Pivotal Impact Factors in Photocatalytic Reduction of CO2 to Value-Added C1 and C2 Products.

Over the past decades, CO2 greenhouse emission has been considerably increased, causing global warming and climate change. Indeed, converting CO2 into valuable chemicals and fuels is a desired option to resolve issues caused by its continuous emission into the atmosphere. Nevertheless, CO2 conversion has been hampered by the ultrahigh dissociation energy of C=O bonds, which makes it thermodynamically and kinetically challenging. From this prospect, photocatalytic approaches appear promising for CO2 reduction in terms of their efficiency compared to other traditional technologies. Thus, many efforts have been made in the designing of photocatalysts with asymmetric sites and oxygen vacancies, which can break the charge distribution balance of CO2 molecule, reduce hydrogenation energy barrier and accelerate CO2 conversion into chemicals and fuels. Here, we review the recent advances in CO2 hydrogenation to C1 and C2 products utilizing photocatalysis processes. We also pin down the key factors or parameters influencing the generation of C2 products during CO2 hydrogenation. In addition, the current status of CO2 reduction is summarized, projecting the future direction for CO2 conversion by photocatalysis processes.

Tuning the Microstructures of ZnO To Enhance Photocatalytic NO Removal Performances.

Effective removal of kinetically inert dilute nitrogen oxide (NO, ppb) without NO2 emission is still a challenging topic in environmental pollution control. One effective approach to reducing the harm of NO is the construction of photocatalysts with diversified microstructures and atomic arrangements that could promote adsorption, activation, and complete removal of NO without yielding secondary pollution. Herein, microstructure regulations of ZnO photocatalysts were attempted by altering the reaction temperature and alkalinity in a unique ionic liquid-based solid-state synthesis and further investigated for the removal of dilute NO upon light irradiation. Microstructure observations indicated that as-tuned photocatalysts displayed unique nucleation, diverse morphologies (spherical nanoparticles, short and long nanorods), defect-related optical characteristics, and enhanced carrier separations. Such defect-related surface-interface aspects, especially Vo″-related defects of ZnO devoted them to the 4.16-fold enhanced NO removal and 2.76 magnitude order decreased NO2 yields, respectively. Improved NO removal and toxic product inhabitation in as-tuned ZnO was disclosed by mechanistic exploitations. It was revealed that regulated microstructures, defect-related charge carrier separation, and strengthened surface interactions were beneficial to active species production and molecular oxygen activation in ZnO, subsequently contributing to the improved NO removal and simultaneous avoidance of NO2 formation. This investigation shed light on the facile regulation of microstructures and the roles of surface chemistry in the oxidation of low concentration NO in the ppb level upon light illumination.

Investigation of the Photocatalytic Hydrogen Production of Semiconductor Nanocrystal-Based Hydrogels.

Destabilization of a ligand-stabilized semiconductor nanocrystal solution with an oxidizing agent can lead to a macroscopic highly porous self-supporting nanocrystal network entitled hydrogel, with good accessibility to the surface. The previously reported charge carrier delocalization beyond a single nanocrystal building block in such gels can extend the charge carrier mobility and make a photocatalytic reaction more probable. The synthesis of ligand-stabilized nanocrystals with specific physicochemical properties is possible, thanks to the advances in colloid chemistry made in the last decades. Combining the properties of these nanocrystals with the advantages of nanocrystal-based hydrogels will lead to novel materials with optimized photocatalytic properties. This work demonstrates that CdSe quantum dots, CdS nanorods, and CdSe/CdS dot-in-rod-shaped nanorods as nanocrystal-based hydrogels can exhibit a much higher hydrogen production rate compared to their ligand-stabilized nanocrystal solutions. The gel synthesis through controlled destabilization by ligand oxidation preserves the high surface-to-volume ratio, ensures the accessible surface area even in hole-trapping solutions and facilitates photocatalytic hydrogen production without a co-catalyst. Especially with such self-supporting networks of nanocrystals, the problem of colloidal (in)stability in photocatalysis is circumvented. X-ray photoelectron spectroscopy and photoelectrochemical measurements reveal the advantageous properties of the 3D networks for application in photocatalytic hydrogen production.

Boosting photocatalytic performances of lamellar BiVO4by constructing S-scheme heterojunctions with AgBr for efficient charge transfer.

