Photoreduction Products Research Articles

Integration of Plasmonic Ag(I) Clusters and Fe(II) Porphyrinates into Metal-Organic Frameworks for Efficient Photocatalytic CO2 Reduction Coupling with Photosynthesis of Pure H2O2.

Efficient photocatalytic CO2 reduction coupled with the photosynthesis of pure H2O2 is a challenging and significant task. Herein, using classical CO2 photoreduction site iron porphyrinate as the linker, Ag(I) clusters were spatially separated and evenly distributed within a new metal-organic framework (MOF), namely Ag27TPyP-Fe. With water as electron donors, Ag27TPyP-Fe exhibited remarkable performances in artificial photosynthetic overall reaction with CO yield of 36.5 μmol g-1 h-1 and ca. 100 % selectivity, as well as H2O2 evolution rate of 35.9 μmol g-1 h-1. Since H2O2 in the liquid phase can be more readily separated from the gaseous products of CO2 photoreduction, high-purity H2O2 with a concentration up to 0.1 mM was obtained. Confirmed by theoretical calculations and the established energy level diagram, the reductive iron(II) porphyrinates and oxidative Ag(I) clusters within an integrated framework functioned synergistically to achieve artificial photosynthesis. Furthermore, photoluminescence spectroscopy and photoelectrochemical measurements revealed that the robust connection of Ag(I) clusters and iron porphyrinate ligands facilitated efficient charge separation and rapid electron transfer, thereby enhancing the photocatalytic activity.

Integration of Plasmonic Ag(I) Clusters and Fe(II) Porphyrinates into Metal–Organic Frameworks for Efficient Photocatalytic CO2 Reduction Coupling with Photosynthesis of Pure H2O2

AbstractEfficient photocatalytic CO2 reduction coupled with the photosynthesis of pure H2O2 is a challenging and significant task. Herein, using classical CO2 photoreduction site iron porphyrinate as the linker, Ag(I) clusters were spatially separated and evenly distributed within a new metal–organic framework (MOF), namely Ag27TPyP‐Fe. With water as electron donors, Ag27TPyP‐Fe exhibited remarkable performances in artificial photosynthetic overall reaction with CO yield of 36.5 μmol g−1 h−1 and ca. 100 % selectivity, as well as H2O2 evolution rate of 35.9 μmol g−1 h−1. Since H2O2 in the liquid phase can be more readily separated from the gaseous products of CO2 photoreduction, high‐purity H2O2 with a concentration up to 0.1 mM was obtained. Confirmed by theoretical calculations and the established energy level diagram, the reductive iron(II) porphyrinates and oxidative Ag(I) clusters within an integrated framework functioned synergistically to achieve artificial photosynthesis. Furthermore, photoluminescence spectroscopy and photoelectrochemical measurements revealed that the robust connection of Ag(I) clusters and iron porphyrinate ligands facilitated efficient charge separation and rapid electron transfer, thereby enhancing the photocatalytic activity.

Optimizing Adsorption‐Redox Sites and Charge Transfer of Ternary Polymer Photocatalyst with P─N Linkage for CO2 Conversion Coupled with Antibiotics Removal

AbstractThe rational design of bifunctional photocatalysts with high adsorption and enrichment characteristics and excellent photocatalytic redox activity is an effective way to address environmental pollution and energy shortage crisis. In this study, cyclophosphazene‐derived porous organic polymer (PCPD) microspheres with P─N linkage are coated with graphene oxide (GO) and loaded with Ag0 nanoparticles (NPs) to prepare covalently bonded xAg‐rGO/PCPD composites. The catalyst with the highest specific surface area (denoted as 2.5Ag‐rGO/PCPD) shows excellent adsorption capacity for fluoroquinolone antibiotics, removing 96.2% of ciprofloxacin (CIP) through adsorption. By applying the catalyst with the best photocatalytic redox activity (denoted as 5Ag‐rGO/PCPD), 82.97% of refractory sulfonamide antibiotics are removed through adsorption‐degradation, and 635.3 µmol g−1 of CO and 162.3 µmol g−1 of CH4 are generated as products of CO2 photoreduction alone. Among the co‐catalytic systems, the highest CO yield of 9.16 µmol g−1 is obtained by coupling CO2 reduction with levofloxacin (LVX) degradation to harness the electron‐donating power of the pollutant molecule. This study is expected to provide useful guidance for the rational design of bifunctional photocatalysts.

