Diverse Fabrication Routs for Sulphur-Assisted Graphitic Carbon Nitride for Contaminants Degradation Through Solar Energy

Diverse Fabrication Routs for Sulphur-Assisted Graphitic Carbon Nitride for Contaminants Degradation Through Solar Energy | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Diverse Fabrication Routs for Sulphur-Assisted Graphitic Carbon Nitride for Contaminants Degradation Through Solar Energy Asif Hussain, Sadam Ahmed, M. Boota, Pir Bukhsh khan, Sadia Nazir, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6535026/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 22 Jul, 2025 Read the published version in Research on Chemical Intermediates → Version 1 posted 9 You are reading this latest preprint version Abstract Advanced industrialization and globalization have conduct to extensive energy and pollution emergencies, demanding the growth for novel solutions. The release of fabricated dyes as an industrial wastage emerged as a worldwide challenge. Significant amounts are discharged in wastewater annually, poising significant risks owing to harmful toxic effects. Semiconductor’s materials have emerged as a sustainable and green remediation solution. Among various materials, graphitic carbon nitride stands out as an extensively investigated material due to ease fabricated and low cost. Here in this study, graphitic carbon nitride with sulphur assistance, its fabrication routes (i.e., thermal polymerization, sonication, chemically oxidation, and step wise thermal polymerization), characterizations, and photocatalytic performance for methyl blue treatment are reported. Exhibited 2.79 eV, 2.72 eV, 2.82 eV, and 2.56 eV band gap energies with 55%, 67%, 70%, 75%, and 99.5% pollutants degradation activity achieved. The chemically oxidation route attributed higher photocatalytic activity (99.5%, in 50 mins) with the reaction rate constant (K = 0.069). The aforementioned results and measurements are supported by UV–vis diffuse reflectance, signifying bandgap energy, XRD for structural and SEM for morphological and EDX for elemental qualitative analysis. The chemical oxidation route demonstrates an excellent method for sulfur-assisted graphitic carbon nitride synthesis. This novel route will advance the scientific community in the fabrication process. Chemical Oxidation Thermal polymerization Sustainability Semiconductor Photocatalysts Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 1. Introduction The photocatalysis have been supposed to a potential route for energy exhaustion and environmental pollution problems and gained huge interest of researchers for sustainable environment. Currently, the photocatalytic technology attained a significance attention for environmental pollutant degradation[ 1 , 2 ], due to its assistance for effective employment solar energy[ 3 , 4 ], low cost, negligible secondary pollution. Several semiconductors’ materials for contaminants degradation[ 3 ], including ZnO[ 5 ], TiO 2 ,[ 6 ] g-C 3 N 4 ,[ 7 ] WO 3 ,[ 8 ] and BiOX[ 1 ], combined with transition metal compounds, including their derivatives. The above-mentioned semiconductors materials have been exhibits a significant potential for degrading organic dyes and pollutant contaminants through photocatalysis process[ 9 ]. Among several semiconductor materials, graphite-based carbon nitride (g-C 3 N 4 ) was recognized as a promising photocatalyst candidate, owing its non-toxicity, higher chemical stability, affordability, and easy to synthesis[ 10 ]. Moreover, carbon nitride polymers encompass five forms of allotropy such as α-C 3 N 4 , β-C 3 N 4 , pseudocubic-C 3 N 4 , g-C 3 N 4 , and cubic-C 3 N 4 polymers. Since, the β-C 3 N 4 is testified for lower compressibility and reported higher hardness similar to diamond, such as β-Si 3 N 4 , here silicon atom replaced with carbon[ 11 ]. The layered structures with ordered stacking of β-C 3 N 4 is corresponding to C 3 N 4 , since the α-C3N 4 and β-C 3 N 4 hold the same properties, including bulk modulus, crystalline structure, and atomic density etc. Among these carbon-based polymers g-C 3 N 4 has been reported as a most stable at normal conditions and resembling to the graphene structure[ 12 ]. Therefore, g-C 3 N 4 considered as a unique organic semiconductor polymer, which has a potential to encouraged as a photocatalyst. Moreover, from the last few decades research concentration has been assigned. The polymeric description of g-C 3 N 4 is basically of tri-s-triazine. The two-dimensional planes made from the tri-s-triazine units undergo π-conjugated interactions which, as a result, contribute to the high thermal and chemical stability of g-C 3 N 4 [ 13 ]. The main elements of g-C 3 N 4 are carbon and nitrogen, making its possible synthesis from nitrogen-rich and carbon-rich precursors like urea, cyanamide, melamine, dicyandiamide, and thiourea[ 14 ]. These precursors give raised to different microstructures during the syntheses, such as g-C 3 N 4 obtained directly from the thermolysis of urea exhibited a remarkable specific surface area of over 200 m²/g and was significantly higher than that of g-C 3 N 4 synthesized from other precursors [ 15 ]. Additionally, g-C 3 N 4 have excellent bandgap for visible light absorption approximately (wavelength; 445 nm)[ 16 , 17 ]. The conduction band (CB) minima are at -1.23 V potential for pure g-C 3 N 4 (normal hydrogen electrode at pH 7), which is not suitable for photocatalytic degradation and CO 2 reduction into hydrocarbons, including formic acid (HCOOH) is at -0.61 V, ethanol (CH 3 CH 2 OH) at -0.33 V, methanol (CH 3 OH) at -0.38 V, formaldehyde (HCHO) at -0.48 V, and methane (CH 4 ) at -0.24 V, and for H 2 evolution, which is -0.41 V at pH 7. Consequently, more negative potential of g-C 3 N 4 not fit for CO 2 and H 2 evolution and even for photodegradation. Moreover, position of the valence band potential of pure g-C 3 N 4 is 1.47 V at pH 7 is more positive than the energy level needed for the oxidation potential of water, Since the g-C 3 N 4 has been utilized as a material for photocatalytic reduction of carbon dioxide and several other processes including photocatalytic water-splitting, degradation of environmental contaminants. Since the Methylene Blue (MB), the redox potential needed is approximately − 0.2 V (NHE) in LUMO form and + 0.5 V (NHE) corresponding to HOMO[ 18 ]. Therefore, the pristine g-C 3 N 4 not exhibit a significant response upon irradiation of visible light. Consequently, lower photocatalytic activity, recently several assessments have been taken to improve photocatalytic activity, including metal and non-mental doping[ 19 ], and metal organic framework (MOF) [ 20 ]. Additionally, modification of structure, sulphur doped heterojunction and additional catalysts have been exercised. Recently, Sanjay et al reported sulphur doped g-C 3 N 4 nanocomposites for degradation of tetracycline [ 21 ]. For nitroarenes reduction reaction, Marziesadat group employed sulphur-doped g-C 3 N 4 incorporation with Cu-MOF and acceptable catalytic efficiency attained[ 22 ]. Om Prakash et al. reported S-doped g-C 3 N 4 /g-C 3 N 4 S-scheme heterojunction for enhance photocatalytic activity. Here, in this article several experimental routs are adopted for the fabrication sulphur assisted graphitic carbon nitride nanocomposites including sonication, chemical oxidation method, and thermal decomposition routes were employed. Experimental measurements confirmed that fabrication route can effectively alter the structural properties and photocatalytic activities. The sulphur assistance reduced the optical bandgap, which is shifted toward positive potential and enhanced optical absorption. Moreover, composite morphology has been changed from nanosheets to a smooth layered structure with flower like flakes, attributing higher catalytic activity. Surface modification, higher optical absorption, altered photogenerated charge transfer route revealed significantly improved photocatalytic efficiency. We have confidence in, that the synthesis route proposed in this study may be useful for the modification of graphitic carbon nitride nanostructures, and figure out an advanced innovative for catalytic activity improvement of several photocatalytic materials, while also developing novel g-C₃N₄-based photocatalysts. 2. Experimental Section 2.1. Materials Carbamide (NH 2 CONH 2 , ≥ 99.0%, CR) was purchased from Sigma Aldrich Chemical Reagent Co., Ltd., while Tetrachloromethane (CCL 4 , ≥ 99.0%), Ethyl Alcohol (C 2 H 5 OH, ≥ 99.0%), Sulphur (S 8 , ≥ 99.0%), distilled water, thiourea (CH 4 N 2 S, ≥ 99.0%), Methylthioninium chloride (C 16 H 18 ClN 3 S, ≥ 99.0%) were bought from Aladdin chemical Co., Ltd. All the materials employed without further purification and modifications. 2.2. g-C 3 N 4 Synthesis In a typical synthesis process, 5 g carbamide was placed into an alumina combustion crucible with a cover. The crucible was heated up to 550 o C for 3 h by maintaining heating rate of 10 o C min − 1 . Allowing the synthesized product to cool at natural temperature[ 7 , 23 ]. Moreover, same annealing process is resumed as mentioned above to obtained g-C 3 N 4 nano sheets. A yellow power was obtained, which is grounded for further utilization as mentioned in Scheme.1(a) . The pure synthesized nanosheets material was identified as GCN. 2.2.1. Synthesis of Sulphur/g-C 3 N 4 with Sonication Generally, 1 g GCN as prepared is added with 0.6 g elemental sulphur, uniformly mixed with granite mortar and pestle. Subsequently, the mixed product is added into 60 mL carbon tetra chloride and continuously sonicated for 3 h. Resulting, precipitates is form, which is extensively washed with deionized water and ethanol. Subsequently, dried at 80 o C for 24 h and annealed 150 o C for 1 h in air environment. Upon cool to room temperature a light brown power is obtained and designated as S/GCN-0. 