Water Oxidation Catalysts Research Articles

Closing Kok’s cycle of nature’s water oxidation catalysis

The Mn4CaO5(6) cluster in photosystem II catalyzes water splitting through the Si state cycle (i = 0–4). Molecular O2 is formed and the natural catalyst is reset during the final S3 → (S4) → S0 transition. Only recently experimental breakthroughs have emerged for this transition but without explicit information on the S0-state reconstitution, thus the progression after O2 release remains elusive. In this report, our molecular dynamics simulations combined with density functional calculations suggest a likely missing link for closing the cycle, i.e., restoring the first catalytic state. Specifically, the formation of closed-cubane intermediates with all hexa-coordinate Mn is observed, which would undergo proton release, water dissociation, and ligand transfer to produce the open-cubane structure of the S0 state. Thereby, we theoretically identify the previously unknown structural isomerism in the S0 state that acts as the origin of the proposed structural flexibility prevailing in the cycle, which may be functionally important for nature’s water oxidation catalysis.

Promoted surface reconstruction of pentlandite via phosphorus-doping for enhanced oxygen evolution reaction

The pentlandite Fe5Ni4S8(abbreviated as FNS) is not efficient for water splitting because of its inferior performance for the oxygen evolution reaction (OER). This issue originates from the low activity and instability of FNS during the OER process but can be solved through appropriate doping. Herein, a P-doping strategy based on annealing in the presence of NaH2PO2as a phosphorus source upstream was employed on FNS to enhance its activity and stability toward OER. The results demonstrated fine-tuned electronic structures of Fe and Ni in FNS through P-doping, resulting in suppressed Fe leaching,improved electrical conductivity of FNS, and easier formation of NiOOH on the surface of the catalyst. In turn, these features enhanced the OER activity and stability. The optimal P-doped FNS catalyst FNSP-40 exhibited a 4-fold greater electrochemical surface area compared to that of FNS, accompanied by an overpotential of 235 mV at 10 mA cm−2. The optimized FNSP-40 catalyst was used as an anode, and platinum-decorated FNS was used as a cathode. This combination demonstrated an electrolysis performance with a cell voltage of 1.57 V, reaching a current density of 100 mA cm−2,which indicates efficient operation. The advantages of P-doping engineering were also verified in simulated seawater with enhanced OER performance. Overall, the proposed strategy looks promising for the fabrication of pentlandite-structured catalysts for efficient alkaline water and seawater oxidation.

Synergistic doping of Iron and selenium on nickel hydroxide nitrate nanoarrays-derived as an efficient electrocatalyst for overall water splitting

The fabrication of highly efficient and stable catalysts for water oxidation is important to promote the development of the hydrogen fuel industry. In this study, dual-element-doped two-dimensional nickel hydroxide nitrate nanoarrays (NiHN) self-supported on nickel foam were fabricated via a facile electrodeposition process. The results demonstrated that Fe and Se were incorporated into the nickel hydroxide structure. The binder-free FeSe-NiHN catalyst exhibited low overpotentials of 129 and 250 mV at 10 mA cm−2 for the hydrogen evolution reaction and at 100 mA cm−2 for the oxygen evolution reaction in 1 M KOH media, respectively. Furthermore, a durability test conducted at 70 mA cm−2 for 28 h showed no evident degradation of the catalyst activity, verifying its exceptional stability. Thus, FeSe-NiHN is a potential water splitting electrocatalyst for inexpensive hydrogen production.

Stabilizing atomic Ru species in conjugated sp2 carbon-linked covalent organic framework for acidic water oxidation

Suppressing the kinetically favorable lattice oxygen oxidation mechanism pathway and triggering the adsorbate evolution mechanism pathway at the expense of activity are the state-of-the-art strategies for Ru-based electrocatalysts toward acidic water oxidation. Herein, atomically dispersed Ru species are anchored into an acidic stable vinyl-linked 2D covalent organic framework with unique crossed π-conjugation, termed as COF-205-Ru. The crossed π-conjugated structure of COF-205-Ru not only suppresses the dissolution of Ru through strong Ru-N motifs, but also reduces the oxidation state of Ru by multiple π-conjugations, thereby activating the oxygen coordinated to Ru and stabilizing the oxygen vacancies during oxygen evolution process. Experimental results including X-ray absorption spectroscopy, in situ Raman spectroscopy, in situ powder X-ray diffraction patterns, and theoretical calculations unveil the activated oxygen with elevated energy level of O 2p band, decreased oxygen vacancy formation energy, promoted electrochemical stability, and significantly reduced energy barrier of potential determining step for acidic water oxidation. Consequently, the obtained COF-205-Ru displays a high mass activity with 2659.3 A g−1, which is 32-fold higher than the commercial RuO2, and retains long-term durability of over 280 h. This work provides a strategy to simultaneously promote the stability and activity of Ru-based catalysts for acidic water oxidation.