Successful construction of heterojunction can improve the utilization efficiency of solar light by broadening the absorption range, facilitating charge-carrier separation, promoting carrier transportation and influencing surface-interface reaction. Herein, visible-light-driven AgBr was deposited on the surface of lamellar BiVO4which was prepared by a facile hydrothermal process to improve charge carrier separation, and subsequent photocatalytic effectiveness. The catalyst with an optimal AgBr/BiVO4ratio exhibited a superbly enhanced photocatalytic decolorization ability (about 6.85 times higher than that of pure BiVO4) and high stability after four cycles. The unique photocatalytic mechanism of S-scheme carrier migration was investigated on the bases of radical trapping tests and photo/electrochemical characterizations. Results showed that the enhanced migration strategy and intimately interfacial collaboration guaranteed the effective charge carriers separation/transfer, leading to magnificent photocatalytic performance as well as excellent stability.

Design and synthesis of TiO2/C nanosheets with a directional cascade carrier transfer.

Directed transfer of carriers, akin to excited charges in photosynthesis, in semiconductors by structural design is challenging. Here, TiO2 nanosheets with interlayered sp2 carbon and titanium vacancies are obtained by low-temperature controlled oxidation calcination. The directed transfer of carriers from the excited position to Ti-vacancies to interlayered carbon is investigated and proven to greatly increase the charge transport efficiency. The TiO2/C obtained demonstrates excellent photocatalytic and photoelectrochemical activity and significant lithium/sodium ion storage performance. Further theoretical calculations reveal that the directional excited position/Ti-vacancies/interlayered carbon facilitate the spatial inside-out cascade electron transfer, resulting in high charge transfer kinetics.

Photocatalytic H2 production and degradation of aqueous 2-chlorophenol over B/N-graphene-coated Cu0/TiO2: A DFT, experimental and mechanistic investigation.

Energy and environmental challenges are global concerns that scientists are interested in alleviating. It is on this premise that we prepared boron/nitrogen graphene-coated Cu0/TiO2 (B/N-graphene-coated Cu/TiO2) photocatalyst of varying B:N ratios with dual functionality of H2 production and 2-Chlorophenol (2-CP) degradation. In-situ coating of Cu0 with B/N-graphene is achieved via solvothermal synthesis and calcination under an inert atmosphere. All B/N-graphene-coated Cu/TiO2 exhibit higher photonic efficiencies (5.68%-7.06% at 300 < λ < 400 nm) towards H2 production than bare TiO2 (0.25% at 300 < λ < 400 nm). Varying the B:N ratio in graphene influences the efficiency of H2 generation. A B:N ratio of 0.08 yields the most active composite exhibiting a photonic efficiency of 7.06% towards H2 evolution and a degradation rate of 4.07 × 10-2 min-1 towards 2-chlorophenol (2-CP). Density functional theory (DFT) investigations determine that B-doping (p-type) enhances graphene stability on Cu0 while N-doping (n-type) increases the reduction potential of Cu0 relative to H+ reduction potential. X-ray photoelectron spectroscopy reveals that increasing the B:N ratio increases p-type BC2O while decreasing n-type pyridinic-N in graphene thus altering the interlayer electron density. Isotopic labelling experiments determine water reduction as the main mechanism by which H2 is produced over B/N-graphene-coated Cu/TiO2. The reactive species involved in the degradation of 2-CP are holes (h+), hydroxyl radical (OH•), and O2•-, of which superoxide (O2•-) plays the major role. This work displays B/N -graphene-coated Cu/TiO2 as a potential photocatalyst for large-scale H2 production and 2-CP degradation.

Effect of Cu2O Substrate on Photoinduced Hydrophilicity of TiO2 and ZnO Nanocoatings.

The effect of a Cu2O substrate on the photoinduced alteration of the hydrophilicity of TiO2 and ZnO surfaces was studied. It was demonstrated that the formation of heterostructures Cu2O/TiO2 and Cu2O/ZnO strongly changed the direction of the photoinduced alteration of surface hydrophilicity: while both TiO2 and ZnO demonstrate surface transition to superhydrophilic state under UV irradiation and no significant alteration of the surface hydrophilicity under visible light irradiation, the formation of Cu2O/TiO2 and Cu2O/ZnO heterostructures resulted in photoinduced decay of the surface hydrophilicity caused by both UV and visible light irradiation. All observed photoinduced changes of the surface hydrophilicity were compared and analyzed in terms of photoinduced alteration of the surface free energy and its polar and dispersive components. Alteration of the photoinduced hydrophilic behavior of TiO2 and ZnO surfaces caused by formation of the corresponding heterostructures with Cu2O are explained within the mechanism of electron transfer and increasing of the electron concentration on the TiO2 and ZnO surfaces.

