Enhancing multifunctional photocatalysis with acetate-assisted cesium doping and unlocking the potential of Z-scheme solar water splitting

Abstract

Graphitic carbon nitride (g-C₃N₄) has been extensively doped with alkali metals to enlarge photocatalytic output, in which cesium (Cs) doping is predicted to be the most efficient. Nevertheless, the sluggish diffusion and doping kinetics of precursors with high melting points, along with imprecise regulation, have raised the debate on whether Cs doping could make sense. For this matter, we attempt to confirm the positive effects of Cs doping on multifunctional photocatalysis by first using cesium acetate with the character of easy manipulation. The optimized Cs-doped g-C₃N₄ (CCN) shows a 41.6-fold increase in visible-light-driven hydrogen evolution reaction (HER) compared to pure g-C₃N₄ and impressive degradation capability, especially with 77% refractory tetracycline and almost 100% rhodamine B degraded within an hour. The penetration of Cs⁺ is demonstrated to be a mode of interlayer doping, and Cs–N bonds (especially with sp² pyridine N in C═N–C), along with robust chemical interaction and electron exchange, are fabricated. This atomic configuration triggers the broadened spectral response, the improved charge migration, and the activated photocatalytic capacity. Furthermore, we evaluate the CCN/cadmium sulfide hybrid as a Z-scheme configuration, promoting the visible HER yield to 9.02 mmol g⁻¹ h⁻¹, which is the highest ever reported among all CCN systems. This work adds to the rapidly expanding field of manipulation strategies and supports further development of mediating served for photocatalysis.

Keywords

acetate-assisted / cesium doping / multifunctional / photocatalysis / Z-scheme

References

[1] Bard AJ, Fox MA. Artificial photosynthesis: solar splitting of water to hydrogen and oxygen. Acc Chem Res. 1995; 28 (3): 141- 145.

[2] Chen M, Guan R, Yang S. Hybrids of fullerenes and 2D nanomaterials. Adv Sci. 2019; 6 (1): 1800941.

[3] Zhang YC, Afzal N, Pan L, Zhang X, Zou JJ. Structure-activity relationship of defective metal-based photocatalysts for water splitting: experimental and theoretical perspectives. Adv Sci. 2019; 6 (10): 1900053.

[4] Hussain MZ, Yang Z, Huang Z, Jia Q, Zhu Y, Xia Y. Recent advances in metal-organic frameworks derived nanocomposites for photocatalytic applications in energy and environment. Adv Sci. 2021; 8 (14): 2100625.

[5] Ma M, Wang Z, Lei Y. An in-depth understanding of photophysics in organic photocatalysts. J Semicond. 2023; 44 (3): 030401.

[6] Yin Z, Hu M, Liu J, Fu H, Wang Z, Tang A. Tunable crystal structure of Cu-Zn-Sn-S nanocrystals for improving photocatalytic hydrogen evolution enabled by copper element regulation. J Semicond. 2022; 43 (3): 032701.

[7] Lin B, Yang G, Yang B, Zhao Y. Construction of novel three dimensionally ordered macroporous carbon nitride for highly efficient photocatalytic activity. Appl Catal B. 2016; 198: 276- 285.

[8] Zhang C, Qin D, Zhou Y, et al. Dual optimization approach to Mo single atom dispersed g-C₃N₄ photocatalyst: morphology and defect evolution. Appl Catal B. 2022; 303: 120904.

[9] Groenewolt M, Antonietti M. Synthesis of g-C₃N₄ nanoparticles in mesoporous silica host matrices. Adv Mater. 2005; 17 (14): 1789- 1792.

[10] Zulqarnain M, Shah A, Khan MA, Jan Iftikhar F, Nisar J. FeCoSe₂ nanoparticles embedded in g-C₃N₄: a highly active and stable bifunctional electrocatalyst for overall water splitting. Sci Rep. 2020; 10: 6328.