Nest-Scheme RuIrLa Nanocrystals by NP-to-NP Oriented Assembly: Coherent Strain Fields-Driven Band Structure Splitting for Efficient Acidic Water Oxidation.

Atomic substructure engineering provides new opportunities for the designing newly and efficient catalysts with diverse atom ensembles, trimmed electron bands, and way-out coordination environments, creating unique contributing to concertedly catalyze water oxidation, which is of great significance for proton exchange membrane water electrolysis (PEMWE). Herein, nest-scheme RuIrLa nanocrystals with dense coherent interfaces as built-in substructures are firstly fabricated by using commercial ZnO particles as acid-removable templates, through a La-stabilized coherent epitaxial growth of nanoparticles (NPs). The obtained nests exhibit a low overpotential of 198mV at 10mA cm-2, and the RuIrLa||Pt/C module equipped in PEMWE operates stably at a cell voltage potential of 1.69V at 100mA cm-2 in 0.5M H2SO4 for 55h, which is far beyond the current IrO2||Pt/C. Within the nests, the position at the interface shows high tensile/compressive strain, significantly reducing the OER activation energy. More importantly, the La termination-stabilized coherent interfaces within the nests creates a unique self-healing process for the outstanding long-term stability. This work provides a promising substructure engineering to develop efficient catalysts with abundant substructures, such as coherent interfaces, dislocations, or grain boundaries, thereby realizing concerted improvement of activity and durability toward water oxidation.

Mineralization of clofibric acid by persulfate-promoted catalytic subcritical water oxidation process using CoFe2O4@SiO2 catalyst

The design and use of innovative treatment processes are very important in preventing the possible toxic effects of organic pollutants in aquatic environments. One of these methods is the subcritical water oxidation method, which has been used recently. In the current study, the mineralization of clofibric acid (CFA) was carried out under more effective and mild conditions using persulfate (PS) as an oxidant and CoFe2O4@SiO2 catalyst by the subcritical water oxidation (sub-CWO) process. Characterization of the synthesized catalyst was performed through XRD, FTIR, TEM and SEM–EDS analyses. In the CFA oxidation with persulfate-promoted catalytic Sub-CWO process, optimum working conditions was determined as 15 mM PS, 40 min, 383 K, and 0.3 g L−1 catalyst dosage using the response surface method and Box–Behnken design. The catalyst's efficiency remained relatively stable after three cycles under optimal conditions, resulting in a 97% total organic carbon (TOC) removal. Decomposition products were determined and a degradation mechanism was proposed.

Dual-site catalysts for water oxidation: A detailed study

Water oxidation stands as a pivotal half-reaction in the complete water-splitting equation, essential for green hydrogen production. Dual-site catalysts, recognized for their active sites, emerge as a potential solution in this domain. Non-noble metal materials, employed in such catalysts, present an auspicious research frontier. However, the underlying mechanisms warrant further clarity. This review concentrates on the fundamental mechanisms and performance of classical dual-site catalysts in water oxidation, aiming to offer newcomers a lucid conceptual framework.

Efficiency Conceptualization Model: A Theoretical Method for Predicting the Turnover of Catalysts.

In recent times, the theoretical prediction of catalytic efficiency is of utmost urgency. With the advent of density functional theory (DFT), reliable computations can delineate a quantitative aspect of the study. To this state-of-the-art approach, valuable incorporation would be a tool that can acknowledge the efficiency of a catalyst. In the current work, we developed the efficiency conceptualization model (ECM) that utilizes the quantum mechanical tool to achieve efficiency in terms of turnover frequency (TOF). Twenty-six experimentally designed transition metal (TM) water oxidation catalysts were chosen under similar experimental conditions of temperature, pressure, and pH to execute the same. The computations conclude that the Fe-based [Fe(OTf)2(Me2Pytacn)] (MWOC-17) is a highly active catalyst and, therefore, can endure for more time in the catalytic cycle. Our results conclude that the Ir-based catalysts [Cp*Ir(κ2-N,O)X] with MWOC-23: X=Cl; and MWOC-24: X=NO3 report the highest computed turnover numbers (TONs), of 406 and 490 against the highest experimental TONs, of 1200 and 2000 respectively, whereas the Co-based [Co(12-TMC)]2+ (MWOC-19) has the lowest TONs ( =19, τexperimental TON=16) among the chosen catalysts and thereby successful in corroborating the previous experimental results.