2.2.2 Synthesis of Sulphur/g-C 3 N 4 with Chemical Oxidation Method Typically, prepared 1 g GCN is mixed with 0.6 g elemental sulphur by granite mortar and pestle. Then product is dissolved into 60 ml tetrachloride solution and subjected to stirred for 3 h at room temperature. Subsequently, the product extensively washed with water and ethanol, then dried at 80 o C for 24 h. and annealed at 200 o C for 2 h, then cool down to a natural temperature. A light brown power is attained named as S/GCN-1. The above processes are repeated except annealing temperature, which is increased from 200 o C to 300 o C, called S/GCN-2. 2.2.3 Synthesis of Sulphur/g-C 3 N 4 with thermal decomposition 10 g carbamide and 0.6 g elemental sulphur thoroughly grounded and placed in a ceramic crucible with cover. The crucible is heated at several temperatures, including 100 o C, 200 o C, 300 o C, and at 550 o C for 1 h, 2h, and 3h, respectively. Subsequently, light brown powder was achieved called as S/GCN-3. 3. Results and Discussion The X-ray diffraction (XRD) spectral profiles analysis for synthesized trials, including GCN, S/GCN-0, S/GCN-1, S/GCN-2, and S/GCN-3, is presented in Fig. 1 . The peak positions at (002) plane slightly differ among the trials, attributing structural changes owning to the sulphur incorporating, subsequently absence of (100) diffraction peaks, suggests a reduction in the symmetry of 3-s-triazine sketch[ 24 ]. The diffraction peak observed at (27.64) o corresponding to the (002) plane for GCN, attributed to the π-π stacking of GCN interlayered structures and is good accordance with the GCN nanocomposites[ 25 ]. Moreover, some additional peaks are observed, which is particularly due to the incorporating sulphur and structural defects merged in sample S/GCN-0, attributing sulphur is not fully incorporated with GCN, as evidence from local enlarge view, peaks at 23.26 o , 26.05 o , and 28.88 o are corresponding to the crystalline sulphur phase as shown in Fig. 1 (b) . Since the sulphur atom has higher atomic radii compared with N and C, consequently enhanced lattice defects and decrease in lattice distance, attributing diffraction peaks are shifted toward higher angle[ 26 ]. Peak position at (002) for S/GCN-1is slightly shifted toward higher angle and no other impurity is found. Moreover, for sample S/GCN-3 peak intensity decreased, wide, and shifted toward lower angle, exhibit decreased crystallite size and enhanced amorphous contents. Higher peak intensity, sharpness, and shifted toward higher angle is indicated for S/GCN-3, corresponding to sulphur incorporation enhanced crystallinity and lower lattice distance, exhibiting strong π-π stacking interactions, which facilitate interlayer charge transfer as compared to pure GCN. The functional groups of the GCN, S/GCN-0, S/GCN-1, S/GCN-2, and S/GCN-3 trials are investigated by employing FTIR spectroscopy. All samples exhibited almost similar patterns except S/GCN-1, S/GCN-2 ranging from 4000 cm − 1 to 500 cm − 1 wave number as shown in Fig. 2 . the wide band from (3000–3300) cm − 1 exhibited O-H and N-H stretching vibrations corresponding to (NH or NH 2 ) residual amino group of g-C 3 N 4 , which are linked triazine ring structures. Moreover, boarding of the peaks is certainly result of moisture absorption and hydrogen bonding. Furthermore, the strong peaks observed at (1601cm − 1 ) C = N, N-H bending, (1405 cm − 1 ) C-N bending, (1320 cm − 1 ) C-N bending, and (1240 cm − 1 ) stretching, matched to C–N aromatic stretching vibrations. The observed strong peak at 803 cm − 1 attributed for tris-triazine cycle, additionally peaks from 600–800 cm − 1 (C-S and N-S bonding), no dominant peak is observed at 1000–1200 cm − 1 , which attributed that sulphur oxide (S = O or sulfone SO 2 ) groups are not observed. In S/GCN-1, S/GCN-2 samples the peaks at (803cm − 1 ) is shifted toward higher wave number such as (810–820) cm⁻¹, indicating tris-triazine cycle is distorted owning to sulphur incorporation, signifying that the regularity of the ring is transformed by sulfur incorporation. Moreover, the reduction in peaks intensities, peaks boarding, and shifting of peaks is correspond to the structural distortion, induction of defects, and hydrogen bonding interactions, respectively; confirming the existence of sulphur incorporation, this observation is consistent with XRD analysis. The microstructures, surface morphology, shape, and size were analyzed by employing Scanning Electron Microscopy (SEM) for GCN, S/GCN-0, S/GCN-1, S/GCN-2, and S/GCN-3 trials as shown in Fig. 3 . GCN (Fig. 3 (a) ) exhibited stacked nanosheets with varying shapes and sizes confirmed layered structures of graphitic carbonitride, which may in result have a non-porous material with low surface area. The S/GCN-0 exhibited an agglomerated, non- porous structure with inhomogeneous-distributed, indicating sulphur element is not uniformly incorporated to the graphitic matrix. The nonappearance of significant porosity and lack of uniformity revealed uneven sulfur incorporation throughout the material as shown in Fig. 3 (b). The non-porosity and uneven incorporation of sulphur is also investigated in the Fig. 3 (c) , incorporation of may introduces mesopores or micropores, which are observed in the Fig. 3 (d and e) . Additionally, as compared to the pristine sample, which exhibits a smooth layered structure with larger flake, while the sulphur assisted sample as in Fig. 3 (d and e) shows reduced thickness and possibly nano sheets or flower like formations are observed, which may be reflecting the higher surface area. The smaller size and flake like structures further confirm the alteration of the graphitic nitride matrix upon incorporation of sulphur. The elemental composition is investigated by employing Energy EDX (Dispersive X-ray Spectroscopy) for qualitative analysis. The elemental mapping is shown in Fig. 4 , representing the existence of the elements including C, N, and S. The elemental weight percentage is listed in Table 1 . The Fig. 4 (d) has no sulphur element, it clearly shows the pure graphitic corban nitride. It is clearly evident from Fig. 4 (e) that S/GCN-0 contains a significant amount of sulfur, which is not incorporated or linked within the GCN. A higher weight percentage (14.94%) is observed. Table 1: Elemental weight percentage for GCN (a), S/GCN-0 (b), S/GCN-1(c), S/GCN-2 (d), and S/GCN-3(e). Similarly, the sample S/GCN-1 demonstrated better results as compared with the sample S/GCN-0, although the sulphur element is incorporated with GCN as shown in Fig. 4 (f) . However, the level of incorporation is inadequate to significantly enhance efficiency. In sample S/GCN-2 and S/GCN-3 Wt% is 0.22 and 0.08, respectively. Nevertheless, sample in S/GCN-2 sulphur is appropriately incorporated, resulting in higher photocatalytic efficiency compared with S/GCN-3 as shown in Fig. 4 (g and h) . The optical bandgap energy of synthesized trials was carried out by employing UV-vis diffuse reflectance spectra (DRS) as shown in Fig. 5 . The E g (bandgap energies) assessed from the photon’s energy vs \(\:{\left(\alpha\:h\upsilon\:\right)\:}^{\raisebox{1ex}{$1$}\!\left/\:\!\raisebox{-1ex}{$2$}\right.}\) plots are as 2.79 eV, 2.72 eV, 2.82 eV, and 2.56 eV, corresponding to GCN, S/GCN-0, and S/GCN-2, respectively as shown in Fig. 5 (a-c) . The S/GCN-2 exhibits more intense absorption compared to the pristine sample and S/GCN-0, as the incorporation of the sulfur element is uneven in the S/GCN-0 sample, resulting in the presence of two individual elements. However, the incorporation of sulfur reduced the bandgap energy, possibly due to the creation of energy states near the band edges, leading to enhanced photocatalytic activity, which is examined by the S/GCN-2 sample. Here, the semiconductor bandgap energy is calculated using expression no (1). $$\:{\left(\alpha\:h\upsilon\:\right)\:}^{n}=A(h\upsilon\:-{E}_{g})$$ 1 Here, variables and parameters, E g , h, A, υ, n, and α, represents bandgap energy, Plank’s constant, constant, frequency, type of bandgap transition, and absorption coefficient, respectively. Whereas, conduction band maxima energy state (E CB ) and valance band minima energy states (E VB ) are estimated by employing the equations ( 2 and 3 ). $$\:{E}_{CB}=\chi\:-{E}_{e}-0.5{E}_{g}$$ 2 $$\:{E}_{VB}={E}_{CB}+{E}_{g}$$ 3 Here, \(\:{E}_{CB},\) \(\:\chi\:,\) \(\:{E}_{e},\) \(\:{E}_{g},\:\) and \(\:{E}_{VB}\) represents conduction band energy, absolute electronegativity (Mulliken), free electrons energy (4.50 eV, on hydrogen scale), bandgap energy, and valance band energy, respectively. Approximately, \(\:\chi\:=4.67\:eV\) energy is recognized for graphitic carbon nitride, the conduction band edges for GCN, S/GCN-2 are lies at 1.45 eV, and 1.43 eV, whereas valance band edges are at -1.34 eV and − 1.12 eV as illustrated in Fig. 5 (d) . the significant valance band energy change (ΔE ⁓ 0.22 eV) is examined, attributing reduced oxidation potential for photogenerated electrons holes pairs[ 27 ]. Moreover, sulfur incorporation may induce localized states close to the valance band edge and conduction band edge, possibly alter the electronic transfer route and improved charge suppression, leading higher catalytic efficiency. Photocatalytic activity of GCN and S/GCN-X (X = 0, 1, 2, 3) composites was estimated by employing photodegradation of methyl blue (MB), absorption spectra for photodegradation is shown in Fig. 5 (e-i) . The significant changes have been observed in the absorption spectra during MB photodegradation experiments, Fig. 5 (e) exhibited significantly low photodegradation rate (⁓ 76% degradation in 60 mins) of MB dye for pristine GCN trial, maybe leading to lower solar energy