[11] Zhou Y, Zhang C, Huang D, et al. Structure defined 2D Mo₂C/2Dg-C₃N₄ Van der Waals heterojunction: oriented charge flow in-plane and separation within the interface to collectively promote photocatalytic degradation of pharmaceutical and personal care products. Appl Catal B. 2022; 301: 120749.

[12] Xu Q, Xia Z, Zhang J, et al. Recent advances in solar-driven CO₂ reduction over g-C₃N₄-based photocatalysts. Carbon Energy. 2023; 5 (2): 205.

[13] He D, Zhang C, Zeng G, et al. A multifunctional platform by controlling of carbon nitride in the core-shell structure: from design to construction, and catalysis applications. Appl Catal B. 2019; 258: 117957.

[14] Tan XQ, Ng SF, Mohamed AR, Ong WJ. Point-to-face contact heterojunctions: interfacial design of 0D nanomaterials on 2D g-C₃N₄ towards photocatalytic energy applications. Carbon Energy. 2022; 4 (5): 665- 730.

[15] Xia Z, Chen C, Qi X, Xu Q, Tang H, Liu G. Delocalized electrons via in situ CNT growth on Au/g-C₃N₄ for boosting photocatalytic H₂ evolution. Adv Sustainable Syst. 2023; 7 (1): 2200134.

[16] Zhang P, Wang T, Chang X, Gong J. Effective charge carrier utilization in photocatalytic conversions. Acc Chem Res. 2016; 49 (5): 911- 921.

[17] Nosaka Y, Nosaka AY. Generation and detection of reactive oxygen species in photocatalysis. Chem Rev. 2017; 117 (17): 11302- 11336.

[18] Wang J, Wang S. A critical review on graphitic carbon nitride (g-C₃N₄)-based materials: preparation, modification and environmental application. Coord Chem Rev. 2022; 453: 214338.

[19] Tan M, Yu C, Li J, et al. Engineering of g-C₃N₄-based photocatalysts to enhance hydrogen evolution. Adv Colloid Interface Sci. 2021; 295: 102488.

[20] Jiang L, Yuan X, Pan Y, et al. Doping of graphitic carbon nitride for photocatalysis: a review. Appl Catal B. 2017; 217: 388- 406.

[21] Deng Y, Liu J, Huang Y, et al. Engineering the photocatalytic behaviors of g/C₃N₄-based metal-free materials for degradation of a representative antibiotic. Adv Funct Mater. 2020; 30 (31): 2002353.

[22] Guo Y, Li H, Ma W, Shi W, Zhu Y, Choi W. Photocatalytic activity enhanced via surface hybridization. Carbon Energy. 2020; 2 (3): 308- 349.

[23] Li C, Li J, Huang Y, et al. Recent development in electronic structure tuning of graphitic carbon nitride for highly efficient photocatalysis. J Semicond. 2022; 43 (2): 021701.

[24] Sun L, Li L, Yang J, Fan J, Xu Q. Fabricating covalent organic framework/CdS S-scheme heterojunctions for improved solar hydrogen generation. Chin J Catal. 2022; 43 (2): 350- 358.

[25] Shen EC, Chen JD, Tian Y, et al. Interfacial energy level tuning for efficient and thermostable CsPbI₂ Br perovskite solar cells. Adv Sci. 2020; 7 (1): 1901952.

[26] Kumar A, Kashyap S, Sharma M, Krishnan V. Tuning the surface and optical properties of graphitic carbon nitride by incorporation of alkali metals (Na, K, Cs and Rb): effect on photocatalytic removal of organic pollutants. Chemosphere. 2022; 287: 131988.

[27] Ai M, Zhang JW, Gao R, Pan L, Zhang X, Zou JJ. MnO_x-decorated 3D porous C₃N₄ with internal donor-acceptor motifs for efficient photocatalytic hydrogen production. Appl Catal B. 2019; 256: 117805.