Structural basis for an early stage of the photosystem II repair cycle in Chlamydomonas reinhardtii

Photosystem II (PSII) catalyzes water oxidation and plastoquinone reduction by utilizing light energy. It is highly susceptible to photodamage under high-light conditions and the damaged PSII needs to be restored through a process known as the PSII repair cycle. The detailed molecular mechanism underlying the PSII repair process remains mostly elusive. Here, we report biochemical and structural features of a PSII-repair intermediate complex, likely arrested at an early stage of the PSII repair process in the green alga Chlamydomonas reinhardtii. The complex contains three protein factors associated with a damaged PSII core, namely Thylakoid Enriched Factor 14 (TEF14), Photosystem II Repair Factor 1 (PRF1), and Photosystem II Repair Factor 2 (PRF2). TEF14, PRF1 and PRF2 may facilitate the release of the manganese-stabilizing protein PsbO, disassembly of peripheral light-harvesting complexes from PSII and blockage of the QB site, respectively. Moreover, an α-tocopherol quinone molecule is located adjacent to the heme group of cytochrome b559, potentially fulfilling a photoprotective role by preventing the generation of reactive oxygen species.

In Situ Tracking of Water Oxidation Generated Nanoscale Dynamics in Layered Double Hydroxides Nanosheets.

Layered double hydroxides (LDHs) are potential catalysts for water oxidation, and it is recognized that they undergo dynamic evolution during the operation. However, little is known about the interfacial behaviors at the nanoscale under working conditions nor the underlying effects on electrocatalytic performance. Herein, using electrochemical atomic force microscopy, we in situ visualize the heterogeneous evolution of LDH nanosheets during oxygen evolution reaction (OER). By further combining density functional theory calculations, we elucidate the origin of the heterogeneous dynamics and their impact on the OER efficiency. Our findings demonstrate that NiCo LDHs transform to the catalytically active NiCoOx(OH)2-x phase during OER, and the redox transition between is accompanied by compressive and tensile strain, leading to in-plane contraction and reversible expansion of the nanosheets. Nonisotropic strain and out-of-plane strain relaxation due to defects and interparticle interactions result in cracking and wrinkling in the nanostructure, which is responsible for the partial activation and long-term deterioration of LDH electrocatalysts toward the OER. With this knowledge, we suggest and validate that engineering defects can precisely tune these dynamic behaviors, improving the OER activity and stability among LDH-based electrocatalysts.

Photochemical Oxidation of Substrate Water Analogs and Halides by Photosystem II

AbstractPhotosystem II (PSII) is a multi‐subunit protein‐pigment complex with diverse redox‐active cofactors, which enabled the biological availability of O2 on Earth. The substrate specificity and the underlying redox chemistry of the Mn4CaO5 catalytic center are investigated using alternate substrates such as small molecules (ammonia and methanol) and halides (Cl‐, Br‐, I‐) instead of the natural substrate water. Changes in the kinetic profiles of steady‐state O2 evolution and of dichlorophenolindophenol (DCIP) photochemical reduction by PSII as well as the detection of modified sites by proteomic analysis implied the possibility of alternate substrate photooxidation. Of particular interest is the role of two chlorides bound close to the putative water channels in the native system. The mutation of D2‐K317 to alanine is believed to impair the binding of a catalytically relevant chloride, eliminating the chloride requirement for water oxidation catalysis. The efficiency of small molecule photooxidation by the OEC is enhanced by the mutated D2‐K317A PSII complex without the competition from chloride. These results provide insight into the role of bound chloride in native PSII as a filter for enhancing the selectivity of water oxidation. The design principles for PSII may be extended to new strategies for developing highly selective catalysts.