Isotope Effects in Photocatalysis: An Underexplored Issue.

In order to improve the performance of well-established photocatalysts and to develop new potential photocatalyst materials, an understanding of the underlying mechanisms of photocatalytic reactions is of the utmost importance. An often neglected method for studying the mechanism is the investigation of isotope effects. Although just a few studies related to isotope effects exist, it has been shown to be a powerful tool for exploring mechanisms of photocatalytic processes. Most of the reports are focused on TiO2, which is the most studied photocatalyst, while there is a lack of data for other photocatalyst materials. This mini-review represents an overview of research utilizing isotope effects in the area of photocatalysis. The benefits and the importance of these studies will be highlighted, and the potential for these processes to be applied for the study of further photocatalytic reactions and different photocatalyst materials will be shown.

Visible light-driven novel Bi2Ti2O7/CaTiO3 composite photocatalyst with enhanced photocatalytic activity towards NO removal.

Photocatalysis is regarded as a promising technology for removal of nitrogen oxide (NO), however, the low photocatalytic efficiencies under visible light irradiation and the deactivation of the photocatalyst are as yet the significant issues that should be addressed. In this work, visible-light-driven Bi2Ti2O7/CaTiO3 heterojunction composites were synthesized by a facile in-situ hydrothermal method. The Bi2Ti2O7/CaTiO3 composites displayed superior visible light photocatalytic activity than pure CaTiO3 and pure Bi2Ti2O7 in the removal of NO at the 600 ppb level in air. Among all the composites, Bi2Ti2O7/CaTiO3 containing 20 wt% Bi2Ti2O7 exhibited the best photocatalytic activity, achieving a maximum removal efficiency of 59%. The improved photocatalytic performance is mainly attributed to the strong visible-light-absorbing ability, the presence of an appropriate density of oxygen vacancy defects and the formation of heterojunction between CaTiO3 and Bi2Ti2O7, resulting in an efficient charge separation at the interface as proven by photoluminescence (PL) and photo-induced current measurements. According to trapping experiments and spin-trapping ESR analysis, the •O2- and h+ are the principal reactive species involved in the photocatalytic NO removal. In addition, the as-obtained Bi2Ti2O7/CaTiO3 composite showed good chemical stability, which is beneficial for practical applications in air pollution removal.

Soft and hard templates assisted synthesis mesoporous CuO/g-C3N4 heterostructures for highly enhanced and accelerated Hg(II) photoreduction under visible light.

Herein, triblock copolymer surfactant (F127) and mesoporous silica (MCM-41) as soft and hard templates were employed to synthesize of mesoporous CuO/g-C3N4 heterostructures with large surface areas for Hg(II) photoreduction in existence of formic acid as a holes sacrificial. TEM image for mesoporous CuO/g-C3N4 indicated that CuO NPs are homogeneously distributed with spherical shape in particle size ~5 nm onto the surface of g-C3N4. Mesoporous 2%CuO/g-C3N4 heterostructure was achieved a high Hg(II) photoreduction rate of 628.74 µmolg-1h-1 and high photoreduction efficiency of ~100% within 50 min compared with the pure either mesoporous CuO NPs (130.11 µmolg-1h-1, 21%) and g-C3N4 (88.54 µmolg-1h-1, 14%). The highest Hg(II) photoreduction rate achieved was 628.74 µmolg-1h-1, which is 4.83 and 7.1 magnitudes stronger than mesoporous CuO NPs and g-C3N4. The excellent photocatalytic performance of mesoporous CuO/g-C3N4 heterostructures for Hg(II) photoreduction is referred to highly dispersed mesoporous CuO NPs with small particle size onto g-C3N4, narrow bandgap, large surface area, a rapid transfer of Hg(II) ions and HCOOH to easily reach the active sites due to the facile penetration through the mesostructure, thus promoting the utilization of porous structure of CuO/g-C3N4 heterostructures for efficient diffusion of Hg(II) ions. The intense interaction between mesoporous CuO NPs and porous g-C3N4 confirms the durability of the CuO/g-C3N4 heterostructures during recyclability for five times.

Nitrogen/Carbon-Coated Zero-Valent Copper as Highly Efficient Co-catalysts for TiO2 Applied in Photocatalytic and Photoelectrocatalytic Hydrogen Production.