absorption or higher recombination rate. Same results have been estimated from the sample S/GCN-0 as shown in Fig. 5 (f) , consequence of incorporation of sulfur element in the GCN as already reported in XRD, FTIR, and EDX mapping. Possibly, similar observations have been examined in samples S/GCN-1, illustrating low degradation percentage ⁓ 80% in 60 mins as shown in Fig. 5 (g) . The sample S/GCN-3 synthesized via the thermal decomposition route exhibit significantly higher photodegradation activity (⁓ 91% in 60 mins). However, enhancement likely due to the incorporation of sulfur into GCN, which increased catalytic sites and alter charge transfer route, resulting in reduced recombination made significantly enhanced catalytic activity for MB dye degradation as shown in Fig. 5 (h) . The sample synthesized through Chemical Oxidation Method exhibit significantly enhanced photocatalytic efficiency owning to better surface chemistry, enhanced charge transfer, active sites development and suppressed charge recombination rate. The photodegradation rate is achieved (99.9% in 60 mins), which very significant as shown in Fig. 5 (i) . Photocatalytic activity of MB dye degradation by employing photocatalysts such as GCN, S/GCN-0, S/GCN-1, S/GCN-2, and S/GCN-3 trials is illustrated in Fig. 6 . Since every sample degraded the MB dye, which is coherent with the reported studied. However, the sample (S/GCN-2) fabricated with chemically oxidation method shown significantly enhanced activity, consequently degraded within 49 mins as shown in Fig. 6 (a) . Mostly, photodegradation of organic pollutants has been investigated by employing Langmuir-Hinshelwood model. Additionally, it was recognized, that photodegradation reaction is take place among pollutants molecules and photogenerated active species (electrons hole pairs, radicals etc.). Nevertheless, first-order kinetics is non-complicated and effective for contaminants degradation modelling, which is expressed by using Equation no (4) . $$\:Ln\:\frac{{C}_{t}}{{C}_{0}}=Kt$$ 4 Here, C t , C 0 , K, and t represents degraded concentration, initial concentration, reaction constant and reaction time, respectively. Surely, this approached is adopted for quantifying reaction rates and photodegradation reaction constant. Aforementioned parameters together exhibit correlates the governing degradation photocatalytic activity with catalytic material under specific conditions. Therefore, the synthesis rout for GCN-2 contribute to altering structural and photocatalytic properties of g-C 3 N 4 , consequently enhanced photocatalytic efficiency, evidenced by “K” value of GCN-2. 4. Possible Photocatalytic Mechanism The photocatalytic mechanism is discussed in detail by analyzing the aforementioned experimental results and measurements. Several routes have been exercised to synthesized graphitic carbonitride, all samples have same XRD profiles as shown in Fig. 1 excepts S/GCN-0, other samples peak positions at (002) plane slightly different owning to sulphur incorporating, the S/GCN-2 is more crystalline and shifting toward a higher angle, attributing decreased lattice interlayer distance of triazine (C₃N₄) framework, which is the consequence of higher photocatalytic activity. Therefore, the smaller inter layer distances of g-C 3 N 4 (framework) lattice atoms suppressed charge recombination, leading to enhanced photocatalytic activity[ 28 ]. Additionally, thickness and interspacing distance in a 2D materials exhibited key role in photocatalytic activity and physical and chemical behavior were significantly influenced by surface modifications. Consequently, S/GCN-2 sample at (803cm − 1 ) peak position is shifted toward higher wave number such as (810–820) cm − 1 , indicating tris-triazine cycle is distorted owning to sulphur incorporation, signifying that the regularity of the ring is transformed by sulfur incorporation as shown in Fig. 2 . Moreover, the reduction in peaks intensities, peaks boarding, and shifting of peaks is correspond to the structural distortion, induction of defects, and hydrogen bonding interactions, respectively; The unique layered structures with lower activation energy grants the catalytic sites on the surface of the photocatalyst as clearly illustrated in Fig. 3 , reduced thickness and possibly nano sheets or flower like formations are observed, which may enhance the solar energy absorption, resultant in higher photocatalytic activity. Since the S/GCN-2 has a reduced bandgap energy (i.e., E g = 2.56 eV), it absorbed significantly more visible light energy. The light absorption is expressed for both sulphur and graphitic carbon nitride as mentioned in reaction Eqs. ( 5 and 6 ) $$\:g-{C}_{3}{N}_{4}+hv\to\:g-{C}_{3}{N}_{4}({e}^{-}+{h}^{+})$$ 5 $$\:\:S+hv\to\:S({e}^{-}+{h}^{+})$$ 6 Since the photogenerated e − and h + pairs transferred to their prospective energy states, such as e − transferred from the GCN conduction band to the conduction band of sulphur and vice versa. Which, suppressed the photogenerated charge recombination, resultant in higher catalytic efficiency. The e − form superoxide (e − + O 2 = O 2 − ) radicals when react with oxygen (O 2 ); similarly, h + react with water (H 2 O) formed (OH) radicals. Therefore, the generated radicals react with the MB dye molecules and break chromophoric structure of MB dye into to smaller molecules, including inorganic ions H 2 O, and CO 2 . The above-mentioned conclusions confirm the appreciated activity of S/GCN-2 photocatalyst, which explored a potential route for synthesis of sulphur assisted graphitic carbonitride. Conclusion Sulfur assisted graphitic carbon nitride is fabricated by using several synthesis routes. The easy fabrication and low cost of the precursors offers sustainable solution for environmental remediation for mitigation the annual release of synthetic dyes into the environment. Incorporating sulfur into heptazine framework improved the photocatalytic activity of GCN by modification its energy bandgap structure, photogenerated charge transfer route. The degradation of synthetic dye methyl blue is examined by all the fabricated trials, S/GCN-2 shown higher catalytic activity, as a result in uniform incorporation of sulphur element, lower energy optical bandgap (2.56 eV), higher crystallinity, and estimated reaction constant (K = 0.069) leads to improved solar energy absorption. Moreover, this study figured out a novel synthesis route for incorporation of co-catalytic element into GCN and carbon-based semiconductor materials. Declarations Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Author Contribution Jianhua Hou; Supervision, Pir Bukhsh khan ; data analysis, Sadia Nazir; review and editing, M. Boota, XRD nd EDX analysis Sadam Ahmed, Experimentation, Thamraa Alshahrani; Characterizations, Mouna Jeridi; data analysis, Asif Hussain; writing and review Acknowledgements The authors extend their appreciation to the Deanship of Research and Graduate Studies at King Khalid University, Saudi Arabia for funding this work through the Small Groups Project under grant number R.G.P1/138/45. 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Journal of Molecular Structure, 2025. 1321 : p. 139763. https://doi.org/10.1016/j.molstruc.2024.139763 Hussain, A., et al., Synergic effect among activated carbon/sulphur-assisted graphitic carbon nitride for enhanced photocatalytic activity. Diamond and Related Materials, 2023. 135 : p. 109836. https://doi.org/10.1016/j.diamond.2023.109836 Song, W., et al., Sulfur-doped g-C 3 N 4 /GaN nn heterojunction for high performance low-power blue-ultraviolet photodetector with ultra-high on/off ratio and detectivity. Carbon, 2024. 228 : p. 119438. https://doi.org/10.1016/j.carbon.2024.119438 Han, Q., et al., A graphitic ‐C 3 N 4 “seaweed ” architecture for enhanced hydrogen evolution. Angewandte Chemie, 2015. 127 (39): p. 11595-11599. https://doi.org/10.1002/ange.201504985 Guo, Y., et al., A rapid microwave ‐assisted thermolysis route to highly crystalline carbon nitrides for efficient hydrogen generation. Angewandte Chemie, 2016. 128 (47): p. 14913-14917. https://doi.org/10.1002/ange.201608453 Pérez-Torres, A.F., et al., Sulfur-Doped g-C 3 N 4 Heterojunctions for Efficient Visible Light Degradation of Methylene Blue. ACS omega, 2023. 8 (50): p. 47821-47834. Xiong, T., et al., Bridging the g-C 3 N 4 interlayers for enhanced photocatalysis. Acs Catalysis, 2016. 