[28] Deng L, Sun J, Sun J, et al. Improved performance of photosynthetic H₂O₂ and photodegradation by K-, P-, O-, and S-co-doped g-C₃N₄ with enhanced charge transfer ability under visible light. Appl Surf Sci. 2022; 597: 153586.

[29] Yang F, Liu D, Li Y, Cheng L, Ye J. Salt-template-assisted construction of honeycomb-like structured g-C₃N₄ with tunable band structure for enhanced photocatalytic H₂ production. Appl Catal B. 2019; 240: 64- 71.

[30] Wang X, Yang L, Fu G, Chen Y, Yang C, Sun J. Experimental and theoretical investigation for the cycloaddition of carbon dioxide to epoxides catalyzed by potassium and boron co-doped carbon nitride. J Colloid Interface Sci. 2022; 609: 523- 534.

[31] Fattahimoghaddam H, Mahvelati-Shamsabadi T, Jeong CS, Lee BK. Coral-like potassium and phosphorous doped graphitic carbon nitride structures with enhanced charge and mass transfer dynamics toward photocatalytic hydrogen peroxide production and microbial disinfection. J Colloid Interface Sci. 2022; 617: 326- 340.

[32] Wang T, Zheng J, Cai J, Liu Q, Zhang X. Visible-light-driven photocatalytic degradation of dye and antibiotics by activated biochar composited with K⁺ doped g-C₃N₄: effects, mechanisms, actual wastewater treatment and disinfection. Sci Total Environ. 2022; 839: 155955.

[33] Xu Y, Gong Y, Ren H, et al. In situ structural modification of graphitic carbon nitride by alkali halides and influence on photocatalytic activity. RSC Adv. 2017; 7 (52): 32592- 32600.

[34] Mahvelati-Shamsabadi T, Fattahimoghaddam H, Lee BK, Ryu H, Jang JI. Caesium sites coordinated in boron-doped porous and wrinkled graphitic carbon nitride nanosheets for efficient charge carrier separation and transfer: photocatalytic H₂ and H₂O₂ production. Chem Eng J. 2021; 423: 130067.

[35] Liu Q, Li H, Zhang H, Shen Z, Ji H. The role of Cs dopants for improved activation of molecular oxygen and degradation of tetracycline over carbon nitride. Chin Chem Lett. 2022; 33 (11): 4756- 4760.

[36] Lee J, Park C, Song I, et al. Highly reproducible alkali metal doping system for organic crystals through enhanced diffusion of alkali metal by secondary thermal activation. Sci Rep. 2018; 8 (1): 7617.

[37] Huang Y, Liu J, Zhao C, et al. Facile synthesis of defect-modified thin-layered and porous g-C₃N₄ with synergetic improvement for photocatalytic H₂ production. ACS Appl Mater Interfaces. 2020; 12 (47): 52603- 52614.

[38] Ma M, Liu J, Zhao H, et al. Broadened photocatalytic capability to near-infrared for CdS hybrids and positioning hydrogen evolution sites. Appl Catal B. 2023; 325: 122327.

[39] Phongamwong T, Barrabés N, Donphai W, Witoon T, Rupprechter G, Chareonpanich M. Chlorophyll-modified Au₂₅(SR)₁₈-functionalized TiO₂ for photocatalytic degradation of rhodamine B. Appl Catal B. 2023; 325: 122336.

[40] Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B. 1996; 54 (16): 11169- 11186.

[41] Kresse G, Joubert D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys Rev B. 1999; 59 (3): 1758- 1775.

[42] Sun H, Yan Z, Tian C, et al. Bixbyite-type Ln₂O₃ as promoters of metallic Ni for alkaline electrocatalytic hydrogen evolution. Nat Commun. 2022; 13: 3857.

[43] Hammer B, Hansen LB, Nørskov JK. Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals. Phys Rev B. 1999; 59 (11): 7413- 7421.