Boosted Sacrificial-Agent-Free Selective Photoreduction of CO2 to CH3OH by Rhenium Atomically Dispersed on Indium Oxide.

Solar-energy-driven photoreduction of CO2 is promising in alleviating environment burden, but suffers from low efficiency and over-reliance on sacrificial agents. Herein, rhenium (Re) is atomically dispersed in In2O3 to fabricate a 2Re-In2O3 photocatalyst. In sacrificial-agent-free photoreduction of CO2 with H2O, 2Re-In2O3 shows a long-term stable efficiency which is enhanced by 3.5 times than that of pure In2O3 and is also higher than those on Au-In2O3, Ag-In2O3, Cu-In2O3, Ir-In2O3, Ru-In2O3, Rh-In2O3 and Pt-In2O3 photocatalysts. Moreover, carbon-based product of the photoreduction overturns from CO on pure In2O3 to CH3OH on 2Re-In2O3. Re promotes charge separation, H2O dissociation and CO2 activation, thus enhancing photoreduction efficiency of CO2 on 2Re-In2O3. During the photoreduction, CO is a key intermediate. CO prefers to desorption rather than hydrogenation on pure In2O3, as CO binds to pure In2O3 very weakly. Re strengthens the interaction of CO with 2Re-In2O3 by 5.0 times, thus limiting CO desorption but enhancing CO hydrogenation to CH3OH. This could be the origin for photoreduction product overturn from CO on pure In2O3 to CH3OH on 2Re-In2O3. The present work opens a new way to boost sacrificial-agent-free photoreduction of CO2.

Boosted Sacrificial‐Agent‐Free Selective Photoreduction of CO2 to CH3OH by Rhenium Atomically Dispersed on Indium Oxide

AbstractSolar‐energy‐driven photoreduction of CO2 is promising in alleviating environment burden, but suffers from low efficiency and over‐reliance on sacrificial agents. Herein, rhenium (Re) is atomically dispersed in In2O3 to fabricate a 2Re‐In2O3 photocatalyst. In sacrificial‐agent‐free photoreduction of CO2 with H2O, 2Re‐In2O3 shows a long‐term stable efficiency which is enhanced by 3.5 times than that of pure In2O3 and is also higher than those on Au‐In2O3, Ag‐In2O3, Cu‐In2O3, Ir‐In2O3, Ru‐In2O3, Rh‐In2O3 and Pt‐In2O3 photocatalysts. Moreover, carbon‐based product of the photoreduction overturns from CO on pure In2O3 to CH3OH on 2Re‐In2O3. Re promotes charge separation, H2O dissociation and CO2 activation, thus enhancing photoreduction efficiency of CO2 on 2Re‐In2O3. During the photoreduction, CO is a key intermediate. CO prefers to desorption rather than hydrogenation on pure In2O3, as CO binds to pure In2O3 very weakly. Re strengthens the interaction of CO with 2Re‐In2O3 by 5.0 times, thus limiting CO desorption but enhancing CO hydrogenation to CH3OH. This could be the origin for photoreduction product overturn from CO on pure In2O3 to CH3OH on 2Re‐In2O3. The present work opens a new way to boost sacrificial‐agent‐free photoreduction of CO2.

CO2 Photoreduction Product Selectivity with TiO2−Cu Nanocatalysts under Different Reaction Media

AbstractThis study explores photocatalytic conversion of CO2 using TiO2−Cu heterojunctions with different Cu contents and investigates influence of different reaction media on the process efficiency. The use of KOH favored liquid products, especially ethanol. An analysis of H2 production as the main competitive reaction was done. Sodium oxalate led to an increase in H2 evolution by approximately 600 μmol g‐1 compared to pure water, in the presence of CO2 in the reaction medium, but the blank test (without CO2) indicates a lower H2 yield (~136 μmol g−1), which suggests that the competitive reaction with CO2 also plays a role in H2 production. This role was related to the decrease of the initial pH from approximately 8.5 to 5.2, stabilizing at 5.5 at the end of the 6 h reaction. In an environment saturated with N2, the pH increases to 9 and stabilizes at 7.8 at the end of the process. In the presence of acetic acid, both CO and H2 production were suppressed, with a significant increase in the selectivity for methane via cleavage of the acid‘s carbon bond. The findings underscore the importance of optimizing reaction conditions to achieve higher yields of desired products in the photocatalytic conversion of CO2.