6 (4): p. 2462-2472. Scheme 1 Scheme 1 is available in the Supplementary Files section. Additional Declarations No competing interests reported. Supplementary Files Graphicalabstract.jpg Graphical abstract scheme1.jpg Scheme 1: Sulphur assisted graphitic carbonitride synthesis routes Cite Share Download PDF Status: Published Journal Publication published 22 Jul, 2025 Read the published version in Research on Chemical Intermediates → Version 1 posted Editorial decision: Revision requested 27 May, 2025 Reviews received at journal 27 May, 2025 Reviews received at journal 23 May, 2025 Reviewers agreed at journal 18 May, 2025 Reviewers agreed at journal 14 May, 2025 Reviewers invited by journal 13 May, 2025 Editor assigned by journal 29 Apr, 2025 Submission checks completed at journal 29 Apr, 2025 First submitted to journal 26 Apr, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6535026","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":456531730,"identity":"d000255e-7980-419f-85ae-935101b58391","order_by":0,"name":"Asif Hussain","email":"","orcid":"","institution":"The University of Lahore","correspondingAuthor":false,"prefix":"","firstName":"Asif","middleName":"","lastName":"Hussain","suffix":""},{"id":456531731,"identity":"e706a4fe-d004-4a6c-b2b1-9dcbcc7af2d1","order_by":1,"name":"Sadam Ahmed","email":"","orcid":"","institution":"The University of Lahore","correspondingAuthor":false,"prefix":"","firstName":"Sadam","middleName":"","lastName":"Ahmed","suffix":""},{"id":456531732,"identity":"5c05248e-d7d1-41a3-b8fd-3e79abbc3b45","order_by":2,"name":"M. Boota","email":"","orcid":"","institution":"The University of Lahore","correspondingAuthor":false,"prefix":"","firstName":"M.","middleName":"","lastName":"Boota","suffix":""},{"id":456531733,"identity":"624cd03f-7e12-4bd6-8691-edb25b3a7a10","order_by":3,"name":"Pir Bukhsh khan","email":"","orcid":"","institution":"The University of Lahore","correspondingAuthor":false,"prefix":"","firstName":"Pir","middleName":"Bukhsh","lastName":"khan","suffix":""},{"id":456531734,"identity":"765f97c6-004f-46db-a5d0-4a720f824196","order_by":4,"name":"Sadia Nazir","email":"","orcid":"","institution":"The University of Lahore","correspondingAuthor":false,"prefix":"","firstName":"Sadia","middleName":"","lastName":"Nazir","suffix":""},{"id":456531735,"identity":"7d6b4560-bced-489f-a9c2-0feaa63dce9a","order_by":5,"name":"Mouna Jeridi","email":"","orcid":"","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Mouna","middleName":"","lastName":"Jeridi","suffix":""},{"id":456531736,"identity":"6be62e45-7e18-4dfd-95d7-a5921f9a0144","order_by":6,"name":"Thamraa Alshahrani","email":"","orcid":"","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Thamraa","middleName":"","lastName":"Alshahrani","suffix":""},{"id":456531737,"identity":"f880e7f5-10ba-4bda-b53a-39ca0a4c6381","order_by":7,"name":"Jianhua Hou","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAtUlEQVRIiWNgGAWjYBACxhk8QLICwpEgQcsZUrQwSAC1MLaRooV5du/Bx7zzDtsbHGA+eJuHwS6PsMPmnEs25t12mNngAFuyNQ9DcjFhLTNyzKSBWtgMDvCYSfMwHEhsIE7LnMM8Bgf4v5GipeGwBNAWNqK1GBvOOZZuIHmYzdhyjkEyYS2GM3IMH7ypsbbnO9788MabCjsitEBUNAODG0QbEFIPBPIQqo4IpaNgFIyCUTBiAQD+tjW0u9z5iAAAAABJRU5ErkJggg==","orcid":"","institution":"Yangzhou University","correspondingAuthor":true,"prefix":"","firstName":"Jianhua","middleName":"","lastName":"Hou","suffix":""}],"badges":[],"createdAt":"2025-04-26 12:38:13","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6535026/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6535026/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s11164-025-05672-8","type":"published","date":"2025-07-22T15:57:05+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":82901387,"identity":"ea8a7601-6548-40e8-8c97-382c0989f59e","added_by":"auto","created_at":"2025-05-16 13:30:57","extension":"jpg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":72062,"visible":true,"origin":"","legend":"\u003cp\u003eXRD profiles for GCN, S/GCN-0, S/GCN-1, S/GCN-2, and S/GCN-3 (a), Local enlarge view from an angle (22\u003csup\u003eo\u003c/sup\u003e-30\u003csup\u003eo\u003c/sup\u003e) for GCN, S/GCN-0, S/GCN-1, S/GCN-2, and S/GCN-3 (b).\u003c/p\u003e","description":"","filename":"1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6535026/v1/4920a5454c4cd1e06003a30d.jpg"},{"id":82899942,"identity":"03a08788-7d1e-4fa3-a8ea-e1f339b20c92","added_by":"auto","created_at":"2025-05-16 13:22:57","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":108813,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectra for GCN, S/GCN-0, S/GCN-1, S/GCN-2, and S/GCN-3 (a) and Local enlarge view from wave number (700-1400) cm\u003csup\u003e-1\u003c/sup\u003e. \u0026nbsp;\u003c/p\u003e","description":"","filename":"2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6535026/v1/9ae05fd23acdbab56983a621.jpg"},{"id":82899203,"identity":"6a984c1a-6d23-4800-8e75-ce4ff9960c7d","added_by":"auto","created_at":"2025-05-16 13:15:06","extension":"jpg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":100469,"visible":true,"origin":"","legend":"\u003cp\u003eSEM Images for GCN (a), S/GCN-0 (b), S/GCN-1(c), S/GCN-2 (d), and S/GCN-3(e)\u003c/p\u003e","description":"","filename":"3.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6535026/v1/930afb55211adee8e586be93.jpg"},{"id":82899204,"identity":"f52b1b71-c179-4530-bb4a-4ae7a8368ceb","added_by":"auto","created_at":"2025-05-16 13:15:08","extension":"jpg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":132426,"visible":true,"origin":"","legend":"\u003cp\u003eEDX mapping for GCN (a), S/GCN-0 (b), S/GCN-1(c), S/GCN-2 (d), and S/GCN-3(e).\u003c/p\u003e","description":"","filename":"4.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6535026/v1/0bce90b32f299bf6a5e276db.jpg"},{"id":82899160,"identity":"bf75d488-06a7-4629-8437-d33ecba09fed","added_by":"auto","created_at":"2025-05-16 13:14:57","extension":"jpg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":139019,"visible":true,"origin":"","legend":"\u003cp\u003eUV-vis spectroscopy plot for GCN (a), S/GCN-0 (b), S/GCN-2 (c), Schematic for electronic band structures (d), Absorption spectra of MB for GCN (e), S/GCN-0 (f), S/GCN-1(g), S/GCN-2 (h), and S/GCN-3(i).\u003c/p\u003e","description":"","filename":"5.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6535026/v1/fba94544e583ed20fac71635.jpg"},{"id":82899948,"identity":"dac81d7e-49ae-4db9-be67-3d09061d3b8e","added_by":"auto","created_at":"2025-05-16 13:22:57","extension":"jpg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":132444,"visible":true,"origin":"","legend":"\u003cp\u003ePhotodegradation of MB, C/C\u003csub\u003eo\u003c/sub\u003e vs Irradiation plot (a), -Ln(C/C\u003csub\u003e0\u003c/sub\u003e) vs irradiation plot (b), percentage degradation and reaction constants (c \u0026amp; d), photodegradation scheme for MB (e), and photodegradation stability test (f).\u003c/p\u003e","description":"","filename":"6.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6535026/v1/5c6c38d463a039c5c19c2e44.jpg"},{"id":87756701,"identity":"1389daf9-016f-406d-bba5-ab2f4b74d1fe","added_by":"auto","created_at":"2025-07-28 16:07:53","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1513536,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6535026/v1/7d0bcdc4-97b5-4c3e-9caa-1eb44f5fbb98.pdf"},{"id":82899153,"identity":"4066de22-eb71-4d40-9dc6-2c0f40c556c3","added_by":"auto","created_at":"2025-05-16 13:14:57","extension":"jpg","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":53124,"visible":true,"origin":"","legend":"\u003cp\u003eGraphical abstract\u003c/p\u003e","description":"","filename":"Graphicalabstract.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6535026/v1/74008a94043a960473c4a5d8.jpg"},{"id":82899155,"identity":"c38c7b2e-529e-4f0c-84fe-6412fab877de","added_by":"auto","created_at":"2025-05-16 13:14:57","extension":"jpg","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":83310,"visible":true,"origin":"","legend":"\u003cp\u003eScheme 1: Sulphur assisted graphitic carbonitride synthesis routes\u003c/p\u003e","description":"","filename":"scheme1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-6535026/v1/acc54c26828a6c72918eaeca.jpg"}],"financialInterests":"No competing interests reported.","formattedTitle":"Diverse Fabrication Routs for Sulphur-Assisted Graphitic Carbon Nitride for Contaminants Degradation Through Solar Energy","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eThe photocatalysis have been supposed to a potential route for energy exhaustion and environmental pollution problems and gained huge interest of researchers for sustainable environment. Currently, the photocatalytic technology attained a significance attention for environmental pollutant degradation[\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e], due to its assistance for effective employment solar energy[\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e], low cost, negligible secondary pollution. Several semiconductors\u0026rsquo; materials for contaminants degradation[\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e], including ZnO[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e], TiO\u003csub\u003e2\u003c/sub\u003e,[\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e] g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e,[\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e] WO\u003csub\u003e3\u003c/sub\u003e,[\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e] and BiOX[\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e], combined with transition metal compounds, including their derivatives. The above-mentioned semiconductors materials have been exhibits a significant potential for degrading organic dyes and pollutant contaminants through photocatalysis process[\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. Among several semiconductor materials, graphite-based carbon nitride (g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e) was recognized as a promising photocatalyst candidate, owing its non-toxicity, higher chemical stability, affordability, and easy to synthesis[\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]. Moreover, carbon nitride polymers encompass five forms of allotropy such as α-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, β-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, pseudocubic-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, and cubic-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e polymers. Since, the β-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e is testified for lower compressibility and reported higher hardness similar to diamond, such as β-Si\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, here silicon atom replaced with carbon[\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]. The layered structures with ordered stacking of β-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e is corresponding to C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, since the α-C3N\u003csub\u003e4\u003c/sub\u003e and β-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e hold the same properties, including bulk modulus, crystalline structure, and atomic density etc. Among these carbon-based polymers g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e has been reported as a most stable at normal conditions and resembling to the graphene structure[\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]. Therefore, g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e considered as a unique organic semiconductor polymer, which has a potential to encouraged as a photocatalyst. Moreover, from the last few decades research concentration has been assigned.