018, Applied Catalysis B: Environmental.

[29]  K. Ohkubo,et al.  Electron-transfer state of 9-mesityl-10-methylacridinium ion with a much longer lifetime and higher energy than that of the natural photosynthetic reaction center. , 2004, Journal of the American Chemical Society.

[30]  E. Rodríguez-Castellón,et al.  Photosensitivity of g-C3N4/S-doped carbon composites: study of surface stability upon exposure to CO2 and/or water in ambient light , 2017 .

[31]  M. Marchewka Infrared and Raman spectra of melaminium chloride hemihydrate , 2002 .

[32]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[33]  Qingling Liu,et al.  NaKA sorbents with high CO(2)-over-N(2) selectivity and high capacity to adsorb CO(2). , 2010, Chemical communications.

[34]  R. Schlögl,et al.  Graphitic carbon nitride materials: variation of structure and morphology and their use as metal-free catalysts , 2008 .

[35]  Xiulian Pan,et al.  Catalytically Active Boron Nitride in Acetylene Hydrochlorination , 2017 .

[36]  C. F. Ng,et al.  Defect Engineered g-C3N4 for Efficient Visible Light Photocatalytic Hydrogen Production , 2015 .

[37]  Dan Wu,et al.  Phosphorylation of g-C3N4 for enhanced photocatalytic CO2 reduction , 2016 .

[38]  David S. Ginley,et al.  Prediction of Flatband Potentials at Semiconductor‐Electrolyte Interfaces from Atomic Electronegativities , 1978 .

[39]  M. Jaroniec,et al.  Ultra-thin nanosheet assemblies of graphitic carbon nitride for enhanced photocatalytic CO2 reduction , 2017 .

[40]  Carlo Cavazzoni,et al.  Advanced capabilities for materials modelling with Quantum ESPRESSO. , 2017, Journal of physics. Condensed matter : an Institute of Physics journal.

[41]  Yuichi Ichihashi,et al.  Photocatalytic reduction of CO2 with H2O on various titanium oxide catalysts , 1995 .

[42]  Zhengxin Liu,et al.  Cathodic and anodic photocurrents generation from melem and its derivatives , 2015 .

[43]  Aijun Du,et al.  Single Atom (Pd/Pt) Supported on Graphitic Carbon Nitride as an Efficient Photocatalyst for Visible-Light Reduction of Carbon Dioxide. , 2016, Journal of the American Chemical Society.

[44]  Youyong Li,et al.  Heptazine-based graphitic carbon nitride as an effective hydrogen purification membrane , 2016 .

[45]  J. Xu,et al.  A Strategy of Enhancing the Photoactivity of g-C3N4 via Doping of Nonmetal Elements: A First-Principles Study , 2012 .

[46]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[47]  Wei You,et al.  Hierarchical Porous O-Doped g-C3 N4 with Enhanced Photocatalytic CO2 Reduction Activity. , 2017, Small.

[48]  G. Henkelman,et al.  A fast and robust algorithm for Bader decomposition of charge density , 2006 .

[49]  Wei Zhao,et al.  Hydrogenated Blue Titania for Efficient Solar to Chemical Conversions: Preparation, Characterization, and Reaction Mechanism of CO2 Reduction , 2018 .

[50]  Blöchl,et al.  Projector augmented-wave method. , 1994, Physical review. B, Condensed matter.

[51]  Zhongfang Chen,et al.  How does the B,F-monodoping and B/F-codoping affect the photocatalytic water-splitting performance of g-C3N4? , 2016, Physical chemistry chemical physics : PCCP.

[52]  Jianlin Shi,et al.  A post-grafting strategy to modify g-C3N4 with aromatic heterocycles for enhanced photocatalytic activity , 2016 .

[53]  T. Schmidt,et al.  Carbon Dioxide and Formic Acid - The couple for an environmental-friendly hydrogen storage? , 2010 .

[54]  Jiaguo Yu,et al.  Sulfur-doped g-C3N4 with enhanced photocatalytic CO2-reduction performance , 2015 .