Exploring the Water Oxidation Catalytic Activity of a Mn-Based Magnetic Metal-Organic Framework: The Role of Proton Conductivity and Oxygen Evolution Reaction Overpotential.

The present work evaluates the water oxidation catalytic activity of a Mn-based metal-organic framework (MOF), which we envisioned to reduce the oxygen evolution reaction (OER) overpotential because of its high electrical conductivity, facilitated by solvent-encapsulated structural features. The presence of Mn centers induces interesting magnetic features in the MOF, which exhibits impressive cryogenic magnetic refrigeration with a ΔSM value of 29.94 J kg-1 K-1 for a field change of ΔH = 5T at 2.3 K. To the best of our knowledge, the ΔSM value of the current system ranked the highest position among the published examples. The crystal structure aligns perfectly with the thematic expectations and features as many as ten metal-coordinated water molecules, forming an extensive web of a hydrogen-bonded network while facing toward the porous channel filled with another set of much-anticipated entrapped lattice water molecules. Such structural features are expected to manifest high proton conductivity, and detailed investigation indeed yields the best value for the system at 1.57 × 10-4 S/cm at 95% humidity and 85 °C. In order to evaluate the thematic notion of a one-to-one relationship between OER and improved electrical conductivity, extensive electrocatalytic water splitting (WS) investigations were carried out. The final results show highly encouraging WS ability of the Mn-MOF, showing the electrocatalytic surface area value of the active species as 0.0686 F/g with a turnover frequency value of 0.043 [(mol. O2) (mol. Mn-MOF)-1 s-1]. Another fascinating aspect of the current communication is the excellent synergy observed between the experimental WS outcomes and the corresponding theoretical data calculated using density functional theory (DFT). Consequently, a plausible mechanism of the overall OER and the role of the Mn-MOF as a water oxidation catalyst, along with the importance of water molecules, have also been derived from the theoretical calculations using DFT.

Photocatalytic water oxidation by iron and copper phthalocyanine complexes immobilized on Fe3O4@SiO2@TiO2 under visible light irradiation

In this research, the heterogeneous catalysts of Fe3O4@SiO@TiO‐FePc and Fe3O4@SiO@TiO‐ CuPcN (FePc = iron (II) phthalocyanine and CuPcN = copper (II) tetraazaphthalocyanine), termed respectively as nanocomposites 1 and 2, were prepared by immobilizing the FePc and CuPcN complexes on the Fe3O4@SiO@TiO surface and used for the photocatalytic water oxidation reaction. Since phthalocyanine complexes have received very little attention as photocatalysts for water oxidation, the advantage of the synthesized photocatalyst owes to the ability of the phthalocyanine complex grafted on the titanium substrate to oxidize water in the photocatalytic reaction. The prepared nanocomposites were then studied by diffraction (XRD), scanning electron microscopy (SEM), energy‐dispersive X‐ray (EDX), Fourier transform infrared (FT‐IR) spectroscopies, thermal gravimetric analysis (TGA), transmission electron microscopy (TEM), inductively coupled plasma‐optical emission spectroscopy (ICP‐OES), Brunauer–Emmett–Teller (BET) analysis, ultraviolet diffuse reflectance (DRS), and photoluminescence (PL) spectroscopies. The photocatalytic response of water oxidation by nanocomposites 1 and 2 was investigated in the presence of silver nitrate as an electron recipient at ambient temperature. The progress of the water oxidation reaction was monitored with an oxygen meter. The amount of oxygen generated in the presence of nanocomposites 1 and 2 under visible light irradiation was found to be 2.6 and 2.1 mg L−1, respectively. Owing to the existence of magnetic material, these nanocomposites can be effortlessly removed from the response medium with an external magnet. The involved nanocomposites can be used up to three times in catalytic water oxidation reactions with no significant change in their photocatalytic activity.

Exploring the Cooperation of the Redox Non-Innocent Ligand and Di-Cobalt Center for the Water Oxidation Reaction Catalyzed by a Binuclear Complex.