\u003c/p\u003e \u003cp\u003eThe polymeric description of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e is basically of tri-s-triazine. The two-dimensional planes made from the tri-s-triazine units undergo π-conjugated interactions which, as a result, contribute to the high thermal and chemical stability of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]. The main elements of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e are carbon and nitrogen, making its possible synthesis from nitrogen-rich and carbon-rich precursors like urea, cyanamide, melamine, dicyandiamide, and thiourea[\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]. These precursors give raised to different microstructures during the syntheses, such as g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e obtained directly from the thermolysis of urea exhibited a remarkable specific surface area of over 200 m\u0026sup2;/g and was significantly higher than that of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e synthesized from other precursors [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. Additionally, g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e have excellent bandgap for visible light absorption approximately (wavelength; 445 nm)[\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. The conduction band (CB) minima are at -1.23 V potential for pure g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e (normal hydrogen electrode at pH 7), which is not suitable for photocatalytic degradation and CO\u003csub\u003e2\u003c/sub\u003e reduction into hydrocarbons, including formic acid (HCOOH) is at -0.61 V, ethanol (CH\u003csub\u003e3\u003c/sub\u003eCH\u003csub\u003e2\u003c/sub\u003eOH) at -0.33 V, methanol (CH\u003csub\u003e3\u003c/sub\u003eOH) at -0.38 V, formaldehyde (HCHO) at -0.48 V, and methane (CH\u003csub\u003e4\u003c/sub\u003e) at -0.24 V, and for H\u003csub\u003e2\u003c/sub\u003e evolution, which is -0.41 V at pH 7. Consequently, more negative potential of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e not fit for CO\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003e evolution and even for photodegradation. Moreover, position of the valence band potential of pure g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e is 1.47 V at pH 7 is more positive than the energy level needed for the oxidation potential of water, Since the g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e has been utilized as a material for photocatalytic reduction of carbon dioxide and several other processes including photocatalytic water-splitting, degradation of environmental contaminants. Since the Methylene Blue (MB), the redox potential needed is approximately \u0026minus;\u0026thinsp;0.2 V (NHE) in LUMO form and +\u0026thinsp;0.5 V (NHE) corresponding to HOMO[\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. Therefore, the pristine g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e not exhibit a significant response upon irradiation of visible light. Consequently, lower photocatalytic activity, recently several assessments have been taken to improve photocatalytic activity, including metal and non-mental doping[\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e], and metal organic framework (MOF) [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. Additionally, modification of structure, sulphur doped heterojunction and additional catalysts have been exercised. Recently, Sanjay et al reported sulphur doped g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e nanocomposites for degradation of tetracycline [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. For nitroarenes reduction reaction, Marziesadat group employed sulphur-doped g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e incorporation with Cu-MOF and acceptable catalytic efficiency attained[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. Om Prakash et al. reported S-doped g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e S-scheme heterojunction for enhance photocatalytic activity.\u003c/p\u003e \u003cp\u003eHere, in this article several experimental routs are adopted for the fabrication sulphur assisted graphitic carbon nitride nanocomposites including sonication, chemical oxidation method, and thermal decomposition routes were employed. Experimental measurements confirmed that fabrication route can effectively alter the structural properties and photocatalytic activities. The sulphur assistance reduced the optical bandgap, which is shifted toward positive potential and enhanced optical absorption. Moreover, composite morphology has been changed from nanosheets to a smooth layered structure with flower like flakes, attributing higher catalytic activity. Surface modification, higher optical absorption, altered photogenerated charge transfer route revealed significantly improved photocatalytic efficiency. We have confidence in, that the synthesis route proposed in this study may be useful for the modification of graphitic carbon nitride nanostructures, and figure out an advanced innovative for catalytic activity improvement of several photocatalytic materials, while also developing novel g-C₃N₄-based photocatalysts.\u003c/p\u003e"},{"header":"2. Experimental Section","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Materials\u003c/h2\u003e \u003cp\u003eCarbamide (NH\u003csub\u003e2\u003c/sub\u003eCONH\u003csub\u003e2\u003c/sub\u003e, \u0026ge; 99.0%, CR) was purchased from Sigma Aldrich Chemical Reagent Co., Ltd., while Tetrachloromethane (CCL\u003csub\u003e4\u003c/sub\u003e, \u0026ge; 99.0%), Ethyl Alcohol (C\u003csub\u003e2\u003c/sub\u003eH\u003csub\u003e5\u003c/sub\u003eOH, \u0026ge; 99.0%), Sulphur (S\u003csub\u003e8\u003c/sub\u003e, \u0026ge; 99.0%), distilled water, thiourea (CH\u003csub\u003e4\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003eS, \u0026ge; 99.0%), Methylthioninium chloride (C\u003csub\u003e16\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003eClN\u003csub\u003e3\u003c/sub\u003eS, \u0026ge; 99.0%) were bought from Aladdin chemical Co., Ltd. All the materials employed without further purification and modifications.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e Synthesis\u003c/h2\u003e \u003cp\u003eIn a typical synthesis process, 5 g carbamide was placed into an alumina combustion crucible with a cover. The crucible was heated up to 550 \u003csup\u003eo\u003c/sup\u003eC for 3 h by maintaining heating rate of 10 \u003csup\u003eo\u003c/sup\u003eC min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Allowing the synthesized product to cool at natural temperature[\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]. Moreover, same annealing process is resumed as mentioned above to obtained g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e nano sheets. A yellow power was obtained, which is grounded for further utilization as mentioned in \u003cb\u003eScheme.1(a)\u003c/b\u003e. The pure synthesized nanosheets material was identified as GCN.\u003c/p\u003e \u003cdiv id=\"Sec5\" class=\"Section3\"\u003e \u003ch2\u003e2.2.1. Synthesis of Sulphur/g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e with Sonication\u003c/h2\u003e \u003cp\u003eGenerally, 1 g GCN as prepared is added with 0.6 g elemental sulphur, uniformly mixed with granite mortar and pestle. Subsequently, the mixed product is added into 60 mL carbon tetra chloride and continuously sonicated for 3 h. Resulting, precipitates is form, which is extensively washed with deionized water and ethanol. Subsequently, dried at 80 \u003csup\u003eo\u003c/sup\u003eC for 24 h and annealed 150 \u003csup\u003eo\u003c/sup\u003eC for 1 h in air environment. Upon cool to room temperature a light brown power is obtained and designated as S/GCN-0.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section3\"\u003e \u003ch2\u003e2.2.2 Synthesis of Sulphur/g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e with Chemical Oxidation Method\u003c/h2\u003e \u003cp\u003eTypically, prepared 1 g GCN is mixed with 0.6 g elemental sulphur by granite mortar and pestle. Then product is dissolved into 60 ml tetrachloride solution and subjected to stirred for 3 h at room temperature. Subsequently, the product extensively washed with water and ethanol, then dried at 80 \u003csup\u003eo\u003c/sup\u003eC for 24 h. and annealed at 200 \u003csup\u003eo\u003c/sup\u003eC for 2 h, then cool down to a natural temperature. A light brown power is attained named as S/GCN-1. The above processes are repeated except annealing temperature, which is increased from 200 \u003csup\u003eo\u003c/sup\u003eC to 300 \u003csup\u003eo\u003c/sup\u003eC, called S/GCN-2.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section3\"\u003e \u003ch2\u003e2.2.3 Synthesis of Sulphur/g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e with thermal decomposition\u003c/h2\u003e \u003cp\u003e10 g carbamide and 0.6 g elemental sulphur thoroughly grounded and placed in a ceramic crucible with cover. The crucible is heated at several temperatures, including 100\u003csup\u003eo\u003c/sup\u003eC, 200 \u003csup\u003eo\u003c/sup\u003eC, 300 \u003csup\u003eo\u003c/sup\u003eC, and at 550 \u003csup\u003eo\u003c/sup\u003eC for 1 h, 2h, and 3h, respectively. Subsequently, light brown powder was achieved called as S/GCN-3.