[55]  Yong Xu,et al.  The absolute energy positions of conduction and valence bands of selected semiconducting minerals , 2000 .

[56]  Wei Xing,et al.  Recent progress in hydrogen production from formic acid decomposition , 2018 .

[57]  Siang-Piao Chai,et al.  Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer To Achieving Sustainability? , 2016, Chemical reviews.

[58]  Jinlong Gong,et al.  CO2 photo-reduction: insights into CO2 activation and reaction on surfaces of photocatalysts , 2016 .

[59]  C. Zhang,et al.  Enriching CO2 Activation Sites on Graphitic Carbon Nitride with Simultaneous Introduction of Electron‐Transfer Promoters for Superior Photocatalytic CO2‐to‐Fuel Conversion , 2017 .

[60]  J. Rimstidt,et al.  X-ray photoelectron spectra of the alkali azides , 1972 .

[61]  Alexander J. Cowan,et al.  Photochemical CO2 reduction using structurally controlled g-C3N4. , 2016, Physical chemistry chemical physics : PCCP.

[62]  J. S. Lee,et al.  A highly active and stable palladium catalyst on a g-C3N4 support for direct formic acid synthesis under neutral conditions. , 2016, Chemical communications.

[63]  Huijuan Liu,et al.  Microstructure of carbon nitride affecting synergetic photocatalytic activity: Hydrogen bonds vs. structural defects , 2017 .

[64]  Hui-Ming Cheng,et al.  Increasing the Visible Light Absorption of Graphitic Carbon Nitride (Melon) Photocatalysts by Homogeneous Self‐Modification with Nitrogen Vacancies , 2014, Advanced materials.

[65]  M. Antonietti,et al.  A metal-free polymeric photocatalyst for hydrogen production from water under visible light. , 2009, Nature materials.

[66]  H. Hattori Heterogeneous Basic Catalysis , 1995 .

[67]  Tierui Zhang,et al.  Alkali‐Assisted Synthesis of Nitrogen Deficient Graphitic Carbon Nitride with Tunable Band Structures for Efficient Visible‐Light‐Driven Hydrogen Evolution , 2017, Advanced materials.

[68]  M. Antonietti,et al.  Polymeric Graphitic Carbon Nitride for Heterogeneous Photocatalysis , 2012 .

[69]  Yanli Wang,et al.  Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials , 2009 .

[70]  Li Wang,et al.  Carbon nitride with simultaneous porous network and O-doping for efficient solar-energy-driven hydrogen evolution , 2015 .

[71]  Fujio Izumi,et al.  VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data , 2011 .

[72]  Chenghua Sun,et al.  Understanding the Influence of Lattice Composition on the Photocatalytic Activity of Defect‐Pyrochlore‐Structured Semiconductor Mixed Oxides , 2015 .

[73]  Hui‐Ming Cheng,et al.  Nitrogen Vacancy-Promoted Photocatalytic Activity of Graphitic Carbon Nitride , 2012 .

[74]  Toshiki Tsubota,et al.  Photoelectrochemical CO2 reduction by a p-type boron-doped g-C3N4 electrode under visible light , 2016 .

[75]  X. Wen,et al.  Unravelling charge carrier dynamics in protonated g-C3N4 interfaced with carbon nanodots as co-catalysts toward enhanced photocatalytic CO2 reduction: A combined experimental and first-principles DFT study , 2017, Nano Research.

[76]  Subhajyoti Samanta,et al.  Facile Synthesis of Au/g‐C3N4 Nanocomposites: An Inorganic/Organic Hybrid Plasmonic Photocatalyst with Enhanced Hydrogen Gas Evolution Under Visible‐Light Irradiation , 2014 .

[77]  Xue-qing Gong,et al.  Selectivity switching resulting in the formation of benzene by surface carbonates on ceria in catalytic gas-phase oxidation of benzyl alcohol. , 2016, Chemical communications.

[78]  W. C. Wilfong,et al.  In situ ATR and DRIFTS studies of the nature of adsorbed CO₂ on tetraethylenepentamine films. , 2014, ACS applied materials & interfaces.