Water oxidation is a crucial reaction in the artificial photosynthesis system. In the present work, density functional calculations were employed to decipher the mechanism of water oxidation catalyzed by a binuclear cobalt complex, which was disclosed to be a homogeneous water oxidation catalyst in pH=7 phosphate buffer. The calculations showed that the catalytic cycle starts from the CoIII,III-OH2 species. Then, a proton-coupled electron transfer followed by a one-electron transfer process leads to the generation of the formal CoIV,IV-OH intermediate. The subsequent PCET produces the active species, namely the formal CoIV,V=O intermediate (4). The oxidation processes mainly occur on the ligand moiety, including the coordinated water moiety, implying a redox non-innocent behavior. Two cobalt centers keep their oxidation states and provide one catalytic center for water activation during the oxidation process. 4 triggers the O-O bond formation via the water nucleophilic attack pathway, in which the phosphate buffer ion functions as the proton acceptor. The O-O bond formation is the rate-limiting step with a calculated total barrier of 17.7 kcal/mol. The last electron oxidation process coupled with an intramolecular electron transfer results in the generation of O2.

Effect of Anchoring Dynamics on Proton-Coupled Electron Transfer in the Ru(bda) Coordination Oligomer on a Graphitic Surface.

The oligomeric ruthenium-based water oxidation catalyst, Ru(bda), is known to be experimentally anchored on graphitic surfaces through CH-π stacking interactions between the auxiliary bda ([2,2'-bipyridine]-6,6'-dicarboxylate) ligand bonded to ruthenium and the hexagonal rings of the surface. This anchoring provides control over their molecular coverage and enables efficient catalysis of water oxidation to dioxygen. The oligomeric nature of the molecule offers multiple anchoring sites at the surface, greatly enhancing the overall stability of the hybrid catalyst-graphitic surface anode through dynamic bonding. However, the impact of this dynamic anchoring on the overall catalytic mechanism is still a topic of debate. In this study, a crucial proton-coupled electron transfer event in the catalytic cycle is investigated using DFT-based molecular dynamics simulations plus metadynamics. The CH-π stacking anchoring plays a critical role not only in stabilizing this hybrid system but also in facilitating the proton-coupled electron transfer event with possible vibronic couplings between the anchoring bonds motion and charge fluctuations at the catalyst - graphitic surface interface. Furthermore, this computational investigation displays the presence of a quartet spin state intermediate that can lead to the experimentally observed and thermodynamically more stable doublet spin state.

Promoting Water Oxidation by Proton Acceptable Groups Surrounding Catalyst on Electrode Surface.

Large-scale hydrogen production through water splitting represents an optimal approach for storing sustainable but intermittent energy sources. However, water oxidation, a complex and sluggish reaction, poses a significant bottleneck for water splitting efficiency. The impact of outer chemical environments on the reaction kinetics of water oxidation catalytic centers remains unexplored. Herein, chemical environment impacts were integrated by featuring methylpyridinium cation group (Py+) around the classic Ru(bpy)(tpy) (bpy = 2,2'-bipyridine, tpy = 2,2':6',2''-terpyridine) water oxidation catalyst on the electrode surface via electrochemical co-polymerization. The presence of Py+ groups could significantly enhance the turnover frequencies of Ru(bpy)(tpy), surpassing the performance of typical proton acceptors such as pyridine and benzoic acid anchored around the catalyst. Mechanistic investigations reveal that the flexible internal proton acceptor anions induced by Py+ around Ru(bpy)(tpy) are more effective than conventionally anchored proton acceptors, which promoted the rate-determining proton transfer process and enhanced the rate of water nucleophilic attack during O-O bond formation. This study may provide a novel perspective on achieving efficient water oxidation systems by integrating cations into the outer chemical environments of catalytic centers.

Charge Transfer Mechanism on a Cobalt-Polyoxometalate-TiO2 Photoanode for Water Oxidation in Acid.

We constructed a photoanode comprising the homogeneous water oxidation catalyst (WOC) Na8K8[Co9(H2O)6(OH)3(HPO4)2(PW9O34)3] (Co9POM) and nanoporous n-type TiO2 photoelectrodes (henceforth "TiO2-Co9POM") by first anchoring the cationic 3-aminopropyltrimethoxysilane (APS) ligand on a metal oxide light absorber, followed by treatment of the metal oxide-APS with a solution of the polyoxometalate WOC. The resulting TiO2-Co9POM photoelectrode exhibits a 3-fold oxygen evolution photocurrent enhancement compared to bare TiO2 in aqueous acidic conditions. Three-element (Co 2p, W 4f, and O 1s) X-ray photoelectron spectroscopy and Raman spectroscopy studies before and after use indicate that surface-bound Co9POM retains its structural integrity throughout all photoelectrochemical water oxidation studies reported here. Extensive charge-transfer mechanistic studies by photoelectrochemical techniques and transient absorption spectroscopy elucidate that Co9POM serves as an efficient WOC, extracting photogenerated holes from TiO2 on the picosecond time scale. This is the first comprehensive mechanistic investigation elucidating the roles of polyoxometalates in POM-photoelectrode hybrid oxygen evolution reaction systems.