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003c/div\u003e"},{"header":"3. Results and Discussion","content":"\u003cp\u003eThe X-ray diffraction (XRD) spectral profiles analysis for synthesized trials, including GCN, S/GCN-0, S/GCN-1, S/GCN-2, and S/GCN-3, is presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. The peak positions at (002) plane slightly differ among the trials, attributing structural changes owning to the sulphur incorporating, subsequently absence of (100) diffraction peaks, suggests a reduction in the symmetry of 3-s-triazine sketch[\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. The diffraction peak observed at (27.64) \u003csup\u003eo\u003c/sup\u003e corresponding to the (002) plane for GCN, attributed to the π-π stacking of GCN interlayered structures and is good accordance with the GCN nanocomposites[\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. Moreover, some additional peaks are observed, which is particularly due to the incorporating sulphur and structural defects merged in sample S/GCN-0, attributing sulphur is not fully incorporated with GCN, as evidence from local enlarge view, peaks at 23.26\u003csup\u003eo\u003c/sup\u003e, 26.05\u003csup\u003eo\u003c/sup\u003e, and 28.88\u003csup\u003eo\u003c/sup\u003e are corresponding to the crystalline sulphur phase as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e\u003cb\u003e(b)\u003c/b\u003e. Since the sulphur atom has higher atomic radii compared with N and C, consequently enhanced lattice defects and decrease in lattice distance, attributing diffraction peaks are shifted toward higher angle[\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]. Peak position at (002) for S/GCN-1is slightly shifted toward higher angle and no other impurity is found. Moreover, for sample S/GCN-3 peak intensity decreased, wide, and shifted toward lower angle, exhibit decreased crystallite size and enhanced amorphous contents. Higher peak intensity, sharpness, and shifted toward higher angle is indicated for S/GCN-3, corresponding to sulphur incorporation enhanced crystallinity and lower lattice distance, exhibiting strong π-π stacking interactions, which facilitate interlayer charge transfer as compared to pure GCN.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe functional groups of the GCN, S/GCN-0, S/GCN-1, S/GCN-2, and S/GCN-3 trials are investigated by employing FTIR spectroscopy. All samples exhibited almost similar patterns except S/GCN-1, S/GCN-2 ranging from 4000 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e to 500 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e wave number as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. the wide band from (3000\u0026ndash;3300) cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e exhibited O-H and N-H stretching vibrations corresponding to (NH or NH\u003csub\u003e2\u003c/sub\u003e) residual amino group of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, which are linked triazine ring structures. Moreover, boarding of the peaks is certainly result of moisture absorption and hydrogen bonding. Furthermore, the strong peaks observed at (1601cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) C\u0026thinsp;=\u0026thinsp;N, N-H bending, (1405 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) C-N bending, (1320 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) C-N bending, and (1240 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) stretching, matched to C\u0026ndash;N aromatic stretching vibrations. The observed strong peak at 803 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e attributed for tris-triazine cycle, additionally peaks from 600\u0026ndash;800 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (C-S and N-S bonding), no dominant peak is observed at 1000\u0026ndash;1200 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which attributed that sulphur oxide (S\u0026thinsp;=\u0026thinsp;O or sulfone SO\u003csub\u003e2\u003c/sub\u003e) groups are not observed. In S/GCN-1, S/GCN-2 samples the peaks at (803cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) is shifted toward higher wave number such as (810\u0026ndash;820) cm⁻\u0026sup1;, indicating tris-triazine cycle is distorted owning to sulphur incorporation, signifying that the regularity of the ring is transformed by sulfur incorporation. Moreover, the reduction in peaks intensities, peaks boarding, and shifting of peaks is correspond to the structural distortion, induction of defects, and hydrogen bonding interactions, respectively; confirming the existence of sulphur incorporation, this observation is consistent with XRD analysis.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe microstructures, surface morphology, shape, and size were analyzed by employing Scanning Electron Microscopy (SEM) for GCN, S/GCN-0, S/GCN-1, S/GCN-2, and S/GCN-3 trials as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. GCN (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e\u003cb\u003e(a)\u003c/b\u003e) exhibited stacked nanosheets with varying shapes and sizes confirmed layered structures of graphitic carbonitride, which may in result have a non-porous material with low surface area. The S/GCN-0 exhibited an agglomerated, non- porous structure with inhomogeneous-distributed, indicating sulphur element is not uniformly incorporated to the graphitic matrix. The nonappearance of significant porosity and lack of uniformity revealed uneven sulfur incorporation throughout the material as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e\u003cb\u003e(b).\u003c/b\u003e The non-porosity and uneven incorporation of sulphur is also investigated in the Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e\u003cb\u003e(c)\u003c/b\u003e, incorporation of may introduces mesopores or micropores, which are observed in the Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e\u003cb\u003e(d and e)\u003c/b\u003e. Additionally, as compared to the pristine sample, which exhibits a smooth layered structure with larger flake, while the sulphur assisted sample as in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e\u003cb\u003e(d and e)\u003c/b\u003e shows reduced thickness and possibly nano sheets or flower like formations are observed, which may be reflecting the higher surface area. The smaller size and flake like structures further confirm the alteration of the graphitic nitride matrix upon incorporation of sulphur. The elemental composition is investigated by employing Energy EDX (Dispersive X-ray Spectroscopy) for qualitative analysis. The elemental mapping is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e, representing the existence of the elements including C, N, and S. The elemental weight percentage is listed in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. The Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e\u003cb\u003e(d)\u003c/b\u003e has no sulphur element, it clearly shows the pure graphitic corban nitride. It is clearly evident from Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e\u003cb\u003e(e)\u003c/b\u003e that S/GCN-0 contains a significant amount of sulfur, which is not incorporated or linked within the GCN. A higher weight percentage (14.94%) is observed.\u003c/p\u003e \u003cp\u003eTable 1: Elemental weight percentage for GCN (a), S/GCN-0 (b), S/GCN-1(c), S/GCN-2 (d), and S/GCN-3(e).\u003c/p\u003e\n\u003cp\u003e\u003cimg 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\" width=\"646\" height=\"117\"\u003e\u003c/p\u003e \u003cp\u003eSimilarly, the sample S/GCN-1 demonstrated better results as compared with the sample S/GCN-0, although the sulphur element is incorporated with GCN as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e\u003cb\u003e(f)\u003c/b\u003e. However, the level of incorporation is inadequate to significantly enhance efficiency. In sample S/GCN-2 and S/GCN-3 Wt% is 0.22 and 0.08, respectively. Nevertheless, sample in S/GCN-2 sulphur is appropriately incorporated, resulting in higher photocatalytic efficiency compared with S/GCN-3 as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e\u003cb\u003e(g and h)\u003c/b\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe optical bandgap energy of synthesized trials was carried out by employing UV-vis diffuse reflectance spectra (DRS) as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e. The E\u003csub\u003eg\u003c/sub\u003e (bandgap energies) assessed from the photon\u0026rsquo;s energy vs \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{\\left(\\alpha\\:h\\upsilon\\:\\right)\\:}^{\\raisebox{1ex}{$1$}\\!\\left/\\:\\!\\raisebox{-1ex}{$2$}\\right.}\\)\u003c/span\u003e\u003c/span\u003e plots are as 2.79 eV, 2.72 eV, 2.82 eV, and 2.56 eV, corresponding to GCN, S/GCN-0, and S/GCN-2, respectively as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e \u003cb\u003e(a-c)\u003c/b\u003e. The S/GCN-2 exhibits more intense absorption compared to the pristine sample and S/GCN-0, as the incorporation of the sulfur element is uneven in the S/GCN-0 sample, resulting in the presence of two individual elements. However, the incorporation of sulfur reduced the bandgap energy, possibly due to the creation of energy states near the band edges, leading to enhanced photocatalytic activity, which is examined by the S/GCN-2 sample. Here, the semiconductor bandgap energy is calculated using expression no (1).\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e\n$$\\:{\\left(\\alpha\\:h\\upsilon\\:\\right)\\:}^{n}=A(h\\upsilon\\:-{E}_{g})$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eHere, variables and parameters, E\u003csub\u003eg\u003c/sub\u003e, h, A, υ, n, and α, represents bandgap energy, Plank\u0026rsquo;s constant, constant, frequency, type of bandgap transition, and absorption coefficient, respectively. Whereas, conduction band maxima energy state (E\u003csub\u003eCB\u003c/sub\u003e) and valance band minima energy states (E\u003csub\u003eVB\u003c/sub\u003e) are estimated by employing the equations (\u003cspan refid=\"Equ2\" class=\"InternalRef\"\u003e2\u003c/span\u003e and \u003cspan refid=\"Equ3\" class=\"InternalRef\"\u003e3\u003c/span\u003e).