Application of ceria materials modified by oxygen vacancies: In photocatalytic process

Cerium-based materials are widely used in various applications such as photocatalytic environmental remediation, CO2 photoreduction and photocatalytic hydrogen production due to their unique optical properties and special oxygen vacancy formation mechanisms. The special external electronic structure of cerium (4f15d16s2f15d16s2), the highly electronic 4f orbital, promotes the formation of oxygen vacancies through Ce4+/Ce3+ conversion, thereby improving the optical properties of the catalyst. Consequently, the application of cerium-based materials in the field of photocatalysis has been of great interest to researchers. In this paper, we briefly review the synthesis of cerium-based photocatalysts and their applications in pollutant removal, CO2 reduction, and hydrogen production, as well as their promising applications.

Construction of Ru Single-Atoms on Ceria to Reform the Products of CO2 Photoreduction.

Highly selective production of CH4 from photocatalytic CO2 reduction is still a great challenge which involves the kinetically unfavorable transfers of 8 protons and 8 electrons. Herein, CeO2 photocatalysts incorporated with isolated Ru single-atoms have been fabricated, which demonstrate dramatically elevated selectivity of CH4 from CO2 reduction. The introduced Ru single-atoms promote carrier separation and accelerate electron transfer, which efficiently enhances the photocatalytic activity. Density functional theory (DFT) calculations and in situ FT-IR analysis manifest that the Ru single-atom active sites play an indispensable role in strengthening the adsorption of *CO intermediate on the catalyst surface and promoting H2O oxidation to generate abundant protons, thus favoring *CO protonation into *CHxO (x = 1, 2, 3) species and final deoxygenation into CH4. This work provides an effective strategy by constructing single-atom active sites to modulate and stabilize the key intermediates of CO2 photoreduction to improve the selectivity of the target products.

Function-oriented bifunctional Mg & MoP modified polymeric carbon nitride for selective photoreduction CO2 to CH4

Constructing photocatalysts with dual-function active sites can coordinate the photogenerated electrons transfer and the adsorption energy of key intermediates, thereby converting CO2 into valuable methane with high efficiency. However, the role that the interfacial position of functional catalysts played in determining the activity and selectivity of CO2 photoreduction remains unclear. Herein, we regulated the action interface and synergistic effect of magnesium nitrate hydroxide and molybdenum phosphide (Mg & MoP) to modify polymeric carbon nitride (PCN), and found the function-oriented Mg-MoP/PCN exhibits superior performance for catalyzing CO2-to-CH4 in pure water, with a rate of 24.45 μmol h−1 g−1 and 95.3 % selectivity. Theoretical and experimental studies reveal that interfacial layer of MoP promotes the evolutionary activity by facilitating the electron transfer while exterior layer of Mg functions as the catalyzing sites to tackle the selectivity challenge by promoting CO2 adsorption and CO* stabilization. The synergistic interaction of function-oriented Mg&MoP realizes selective CH4 evolution with high efficiency via a Z-scheme pathway. The interfacial position of bifunctional catalysts is vital for regulating CO2 photoreduction activity and product selectivity.

Mixed phase anatase nanosheets/brookite nanorods TiO2 photocatalysts for enhanced gas phase CO2 photoreduction and H2 production

CO2 photoreduction and H2 photocatalytic production reactions have been studied on different TiO2 polymorphs (anatase and brookite) engineered with specific nanocrystal shape. Anatase TiO2 materials of nanosheet morphology and brookite TiO2 of nanorod morphology were developed via a hydrothermal synthesis process. Mixed-phase anatase/brookite TiO2 materials of the above extreme cases were also developed, controlling the phase composition. The materials were fully characterized by a variety of techniques including structural, morphological, textural and electronic properties characterization. N2 physisorption analysis and CO2 adsorption isotherms have shown that minimum amount of brookite phase (i.e. ca. 7 wt%) in the final material improved the textural properties and the CO2 uptake ability. Electron paramagnetic spectroscopy (EPR) provided evidences for improvements in the formation and availability of photogenerated electrons in the mixed-phase materials. CO2 photoreduction was increased by ca. 220% in the optimized mixed-phase anatase/brookite TiO2. Photocatalytic H2 production rates were also improved by ca. 140%. The results in the present study have shown that the TiO2 phase as well as the amount of each TiO2 polymorph plays vital role in photocatalytic efficiency and that the photocatalytic improvement depends greatly on the specific reactions. The new insights provided herein would be of interest for studied focusing on materials shape engineering and phase composition and their effect on activity.