Zero-valent copper (Cu0) is a promising co-catalyst in semiconductor-based photocatalysis as it is inexpensive and exhibits electronic properties similar to those of Ag and Au. However, its practical application in photocatalytic hydrogen production is limited by its susceptibility to oxidation, forming less active Cu species. Herein, we have carried out in situ encapsulation of Cu0 nanoparticles with N-graphitic carbon layers (14.4% N) to stabilize Cu0 nanoparticles (N/C-coated Cu) and improve the electronic communication with a TiO2 photocatalyst. A facile solvothermal procedure is used to coat the Cu0 nanoparticles at 200 °C, while graphitization is achieved by calcination at 550 °C under an inert atmosphere. The resultant N/C-coated Cu/TiO2 composites outperform the uncoated Cu counterparts, exhibiting a 27-fold enhancement of the hydrogen evolution rate compared to TiO2 and achieving a rate of 19.03 mmol g-1 h-1 under UV-vis irradiation. Likewise, the N/C-coated Cu co-catalyst exhibits a less negative onset potential of -0.05 V toward hydrogen evolution compared to uncoated Cu (ca. -0.30 V). This superior activity is attributed to coating Cu0 with N/C, which enhances the stability, electronic communication with TiO2, conductivity, and interfacial charge transfer processes. The reported synthetic approach is simple and scalable, yielding an efficient and affordable Cu0 co-catalyst for TiO2.

Pb-Free Cs3Bi2I9 Perovskite as a Visible-Light-Active Photocatalyst for Organic Pollutant Degradation.

In our work, we employed Cs3Bi2I9 as a visible-light-active photocatalyst, synthesized with a low-temperature solvothermal method. The morphological and structural properties of the as-prepared perovskite were investigated, and the results were compared to previous studies to confirm its nature and the quality of the synthesis procedure. Transient absorption spectroscopy was applied in order to investigate the generation and lifetime of photogenerated charge carriers, revealing their formation after visible light excitation. The potential photocatalytic activity of the as-prepared metal halide perovskite was applied for the removal of Rhodamine B in aqueous solution, demonstrating an excellent activity of 93% after 180 min under visible-light irradiation. The current research aims to provide insights into the design of a new visible-light-active photocatalyst, Cs3Bi2I9, selected for its high application value in the field of advanced materials for light harvesting.

Ag(I) ions working as a hole-transfer mediator in photoelectrocatalytic water oxidation on WO3 film.

Ag(I) is commonly employed as an electron scavenger to promote water oxidation. In addition to its straightforward role as an electron acceptor, Ag(I) can also capture holes to generate the high-valent silver species. Herein, we demonstrate photoelectrocatalytic (PEC) water oxidation and concurrent dioxygen evolution by the silver redox cycle where Ag(I) acts as a hole-transfer mediator. Ag(I) enhances the PEC performance of WO3 electrodes at 1.23 V vs. RHE with increasing O2 evolution, while forming Ag(II) complexes (AgIINO3+). Upon turning off both light and potential bias, the photocurrent immediately drops to zero, whereas O2 evolution continues over ~10 h with gradual bleaching of the colored complexes. This phenomenon is observed neither in the Ag(I)-free PEC reactions nor in the photocatalytic (i.e., bias-free) reactions with Ag(I). This study finds that the role of Ag(I) is not limited as an electron scavenger and calls for more thorough studies on the effect of Ag(I).

UV/Vis Light Induced Degradation of Oxytetracycline Hydrochloride Mediated byCo-TiO2 Nanoparticles.

Pharmaceuticals, especially antibiotics, constitute an important group of aquatic contaminants given their environmental impact. Specifically, tetracycline antibiotics (TCs) are produced in great amounts for the treatment of bacterial infections in both human and veterinary medicine. Several studies have shown that, among all antibiotics, oxytetracycline hydrochloride (OTC HCl) is one of the most frequently detected TCs in soil and surface water. The results of the photocatalytic degradation of OTC HCL in aqueous suspensions (30 mg·L-1) of 0.5 wt.% cobalt-doped TiO2 catalysts are reported in this study. The heterogeneous Co-TiO2 photocatalysts were synthesized by two different solvothermal methods. Evonik Degussa Aevoxide P25 and self-prepared TiO2 modified by the same methods were used for comparison. The synthesized photocatalysts were characterized by X-ray powder diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), UV/vis diffuse reflectance spectroscopy (DRS), and N2 adsorption (BET) for specific surface area determination. The XRD and Raman results suggest that Ti4+ was substituted by Co2+ in the TiO2 crystal structure. Uv/visible spectroscopy of Co-TiO2-R showed a substantial redshift in comparison with bare TiO2-R. The photocatalytic performance of the prepared photocatalysts in OTC HCL degradation was investigated employing Uv/vis spectroscopy and high-performance liquid chromatography (HPLC). The observed initial reaction rate over Co-TiO2-R was higher compared with that of Co-TiO2-HT, self-prepared TiO2, and the commercial P25. The enhanced photocatalytic activity was attributed to the high surface area (153 m2·g-1) along with the impurity levels within the band gap (2.93 eV), promoting the charge separation and improving the charge transfer ability. From these experimental results, it can be concluded that Co-doping under reflux demonstrates better photocatalytic performances than with the hydrothermal treatment.