\u003cdiv id=\"Equ2\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ2\" name=\"EquationSource\"\u003e\n$$\\:{E}_{CB}=\\chi\\:-{E}_{e}-0.5{E}_{g}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e2\u003c/div\u003e\u003c/div\u003e\u003cdiv id=\"Equ3\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ3\" name=\"EquationSource\"\u003e\n$$\\:{E}_{VB}={E}_{CB}+{E}_{g}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e3\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eHere, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{E}_{CB},\\)\u003c/span\u003e\u003c/span\u003e \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\chi\\:,\\)\u003c/span\u003e\u003c/span\u003e \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{E}_{e},\\)\u003c/span\u003e\u003c/span\u003e \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{E}_{g},\\:\\)\u003c/span\u003e\u003c/span\u003e and \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{E}_{VB}\\)\u003c/span\u003e\u003c/span\u003e represents conduction band energy, absolute electronegativity (Mulliken), free electrons energy (4.50 eV, on hydrogen scale), bandgap energy, and valance band energy, respectively. Approximately, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\chi\\:=4.67\\:eV\\)\u003c/span\u003e\u003c/span\u003e energy is recognized for graphitic carbon nitride, the conduction band edges for GCN, S/GCN-2 are lies at 1.45 eV, and 1.43 eV, whereas valance band edges are at -1.34 eV and \u0026minus;\u0026thinsp;1.12 eV as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e \u003cb\u003e(d)\u003c/b\u003e. the significant valance band energy change (ΔE ⁓ 0.22 eV) is examined, attributing reduced oxidation potential for photogenerated electrons holes pairs[\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]. Moreover, sulfur incorporation may induce localized states close to the valance band edge and conduction band edge, possibly alter the electronic transfer route and improved charge suppression, leading higher catalytic efficiency.\u003c/p\u003e \u003cp\u003ePhotocatalytic activity of GCN and S/GCN-X (X\u0026thinsp;=\u0026thinsp;0, 1, 2, 3) composites was estimated by employing photodegradation of methyl blue (MB), absorption spectra for photodegradation is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e \u003cb\u003e(e-i)\u003c/b\u003e. The significant changes have been observed in the absorption spectra during MB photodegradation experiments, Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e \u003cb\u003e(e)\u003c/b\u003e exhibited significantly low photodegradation rate (⁓ 76% degradation in 60 mins) of MB dye for pristine GCN trial, maybe leading to lower solar energy absorption or higher recombination rate. Same results have been estimated from the sample S/GCN-0 as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e \u003cb\u003e(f)\u003c/b\u003e, consequence of incorporation of sulfur element in the GCN as already reported in XRD, FTIR, and EDX mapping. Possibly, similar observations have been examined in samples S/GCN-1, illustrating low degradation percentage ⁓ 80% in 60 mins as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e \u003cb\u003e(g)\u003c/b\u003e. The sample S/GCN-3 synthesized via the thermal decomposition route exhibit significantly higher photodegradation activity (⁓ 91% in 60 mins). However, enhancement likely due to the incorporation of sulfur into GCN, which increased catalytic sites and alter charge transfer route, resulting in reduced recombination made significantly enhanced catalytic activity for MB dye degradation as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e \u003cb\u003e(h)\u003c/b\u003e. The sample synthesized through Chemical Oxidation Method exhibit significantly enhanced photocatalytic efficiency owning to better surface chemistry, enhanced charge transfer, active sites development and suppressed charge recombination rate. The photodegradation rate is achieved (99.9% in 60 mins), which very significant as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e \u003cb\u003e(i)\u003c/b\u003e. Photocatalytic activity of MB dye degradation by employing photocatalysts such as GCN, S/GCN-0, S/GCN-1, S/GCN-2, and S/GCN-3 trials is illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e. Since every sample degraded the MB dye, which is coherent with the reported studied. However, the sample (S/GCN-2) fabricated with chemically oxidation method shown significantly enhanced activity, consequently degraded within 49 mins as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e \u003cb\u003e(a)\u003c/b\u003e. Mostly, photodegradation of organic pollutants has been investigated by employing Langmuir-Hinshelwood model. Additionally, it was recognized, that photodegradation reaction is take place among pollutants molecules and photogenerated active species (electrons hole pairs, radicals etc.). Nevertheless, first-order kinetics is non-complicated and effective for contaminants degradation modelling, which is expressed by using Equation no \u003cb\u003e(4)\u003c/b\u003e.\u003cdiv id=\"Equ4\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ4\" name=\"EquationSource\"\u003e\n$$\\:Ln\\:\\frac{{C}_{t}}{{C}_{0}}=Kt$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e4\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eHere, C\u003csub\u003et\u003c/sub\u003e, C\u003csub\u003e0\u003c/sub\u003e, K, and t represents degraded concentration, initial concentration, reaction constant and reaction time, respectively. Surely, this approached is adopted for quantifying reaction rates and photodegradation reaction constant. Aforementioned parameters together exhibit correlates the governing degradation photocatalytic activity with catalytic material under specific conditions. Therefore, the synthesis rout for GCN-2 contribute to altering structural and photocatalytic properties of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, consequently enhanced photocatalytic efficiency, evidenced by \u0026ldquo;K\u0026rdquo; value of GCN-2.\u003c/p\u003e"},{"header":"4. Possible Photocatalytic Mechanism","content":"\u003cp\u003eThe photocatalytic mechanism is discussed in detail by analyzing the aforementioned experimental results and measurements. Several routes have been exercised to synthesized graphitic carbonitride, all samples have same XRD profiles as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e excepts S/GCN-0, other samples peak positions at (002) plane slightly different owning to sulphur incorporating, the S/GCN-2 is more crystalline and shifting toward a higher angle, attributing decreased lattice interlayer distance of\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003etriazine (C₃N₄) framework, which is the consequence of higher photocatalytic activity. Therefore, the smaller inter layer distances of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e (framework) lattice atoms suppressed charge recombination, leading to enhanced photocatalytic activity[\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]. Additionally, thickness and interspacing distance in a 2D materials exhibited key role in photocatalytic activity and physical and chemical behavior were significantly influenced by surface modifications. Consequently, S/GCN-2 sample at (803cm\u003csup\u003e− 1\u003c/sup\u003e) peak position is shifted toward higher wave number such as (810–820) cm\u003csup\u003e− 1\u003c/sup\u003e, indicating tris-triazine cycle is distorted owning to sulphur incorporation, signifying that the regularity of the ring is transformed by sulfur incorporation as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. Moreover, the reduction in peaks intensities, peaks boarding, and shifting of peaks is correspond to the structural distortion, induction of defects, and hydrogen bonding interactions, respectively; The unique layered structures with lower activation energy grants the catalytic sites on the surface of the photocatalyst as clearly illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, reduced thickness and possibly nano sheets or flower like formations are observed, which may enhance the solar energy absorption, resultant in higher photocatalytic activity. Since the S/GCN-2 has a reduced bandgap energy (i.e., E\u003csub\u003eg\u003c/sub\u003e= 2.56 eV), it absorbed significantly more visible light energy. The light absorption is expressed for both sulphur and graphitic carbon nitride as mentioned in reaction Eqs.\u0026nbsp;(\u003cspan refid=\"Equ5\" class=\"InternalRef\"\u003e5\u003c/span\u003e and \u003cspan refid=\"Equ6\" class=\"InternalRef\"\u003e6\u003c/span\u003e)\u003c/p\u003e\u003cdiv id=\"Equ5\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ5\" name=\"EquationSource\"\u003e\n$$\\:g-{C}_{3}{N}_{4}+hv\\to\\:g-{C}_{3}{N}_{4}({e}^{-}+{h}^{+})$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e5\u003c/div\u003e\u003c/div\u003e\u003cdiv id=\"Equ6\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ6\" name=\"EquationSource\"\u003e\n$$\\:\\:S+hv\\to\\:S({e}^{-}+{h}^{+})$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e6\u003c/div\u003e\u003c/div\u003e\u003cp\u003e\u003c/p\u003e \u003cp\u003eSince the photogenerated e\u003csup\u003e−\u003c/sup\u003e and h\u003csup\u003e+\u003c/sup\u003e pairs transferred to their prospective energy states, such as e\u003csup\u003e−\u003c/sup\u003e transferred from the GCN conduction band to the conduction band of sulphur and vice versa. Which, suppressed the photogenerated charge recombination, resultant in higher catalytic efficiency. The e\u003csup\u003e−\u003c/sup\u003e form superoxide (e\u003csup\u003e−\u003c/sup\u003e + O\u003csub\u003e2\u003c/sub\u003e = O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e−\u003c/sup\u003e) radicals when react with oxygen (O\u003csub\u003e2\u003c/sub\u003e); similarly, h\u003csup\u003e+\u003c/sup\u003e react with water (H\u003csub\u003e2\u003c/sub\u003eO) formed (OH) radicals. Therefore, the generated radicals react with the MB dye molecules and break chromophoric structure of MB dye into to smaller molecules, including inorganic ions H\u003csub\u003e2\u003c/sub\u003eO, and CO\u003csub\u003e2\u003c/sub\u003e. The above-mentioned conclusions confirm the appreciated activity of S/GCN-2 photocatalyst, which explored a potential route for synthesis of sulphur assisted graphitic carbonitride.