The influence of the addition of carbon spheres on photoactivity of TiO2 and ZnO in CO2 reduction process

The development of an effective photocatalyst for CO2 reduction is currently being addressed by many scientists. This study concerns the influence of the addition of carbon spheres (CS) on photoactivity of TiO2 and ZnO. The photocatalysts were tested in a liquid phase system in an alkaline environment. The suspensions of the tested materials were irradiated with UV–Vis light for 6 h. Then, the amount of the obtained products in the gas phase was analysed by gas chromatography. The identified products of CO2 photoreduction were hydrogen, carbon monoxide, and methane. Based on the results, it was found that CS/TiO2 and CS/ZnO showed similar activity in carbon dioxide reduction processes, however, more product amounts were obtained in experiments with the use of CS/TiO2 materials. The addition of carbon spheres to titanium dioxide improved its activity in carbon monoxide production. The maximum photoactivity of CS/TiO2 was observed for the addition of 0.1 g of CS. On the other hand, in the case of CS/ZnO materials, carbon spheres did not positively affect their performance. Nevertheless, their activity increased with the CS amount.

Designing reliable and accurate isotope-tracer experiments for CO2 photoreduction

The photoreduction of carbon dioxide (CO2) into renewable synthetic fuels is an attractive approach for generating alternative energy feedstocks that may compete with and eventually displace fossil fuels. However, it is challenging to accurately trace the products of CO2 photoreduction on account of the poor conversion efficiency of these reactions and the imperceptible introduced carbon contamination. Isotope-tracing experiments have been used to solve this problem, but they frequently yield false-positive results because of improper experimental execution and, in some cases, insufficient rigor. Thus, it is imperative that accurate and effective strategies for evaluating various potential products of CO2 photoreduction are developed for the field. Herein, we experimentally demonstrate that the contemporary approach toward isotope-tracing experiments in CO2 photoreduction is not necessarily rigorous. Several examples of where pitfalls and misunderstandings arise, consequently making isotope product traceability difficult, are demonstrated. Further, we develop and describe standard guidelines for isotope-tracing experiments in CO2 photoreduction reactions and then verify the procedure using some reported photoreduction systems.

BiOCl Nanoflowers with High Levels of Oxygen Vacancy for Photocatalytic CO2 Reduction

CO2 photoreduction products, such as CO and CH4, have the potential to be further processed into valuable products and fuels, making this process a promising, environmentally friendly, and economically viable energy conversion technology. In this study, uniform BiOCl hierarchical nanoflowers with tunable thickness and abundant oxygen vacancies (OVs) were synthesized using a poly(vinylpyrrolidone)/ethylene glycol-assisted self-assembly method. The OV-rich BiOCl nanoflower (BiOCl-3) showed a 4-fold increase in photocatalytic conversion of CO2 to CO compared to BiOCl nanosheets (BiOCl-1). Density functional theory (DFT) calculations and energy band analysis reveal anisotropy in the CO2 reduction activity across different crystal facets, and the morphology can affect both the conduction band (CB) and band gap, resulting in a more negative CB edge for BiOCl compared to the reduction potential of CO2 photoreduction to CO. This work provides a comprehensive analysis and explanation of the OV-rich BiOCl photocatalytic CO2 reduction from both experimental and theoretical perspectives.

Mercury photoreduction and photooxidation kinetics in estuarine water: Effects of salinity and dissolved organic matter