[44] Krull C, Castelli M, Hapala P, et al. Iron-based trinuclear metal-organic nanostructures on a surface with local charge accumulation. Nat Commun. 2018; 9: 3211.

[45] Qiu G, Ng SP, Wu CML. Label-free surface plasmon resonance biosensing with titanium nitride thin film. Biosens Bioelectron. 2018; 106: 129- 135.

[46] Ding Z, Chen X, Antonietti M, Wang X. Synthesis of transition metal-modified carbon nitride polymers for selective hydrocarbon oxidation. ChemSusChem. 2011; 4 (2): 274- 281.

[47] Wang W, Niu Q, Zeng G, et al. 1D porous tubular g-C₃N₄ capture black phosphorus quantum dots as 1D/0D metal-free photocatalysts for oxytetracycline hydrochloride degradation and hexavalent chromium reduction. Appl Catal B. 2020; 273: 119051.

[48] Liu Y, Zhang Y, Kou Q, et al. Highly efficient, low-cost, and magnetically recoverable FePt-Ag nanocatalysts: towards green reduction of organic dyes. Nanomaterials. 2018; 8 (5): 329.

[49] Lima Fernandes I, Bouaziz J, Blügel S, Lounis S. Universality of defect-skyrmion interaction profiles. Nat Commun. 2018; 9: 4395.

[50] Wang DY, Guo W, Fu Y. Organosulfides: an emerging class of cathode materials for rechargeable lithium batteries. Acc Chem Res. 2019; 52 (8): 2290- 2300.

[51] Kim CK, Zhou H, Kowalewski T, Matyjaszewski K, Kim HK. Soft-templated tellurium-doped mesoporous carbon as a Pt-free electrocatalyst for high-performance dye-sensitized solar cells. ACS Appl Mater Interfaces. 2019; 11 (2): 2093- 2102.

[52] Shakourian-Fard M, Kamath G, Sankaranarayanan SKRS. Evaluating the free energies of solvation and electronic structures of lithium-ion battery electrolytes. ChemPhysChem. 2016; 17 (18): 2916- 2930.

[53] Qin J, Barrio J, Peng G, et al. Direct growth of uniform carbon nitride layers with extended optical absorption towards efficient water-splitting photoanodes. Nat Commun. 2020; 11: 4701.

[54] Zhou C, Xu P, Lai C, et al. Rational design of graphic carbon nitride copolymers by molecular doping for visible-light-driven degradation of aqueous sulfamethazine and hydrogen evolution. Chem Eng J. 2019; 359: 186- 196.

[55] You Z, Li G, Wang C, Li Q, Zheng Y. The synergistic effect of potassium ions and nitrogen defects on carbon nitride for enhanced photocatalytic hydrogen evolution. Int J Hydrogen Energy. 2023; 48 (42): 15934- 15943.

[56] Zhu B, Cheng B, Zhang L, Yu J. Review on DFT calculation of s-triazine-based carbon nitride. Carbon Energy. 2019; 1 (1): 32- 56.

[57] Cui L, Song J, McGuire AF, et al. Constructing highly uniform onion-ring-like graphitic carbon nitride for efficient visible-light-driven photocatalytic hydrogen evolution. ACS Nano. 2018; 12 (6): 5551- 5558.

[58] Xiong T, Cen W, Zhang Y, Dong F. Bridging the g-C₃N₄ interlayers for enhanced photocatalysis. ACS Catal. 2016; 6 (4): 2462- 2472.

[59] Yang X, Guo Z, Zhang X, et al. The effect of indium doping on the hydrogen evolution performance of g-C₃N₄ based photocatalysts. New J Chem. 2021; 45 (2): 544- 550.

[60] Zhang G, Huang C, Wang X. Dispersing molecular cobalt in graphitic carbon nitride frameworks for photocatalytic water oxidation. Small. 2015; 11 (9-10): 1215- 1221.