Unraveling the photocatalytic properties of TiO2/WO3 mixed oxides.

TiO2/WO3 heterojunctions are one of the most investigated systems for photocatalytic applications. However, distinct behavior can be found in the literature depending on the pollutant to be degraded and the photocatalyst preparation conditions. Some authors reported improved photocatalytic activities in relation to TiO2, while others a deleterious effect. Different factors have been identified to influence the activity of such systems. In this work, a systematic investigation of TiO2/WO3 samples with different W/Ti ratios (0-100%) was carried out using different pollutants as targets (gaseous NO, acetaldehyde and aqueous methylene blue solutions). A detailed structural investigation along with transient absorption studies and photoelectrochemical measurements allowed the rationalization of some of the previously reported factors that control the TiO2/WO3 photoactivity, i.e. the inability to reduce molecular oxygen, the stabilization of the anatase phase and the adsorption surface properties. The investigations also identified a factor not previously reported: in TiO2/WO3 systems, a fraction of long-lived holes do not take part in the interfacial charge transfer to efficient hole quenchers, such as methanol. This behavior seems to be related to the doping of the TiO2 matrix with W(vi) and plays a key role in the photocatalytic activity.

Influence of the preparation conditions on the morphology and photocatalytic performance Pt-modified hexaniobate composites.

The preparation of lamellar nanostructures through exfoliation of stacked niobates is an interesting approach to the development of photocatalysts for energy conversion and environmental remediation. These materials exhibit a rich surface chemistry and several nanocomposites can be produced through intercalation or impregnation of suitable precursors. In this work, the influence of the physico-chemical preparation conditions on the photocatalytic activity of Pt-hexaniobate nanocomposites was investigated aiming at the establishment of the main factors that control their photoreactivities. Modification of hexaniobate layers were carried out by adsorption and impregnation methods, using [Pt(NH3)4]Cl2 (Pt1) and H2PtCl6 (Pt2), respectively. The addition of platinum precursors (1% wt.) were performed in the presence of the exfoliating agent tert-butylammonium hydroxide, sNb, or after acidic precipitation followed by resuspension in plain water, eNb. All samples were submitted to photoirradiation to reduce the platinum precursors and the effect of a previous thermal treatment was also evaluated. It was observed that H2 evolution from aqueous methanol solutions is more favored on hexaniobate nanosheets (eNb-Pt1 and eNb-Pt2) instead of scrolled layers (sNb-Pt1 and sNb-Pt2), independent on the platinum precursor. Moreover, residual tert-butylammonium can act as hole scavenger and decrease the degradation rates for methanol oxidation in sNb samples. The curled layers observed for sNb samples seem to favor the photodegradation of cationic species, such as methylene blue. Thermal treatment at 500 °C leads to morphological changes with a decrease of the specific surface area due to restacking of the individual layers along with some curling. As a result, the H2 evolution rates strongly decreases in relation to the non-sintered samples, suggesting that the 'soft' photoreduction of platinum precursors is the best method for preparation of these photocatalysts. The correlations between the preparation conditions and the photocatalytic activity for different photoreactions can allow the development of optimized materials for specific applications.

Two-Dimensional Layered Zinc Silicate Nanosheets with Excellent Photocatalytic Performance for Organic Pollutant Degradation and CO2 Conversion.

Two-dimensional (2D) photocatalysts are highly attractive for their great potential in environmental remediation and energy conversion. Herein, we report a novel layered zinc silicate (LZS) photocatalyst synthesized by a liquid-phase epitaxial growth route using silica derived from vermiculite, a layered silicate clay mineral, as both the lattice-matched substrate and Si source. The epitaxial growth of LZS is limited in the 2D directions, thus generating the vermiculite-type crystal structure and ultrathin nanosheet morphology with thicknesses of 8-15 nm and a lateral size of about 200 nm. Experimental observations and DFT calculations indicated that LZS has a superior band alignment for the degradation of organic pollutants and reduction of CO2 to CO. The material exhibited efficient photocatalytic performance for 4-chlorophenol (4-CP) degradation and CO2 conversion into CO and is the first example of a claylike 2D photocatalyst with strong photooxidation and photoreduction capabilities.