Net photoreduction of divalent mercury (Hg(II)) and volatilization of photoreduction products (i.e., elemental mercury (Hg(0))/dissolved gaseous mercury (DGM)) is a mechanism by which mercury burdens in ecosystems are lessened. The effects of salinity on mercury photoreactions were investigated while controlling the concentration of DOM (>1 kDa) using natural surface water from the tidal Jijuktu'kwejk (Cornwallis River) and processed with a tangential ultrafiltration-dilution technique. Pseudo first-order rate constants in estuarine water salinity dilutions ranged between 0.22 h−1 and 0.73 h−1. The amount of mercury available for photoreduction (Hg(II)RED) ranged between 67.2 and 265.9 pg. Pseudo first-order rate constants decreased with increasing salinity treatments (0–13.5 g L−1), with minimal change in rate constants occurring in higher salinity treatments (e.g. 20.3 or 26.8 g L−1), while Hg(II)RED increased with salinity. In lower salinity treatments, DOM was more photoactive. Taken together, results suggest changes in the mercury photoreduction mechanism from DOM-bound electron transfer to photochemically produced secondary reduction products with increasing salinity. Experiments examining photooxidation showed decreases in Hg (0) with longer exposure time, suggesting transformation of Hg(II)RED into a non-reducible form. This research highlights the importance of salinity and DOM interactions in estuarine surface water and their effects on mercury photochemistry.

Overturning photoreduction product of CO2 by defect- and COOH-functionalized multi-wall carbon nanotubes

We functionalize MWCNTs with defects and COOH groups to form MWCNTs30 through a novel discharge process. In the photoreduction of CO2 with pure H2O in the absence of sacrificial reagent, with CdS as light absorber, MWCNTs30 triggers a selective CH3OH production, with a CH3OH selectivity of 100% and an internal quantum efficiency of 3.9%, but CO is the only C-based product by using pristine MWCNTs without functionalization. The defects on MWCNTs30 are active sites for enhancing CO2 adsorption, H2O dissociation to produce H and H transfer to CO2, thus boosting CO2 hydrogenation to CH3OH. The COOH groups on MWCNTs30 provide H for promoting CO2 hydrogenation to CH3OH. The multiple roles of defects and COOH groups overturn the photoreduction product from CO to CH3OH. The results open a new way to achieve more efficient photoreduction of CO2 in the absence of noble metal and sacrificial reagent.

Tandem utilization of CO2 photoreduction products for the carbonylation of aryl iodides

Photocatalytic CO2 reduction reaction has been developed as an effective strategy to convert CO2 into reusable chemicals. However, the reduction products of this reaction are often of low utilization value. Herein, we effectively connect photocatalytic CO2 reduction and amino carbonylation reactions in series to reconvert inexpensive photoreduction product CO into value-added and easily isolated fine chemicals. In this tandem transformation system, we synthesize an efficient photocatalyst, NNU-55-Ni, which is transformed into nanosheets (NNU-55-Ni-NS) in situ to improve the photocatalytic CO2-to-CO activity significantly. After that, CO serving as reactant is further reconverted into organic molecules through the coupled carbonylation reactions. Especially in the carbonylation reaction of diethyltoluamide synthesis, CO conversion reaches up to 85%. Meanwhile, this tandem transformation also provides a simple and low-cost method for the 13C isotopically labeled organic molecules. This work represents an important and feasible pathway for the subsequent separation and application of CO2 photoreduction product.

Emerging Strategies for CO2 Photoreduction to CH4: From Experimental to Data‐Driven Design

AbstractThe solar‐energy‐driven photoreduction of CO2 has recently emerged as a promising approach to directly transform CO2 into valuable energy sources under mild conditions. As a clean‐burning fuel and drop‐in replacement for natural gas, CH4 is an ideal product of CO2 photoreduction, but the development of highly active and selective semiconductor‐based photocatalysts for this important transformation remains challenging. Hence, significant efforts have been made in the search for active, selective, stable, and sustainable photocatalysts. In this review, recent applications of cutting‐edge experimental and computational materials design strategies toward the discovery of novel catalysts for CO2 photocatalytic conversion to CH4 are systematically summarized. First, insights into effective experimental catalyst engineering strategies, including heterojunctions, defect engineering, cocatalysts, surface modification, facet engineering, and single atoms, are presented. Then, data‐driven photocatalyst design spanning density functional theory (DFT) simulations, high‐throughput computational screening, and machine learning (ML) is presented through a step‐by‐step introduction. The combination of DFT, ML, and experiments is emphasized as a powerful solution for accelerating the discovery of novel catalysts for photocatalytic reduction of CO2. Last, challenges and perspectives concerning the interplay between experiments and data‐driven rational design strategies for the industrialization of large‐scale CO2 photoreduction technologies are described.