[79]  S. Trasatti The absolute electrode potential: an explanatory note (Recommendations 1986) , 1986 .

[80]  F. Dong,et al.  Steering the interlayer energy barrier and charge flow via bioriented transportation channels in g-C3N4: Enhanced photocatalysis and reaction mechanism , 2017 .

[81]  M. Humayun,et al.  Synthesis of SnO2/B-P codoped g-C3N4 nanocomposites as efficient cocatalyst-free visible-light photocatalysts for CO2 conversion and pollutant degradation , 2017 .

[82]  Qian Li,et al.  Enhanced CO2 photocatalytic reduction on alkali-decorated graphitic carbon nitride , 2017 .

[83]  Jacek K. Stolarczyk,et al.  Urea‐Modified Carbon Nitrides: Enhancing Photocatalytic Hydrogen Evolution by Rational Defect Engineering , 2017 .

[84]  Jiaguo Yu,et al.  Adsorption investigation of CO2 on g-C3N4 surface by DFT calculation , 2017 .

[85]  Yuxin Zhang,et al.  Bridging the g-C3N4 Interlayers for Enhanced Photocatalysis , 2016 .

[86]  C. Adamo,et al.  Modeling composite electrolytes for low-temperature solid oxide fuel cell application: structural, vibrational and electronic features of carbonate–oxide interfaces , 2016 .

[87]  G. Qiao,et al.  Component-controllable synthesis of Co(SxSe1−x)2 nanowires supported by carbon fiber paper as high-performance electrode for hydrogen evolution reaction , 2015 .

[88]  Jianjun Liu Effect of phosphorus doping on electronic structure and photocatalytic performance of g-C3N4: Insights from hybrid density functional calculation , 2016 .

[89]  Y. Jiao,et al.  Molecule-Level g-C3N4 Coordinated Transition Metals as a New Class of Electrocatalysts for Oxygen Electrode Reactions. , 2017, Journal of the American Chemical Society.

[90]  S. Carabineiro,et al.  Boron doped graphitic carbon nitride with acid-base duality for cycloaddition of carbon dioxide to epoxide under solvent-free condition , 2017 .

[91]  Shaozheng Hu,et al.  Enhanced visible light photocatalytic performance of g-C3N4 photocatalysts co-doped with iron and phosphorus , 2014 .

[92]  G. Scuseria,et al.  Hybrid functionals based on a screened Coulomb potential , 2003 .

[93]  C. Zhang,et al.  Boron doped g-C3N4 as an effective metal-free solid base catalyst in Knoevenagel condensation , 2018, Catalysis Today.

[94]  Artur F Izmaylov,et al.  Influence of the exchange screening parameter on the performance of screened hybrid functionals. , 2006, The Journal of chemical physics.

[95]  Fu Wang,et al.  Effective photocatalytic H2O2 production under visible light irradiation at g-C3N4 modulated by carbon vacancies , 2016 .

[96]  A. D. Corso Pseudopotentials periodic table: From H to Pu , 2014 .

[97]  Chenghua Sun,et al.  A DFT study of planar vs. corrugated graphene-like carbon nitride (g-C3N4) and its role in the catalytic performance of CO2 conversion. , 2016, Physical chemistry chemical physics : PCCP.

[98]  Lianzhou Wang,et al.  Titania-based photocatalysts—crystal growth, doping and heterostructuring , 2010 .

[99]  Rasit Turan,et al.  Bias in bonding behavior among boron, carbon, and nitrogen atoms in ion implanted a-BN, a-BC, and diamond like carbon films , 2011 .

[100]  Jiaguo Yu,et al.  A direct Z-scheme g-C3N4/SnS2 photocatalyst with superior visible-light CO2 reduction performance , 2017 .

[101]  M. Antonietti,et al.  Synthesis of boron doped polymeric carbon nitride solids and their use as metal-free catalysts for aliphatic C–H bond oxidation , 2011 .

[102]  Di Li,et al.  Catalytic properties of sprayed Ru/Al2O3 and promoter effects of alkali metals in CO2 hydrogenation , 1998 .