Photodegradation of Microcystin-LR Using Visible Light-Activated C/N-co-Modified Mesoporous TiO2 Photocatalyst.

Microcystin-LR (MC-LR), a potent hepatotoxin produced by the cyanobacteria, is of increasing concern worldwide because of severe and persistent impacts on humans and animals by inhalation and consumption of contaminated waters and food. In this work, MC-LR was removed completely from aqueous solution using visible-light-active C/N-co-modified mesoporous anatase/brookite TiO2 photocatalyst. The co-modified TiO2 nanoparticles were synthesized by a one-pot hydrothermal process, and then calcined at different temperatures (300, 400, and 500 °C). All the obtained TiO2 powders were analyzed by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscope (TEM), specific surface area (SSA) measurements, ultraviolet-visible diffuse reflectance spectra (UV-vis DRS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, and photoluminescence (PL) analysis. It was found that all samples contained mixed-phase TiO2 (anatase and brookite), and the content of brookite decreased with an increase in calcination temperature, as well as the specific surface area and the content of non-metal elements. The effects of initial pH value, the TiO2 content, and MC-LR concentration on the photocatalytic activity were also studied. It was found that the photocatalytic activity of the obtained TiO2 photocatalysts declined with increasing temperature. The complete degradation (100%) of MC-LR (10 mg L-1) was observed within 3 h, using as-synthesized co-modified TiO2 (0.4 g L-1) at pH 4 under visible light. Based on the obtained results, the mechanism of MC-LR degradation has been proposed.

ZnO@ porous graphite nanocomposite from waste for superior photocatalytic activity.

In this work, a new type of advanced 3D mesoporous carbon nanocomposites derived from Zn dust/PET bottle mixed waste with a high surface area is created. Interestingly, simultaneous transformation of Zn metal into ZnO nanoparticles and PET bottle waste to porous carbon materials occurred upon thermal treatment at 700 °C. The effect of the amount of Zn metal on the prepared materials has been studied. The carbon material-based waste presented very large surface area (up to 684.5 m2/g) with pore size distribution (18.47-16.88 nm). The SEM and TEM analysis revealed that the produced carbon materials have 3D porous dense layers with a gradient pore structure. The created waste-based nanocomposite exhibited an enhanced photocatalytic performance for the degradation of organic dyes (methylene blue and malachite green). It is believed that the presented work not only provides a sustainable approach to the creation of new nanocomposites of ZnO-mesoporous carbon materials for the application in photocatalysis but also introduces a new way of upcycling of mixed waste materials.

A novel L-Histidine (C, N) codoped-TiO2-CdS nanocomposite for efficient visible photo-degradation of recalcitrant compounds from wastewater.

The aim of current study is to synthesis novel visible driven photocatalysts (L-Histidine (C, N) codoped-TiO2-CdS) with different loadings of L-Hisitdine (1, 2, and 3 wt.%) and CdS (1:9, 7:1, and 1:5 mass ratios of CdS to TiO2). Then, their application for photo-degradation of methyl orange (MO) and biologically treated palm oil mill effluent (POME) were studied. The structure, optical properties, and morphology of the prepared nanocomposites were also characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Fourier transform infrared (FT-IR), photoluminescence spectroscopy (PL), and diffuse reflectance spectra (DRS). DRS results indicated that all the modified samples with different L-Hisitdine and CdS loadings showed a red shift to visible region. The results of photo-degradation experiments showed that L-Hisitdine with a weight fraction of 2% and mass ratio of TiO2 to CdS of 7:1 were the optimum amount of the modifiers in the photocatalyst network. The PL intensity of the photocatalyst decreased with addition of L-Hisitdine and CdS nanoparticles due to a decrease in e-/h+ recombination. The effects of organic pollutant concentration, initial pH, catalyst concentration, and irradiation time on the photo-degradation process of MO and POME were studied using full faced centered central composite design (CCFD) under response surface methodology (RSM). The obtained results showed that MO was completely removed at initial concentration of 10 mg/L, acidic pH, and catalyst loading of 1.5 g/L after 120 min. The complete degradation of biologically treated POME was achieved at original pH, 300 mg/L of chemical oxygen demand (COD) concentration, catalyst loading of 2 g/L, and irradiation time of 2 h.