\u003c/p\u003e "},{"header":"Conclusion","content":"\u003cp\u003eSulfur assisted graphitic carbon nitride is fabricated by using several synthesis routes. The easy fabrication and low cost of the precursors offers sustainable solution for environmental remediation for mitigation the annual release of synthetic dyes into the environment. Incorporating sulfur into heptazine framework improved the photocatalytic activity of GCN by modification its energy bandgap structure, photogenerated charge transfer route. The degradation of synthetic dye methyl blue is examined by all the fabricated trials, S/GCN-2 shown higher catalytic activity, as a result in uniform incorporation of sulphur element, lower energy optical bandgap (2.56 eV), higher crystallinity, and estimated reaction constant (K = 0.069) leads to improved solar energy absorption. Moreover, this study figured out a novel synthesis route for incorporation of co-catalytic element into GCN and carbon-based semiconductor materials.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eDeclaration of competing interest\u003c/h2\u003e \u003cp\u003eThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eJianhua Hou; Supervision, Pir Bukhsh khan ; data analysis, Sadia Nazir; review and editing, M. Boota, XRD nd EDX analysis Sadam Ahmed, Experimentation, Thamraa Alshahrani; Characterizations, Mouna Jeridi; data analysis, Asif Hussain; writing and review\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e \u003cp\u003eThe authors extend their appreciation to the Deanship of Research and Graduate Studies at King Khalid University, Saudi Arabia for funding this work through the Small Groups Project under grant number R.G.P1/138/45.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eHussain, A., et al., \u003cem\u003eRecent advances in BiOX-based photocatalysts to enhanced efficiency for energy and environment applications.\u003c/em\u003e Catalysis Reviews, 2024. \u003cstrong\u003e66\u003c/strong\u003e(1): p. 119-173. https://doi.org/10.1080/01614940.2022.2041836\u003c/li\u003e\n\u003cli\u003eHussain, A., et al., \u003cem\u003eFine-tuning internal electric field of BiOBr for suppressed charge recombination.\u003c/em\u003e Journal of Environmental Chemical Engineering, 2021. \u003cstrong\u003e9\u003c/strong\u003e(1): p. 104766. https://doi.org/10.1016/j.jece.2020.104766\u003c/li\u003e\n\u003cli\u003eHussain, A., et al., \u003cem\u003eDiverse morphological study for nonmetal-doped g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e composites with narrow bandgap for improved photocatalytic activity.\u003c/em\u003e Research on Chemical Intermediates, 2022. \u003cstrong\u003e48\u003c/strong\u003e(7): p. 2857-2870. https://doi.org/10.1007/s11164-022-04750-5\u003c/li\u003e\n\u003cli\u003eHou, J., et al., \u003cem\u003eFast preparation of oxygen vacancy-rich 2D/2D bismuth oxyhalides-reduced graphene oxide composite with improved visible-light photocatalytic properties by solvent-free grinding.\u003c/em\u003e Journal of Cleaner Production, 2021. \u003cstrong\u003e328\u003c/strong\u003e: p. 129651. https://doi.org/10.1016/j.jclepro.2021.129651\u003c/li\u003e\n\u003cli\u003eHasan, M., et al., \u003cem\u003eStructural, optical, electrical and magnetic tuning based on Zn substitution at a site in yttrium doped spinel ferrites.\u003c/em\u003e Materials Chemistry and Physics, 2023. \u003cstrong\u003e301\u003c/strong\u003e: p. 127538. https://doi.org/10.1016/j.matchemphys.2023.127538\u003c/li\u003e\n\u003cli\u003eRehman, Z.U., et al., \u003cem\u003ePhotocatalytic CO\u003csub\u003e2\u003c/sub\u003e reduction using TiO\u003csub\u003e2\u003c/sub\u003e-based photocatalysts and TiO\u003csub\u003e2\u003c/sub\u003e Z-scheme heterojunction composites: a review.\u003c/em\u003e Molecules, 2022. \u003cstrong\u003e27\u003c/strong\u003e(7): p. 2069. https://doi.org/10.3390/molecules27072069\u003c/li\u003e\n\u003cli\u003eHussain, A., et al., \u003cem\u003eInvestigation of transition metal-doped graphitic carbon nitride for MO dye degradation.\u003c/em\u003e Diamond and Related Materials, 2023. \u003cstrong\u003e132\u003c/strong\u003e: p. 109648. https://doi.org/10.1016/j.diamond.2022.109648\u003c/li\u003e\n\u003cli\u003eul Hassan, H.M., et al., \u003cem\u003eReduce the recombination rate by facile synthesis of MoS\u003csub\u003e2\u003c/sub\u003e/g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e heterostructures as a solar light responsive catalyst for organic dye degradation.\u003c/em\u003e Diamond and Related Materials, 2023. \u003cstrong\u003e140\u003c/strong\u003e: p. 110420. https://doi.org/10.1016/j.diamond.2023.110420\u003c/li\u003e\n\u003cli\u003eZhang, T., et al., \u003cem\u003eChemical precipitation synthesis of Bi\u003csub\u003e0.7\u003c/sub\u003eFe\u003csub\u003e0.3\u003c/sub\u003eOCl nanosheets via Fe (III)-doped BiOCl for highly visible light photocatalytic performance.\u003c/em\u003e Materials Today Communications, 2021. \u003cstrong\u003e26\u003c/strong\u003e: p. 102145. https://doi.org/10.1016/j.mtcomm.2021.102145\u003c/li\u003e\n\u003cli\u003eCao, S. and J. 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The release of fabricated dyes as an industrial wastage emerged as a worldwide challenge. Significant amounts are discharged in wastewater annually, poising significant risks owing to harmful toxic effects. Semiconductor\u0026rsquo;s materials have emerged as a sustainable and green remediation solution. Among various materials, graphitic carbon nitride stands out as an extensively investigated material due to ease fabricated and low cost. Here in this study, graphitic carbon nitride with sulphur assistance, its fabrication routes (i.e., thermal polymerization, sonication, chemically oxidation, and step wise thermal polymerization), characterizations, and photocatalytic performance for methyl blue treatment are reported. Exhibited 2.79 eV, 2.72 eV, 2.82 eV, and 2.56 eV band gap energies with 55%, 67%, 70%, 75%, and 99.5% pollutants degradation activity achieved. The chemically oxidation route attributed higher photocatalytic activity (99.5%, in 50 mins) with the reaction rate constant (K\u0026thinsp;=\u0026thinsp;0.069). The aforementioned results and measurements are supported by UV\u0026ndash;vis diffuse reflectance, signifying bandgap energy, XRD for structural and SEM for morphological and EDX for elemental qualitative analysis. The chemical oxidation route demonstrates an excellent method for sulfur-assisted graphitic carbon nitride synthesis. This novel route will advance the scientific community in the fabrication process.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e","manuscriptTitle":"Diverse Fabrication Routs for Sulphur-Assisted Graphitic Carbon Nitride for Contaminants Degradation Through Solar Energy","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-05-16 13:14:52","doi":"10.21203/rs.3.rs-6535026/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-05-28T02:05:28+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-05-27T14:19:53+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-05-23T17:17:15+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"323161840876673569674478688846055214800","date":"2025-05-18T18:08:41+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"27347614993346615797575404104719758926","date":"2025-05-14T12:18:55+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-05-14T01:50:35+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-04-29T12:17:25+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-04-29T12:11:40+00:00","index":"","fulltext":""},{"type":"submitted","content":"Research on Chemical Intermediates","date":"2025-04-26T12:28:19+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"research-on-chemical-intermediates","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"rint","sideBox":"Learn more about [Research on Chemical Intermediates](http://link.springer.com/journal/11164)","snPcode":"11164","submissionUrl":"https://submission.nature.com/new-submission/11164/3","title":"Research on Chemical Intermediates","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"709f90ac-9374-446d-bc30-0fb6afe035e5","owner":[],"postedDate":"May 16th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-07-28T16:02:09+00:00","versionOfRecord":{"articleIdentity":"rs-6535026","link":"https://doi.org/10.1007/s11164-025-05672-8","journal":{"identity":"research-on-chemical-intermediates","isVorOnly":false,"title":"Research on Chemical Intermediates"},"publishedOn":"2025-07-22 15:57:05","publishedOnDateReadable":"July 22nd, 2025"},"versionCreatedAt":"2025-05-16 13:14:52","video":"","vorDoi":"10.1007/s11164-025-05672-8","vorDoiUrl":"https://doi.org/10.1007/s11164-025-05672-8","workflowStages":[]},"version":"v1","identity":"rs-6535026","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6535026","identity":"rs-6535026","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}