Removing trace chromium from high concentration vanadium solution by photoreduction deposition with Ti–Zr solid solution

The preparation of ultrahigh-purity vanadium (>99.99 wt%) requires the removal of trace amounts of chromium, but economical vanadium purification is difficult to achieve using crude vanadium mother liquors (>98 wt%) because of the similar properties of V(V) and Cr(IV) ions. In this study, a Ti–Zr solid solution was used for the deep purification of high-concentration ammonium polyvanadate by removing trace chromium using photocatalytic reduction process. The results show that V(V) and Cr(VI) are competitively adsorbed and photoreduced, but V(V) adsorption is preferred and occurs more rapidly than that of Cr(VI). However, after the photoreduction product of V(V), V(IV) is desorbed, whereas after that of Cr(VI), Cr(III) is deposited on the photocatalyst, achieving the separation of vanadium and chromium. The 2 h removal efficiency of chromium exceeds 80%, and the chromium content in the obtained vanadium is less than 0.04 wt%. After precipitation, the chromium content in the obtained ammonium metavanadate is less than 0.001 wt%, and the purity of the final V2O5 product exceeds 99.99%, which meets the requirement for ultrahigh-purity vanadium products. The used photocatalyst can be regenerated and reused with stable performance. This work provides a reference method for ultrahigh-purity vanadium production and an example of the industrial application of the photoreduction process.

Bi2O2CO3/red phosphorus S-scheme heterojunction for H2 evolution and Cr(VI) reduction

Red phosphorus (RP) has a suitable energy band structure and excellent photocatalytic properties. However, there are some problems, such as low quantum efficiency and serious photogenerated electron-hole recombination. The S-scheme heterostructure shows great potential in facilitating the separation and transfer of photogenerated carriers and obtaining strong photo-redox ability. Herein, hydrothermally treated red phosphorus (HRP) was combined with Bi2O2CO3 to construct Bi2O2CO3/HRP S-scheme heterojunction composite. The Bi2O2CO3 content was optimized, and the 5 %Bi2O2CO3/HRP composite obtained at 5 %Bi2O2CO3 mass fraction exhibited the strongest photoreduction ability. The Cr(VI) photoreduction and photolytic hydrogen production rates were as high as 0.22 min−1 and 157.2 μmol •h−1, which were 7.3 and 3.0 times higher than those of HRP, respectively. The promoted photocatalytic activity could be attributed to the formation of S-scheme heterojunctions, which accelerated the separation and transfer of useful photogenerated electron-hole pairs, while enhancing the recombination of relatively useless photogenerated electron-hole pairs, thereby resulting in the highest photocurrent density (17.3 μA/cm2) of the 5 %Bi2O2CO3/HRP composite, which was 1.6 and 4.3 times higher than pure Bi2O2CO3 (10.5 μA/cm2) and pure HRP (4.0 μA/cm2), respectively. This work would provide an advanced approach to enhance the photocatalytic activity of RP.

Novel Dyadic Amorphous-Crystalline Nano-Titania Hybrids for Sacrifiers-Stored Photocatalysis

Sacrifiers-promoted photocatalysis is a useful way to achieve high efficiency photoreduction and photocatalytic hydrogen production for photocatalysts of weak reductive power such as TiO2. Herein we report a new method to fabricate a unique dyadic hybrid consisting of closely compacted crystalline (anatase) and titanium glycerolate (TiG)-derived organic group-retained amorphous nanoparticles to validate adsorption-stored sacrifiers-promoted photocatalysis instead of using sacrifiers in bulk solution. It was found that ascorbic acid (AA)-modified TiG prepared at a small fraction of glycerol, characterized by peculiar cocoon/open nanocontainer-type morphologies, varieties of oxygen containing groups, and remarkably high specific surface area, is suitable for precursing such hybrids. AA can change crystallization processes and particle morphologies by terminating chain linkages in TiG structure, which increases porosity and brings about visible light responsive photocatalysis for the dyadic hybrid. Benefiting from good adsorption affinity to organic sacrifiers, the sacrifier-prestored hybrid can catalyze significantly enhanced photoreduction with good reproducibility toward dye molecules via the synergy of sacrifier enrichment and photocatalysis. AA modified TiG also exhibits good self-reducibility enabling pre-loading of highly dispersed and localized platinum nanoparticles, and the resulted dyadic hybrid facilitates photocatalytic hydrogen production of extremely higher turn-off frequency and better impurities interference-resistivity compared to the P25-based commercial catalyst.