[61] Zhao D, Dong CL, Wang B, et al. Synergy of dopants and defects in graphitic carbon nitride with exceptionally modulated band structures for efficient photocatalytic oxygen evolution. Adv Mater. 2019; 31 (43): 1903545.

[62] Liu Z, Zhao B, Huang Y, Qi X, Lou F. Cooling capacity test for MIL-101(Cr)/CaCl₂ for adsorption refrigeration system. Molecules. 2020; 25 (17): 3975.

[63] Wu Q, Cao J, Wang X, et al. A metal-free photocatalyst for highly efficient hydrogen peroxide photoproduction in real seawater. Nat Commun. 2021; 12: 483.

[64] Lee CH, Yang CK, Lin MF, Chang CP, Su WS. Structural and electronic properties of graphene nanotube-nanoribbon hybrids. Phys Chem Chem Phys. 2011; 13 (9): 3925- 3931.

[65] Zhao D, Wang Y, Dong CL, et al. Electron-deficient Zn-N₆ configuration enabling polymeric carbon nitride for visible-light photocatalytic overall water splitting. Nano-Micro Lett. 2022; 14 (1): 223.

[66] Kabir MH, Ibrahim H, Ayon SA, Billah MM, Neaz S. Structural, nonlinear optical and antimicrobial properties of sol-gel derived, Fe-doped CuO thin films. Heliyon. 2022; 8 (9): e10609.

[67] Chen L, Zhu D, Li J, et al. Sulfur and potassium co-doped graphitic carbon nitride for highly enhanced photocatalytic hydrogen evolution. Appl Catal B. 2020; 273: 119050.

[68] Wu Y, Xu W, W N, et al. Bridging and bonding: zinc and potassium co-assisted crystalline g-C₃N₄ for significant highly efficient upon photocatalytic hydrogen evolution. Appl Surf Sci. 2021; 542: 148620.

[69] Li L, Ma D, Xu Q, Huang S. Constructing hierarchical ZnIn₂S₄/g-C₃N₄ S-scheme heterojunction for boosted CO₂ photoreduction performance. Chem Eng J. 2022; 437: 135153.

[70] Chen P, Liu H, Sun Y, et al. Bi metal prevents the deactivation of oxygen vacancies in Bi₂O₂CO₃ for stable and efficient photocatalytic NO abatement. Appl Catal B. 2020; 264: 118545.

[71] Shi W, Liu C, Lei A. Transition-metal catalyzed oxidative cross-coupling reactions to form C-C bonds involving organometallic reagents as nucleophiles. Chem Soc Rev. 2011; 40 (5): 2761- 2776.

[72] Li J, Zhan G, Yu Y, Zhang L. Superior visible light hydrogen evolution of Janus bilayer junctions via atomic-level charge flow steering. Nat Commun. 2016; 7: 11480.

[73] Yang J, Wang D, Han H, Li C. Roles of cocatalysts in photocatalysis and photoelectrocatalysis. Acc Chem Res. 2013; 46 (8): 1900- 1909.

[74] Corby S, Francàs L, Selim S, et al. Water oxidation and electron extraction kinetics in nanostructured tungsten trioxide photoanodes. J Am Chem Soc. 2018; 140 (47): 16168- 16177.

[75] Zhang P, Sun D, Cho A, et al. Modified carbon nitride nanozyme as bifunctional glucose oxidase-peroxidase for metal-free bioinspired cascade photocatalysis. Nat Commun. 2019; 10: 940.

[76] Kong N, Fan X, Liu F, et al. Single vanadium atoms anchored on graphitic carbon nitride as a high-performance catalyst for non-oxidative propane dehydrogenation. ACS Nano. 2020; 14 (5): 5772- 5779.

[77] Cai X, Zhu Z, Yu W, et al. Stable GaSe-like phosphorus carbide monolayer with tunable electronic and optical properties from ab initio calculations. Materials. 2018; 11 (10): 1937.

RIGHTS & PERMISSIONS

2023 2023 The Authors. Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.