Role of Intragap States in Sensitized Sb-Doped Tin Oxide Photoanodes for Solar Fuels Production.

In view of developing photoelectrosynthetic cells which are able to store solar energy in chemical bonds, water splitting is usually the reaction of choice when targeting hydrogen production. However, alternative approaches can be considered, aimed at substituting the anodic reaction of water oxidation with more commercially capitalizable oxidations. Among them, the production of bromine from bromide ions was investigated long back in the 1980s by Texas Instruments. Herein we present optimized perylene-diimide (PDI)-sensitized antimony-doped tin oxide (ATO) photoanodes enabling the photoinduced HBr splitting with >4 mA/cm2 photocurrent densities under 0.1 W/cm2 AM1.5G illumination and 91 ± 3% faradaic efficiencies for bromine production. These remarkable results, among the best currently reported for the photoelectrochemical Br- oxidation by dye sensitized photoanodes, are strongly related to the occupancy extent of ATO's intragap (IG) states, generated upon Sb-doping, as demonstrated by comparing their performances with PDI-sensitized analogues on both undoped SnO2- and TiO2-passivated ATO scaffolds by means of (spectro)electrochemistry and electrochemical impedance spectroscopy. The architecture of the ATO-PDI photoanodic assembly was further modified via the introduction of a molecular iridium-based water oxidation catalyst, thus proving the versatility of the proposed hybrid interfaces as photoanodic platforms for photoinduced oxidations in PEC devices.

Rational Design of Improved Ru Containing Fe-Based Metal-Organic Framework (MOF) Photoanode for Artificial Photosynthesis.

Metal-Organic Frameworks (MOFs) recently emerged as a new platform for the realization of integrated devices for artificial photosynthesis. However, there remain few demonstrations of rational tuning of such devices for improved performance. Here, a fast molecular water oxidation catalyst working via water nucleophilic attack is integrated into the MOF MIL-142, wherein Fe3O nodes absorb visible light, leading to charge separation. Materials are characterized by a range of structural and spectroscopic techniques. New, [Ru(tpy)(Qc)(H2O)]+ (tpy = 2,2':6',2″-terpyridine and Qc = 8-quinolinecarboxylate)-doped Fe MIL-142 achieved a high photocurrent (1.6 × 10-3 A·cm-2) in photo-electrocatalytic water splitting at pH = 1. Unassisted photocatalytic H2 evolution is also reported with Pt as the co-catalyst (4.8 µmol g-1 min-1). The high activity of this new system enables hydrogen gas capture from an easy-to-manufacture, scaled-up prototype utilizing MOF deposited on FTO glass as a photoanode. These findings provide insights for the development of MOF-based light-driven water-splitting assemblies utilizing a minimal amount of precious metals and Fe-based photosensitizers.

Covalent graft of Polypyridineruthenium(II) Complex-ZnTPP dyad with fullerol and immobilization onto TiO2 for enhanced photoassisted water oxidation activity

The covalent linkage of the light-harvester with the water oxidation catalyst is an effective way to construct heterogeneous catalysts with both light harvesting ability and catalytic oxygen evolution activity, and remains a challenge for simulated photosynthesis systems. Herein, two heterogeneous composite catalysts of ZnTPPtpyRubpyPHFTiO2 and ZnTPPtpyRubpyTiO2, with both the light harvesting capability and the catalytic water oxidation (CWE) performance, were successfully designed and prepared, and were fully characterized. Research indicated that the transfer mode of the photo-generated carrier for the two photo-assisted heterogeneous catalysts follows the type II mechanism, and the photo-generated holes promote the CWE activity. Compared to the dark condition (with TOF values of 42.3 and 41.8, respectively), ZnTPPtpyRubpyPHFTiO2 and ZnTPPtpyRubpyTiO2 exhibit superior CWE activity and efficiency in the illumination condition (with TOF values of 120 and 48.31, respectively). Fullerol, playing the role of an electron acceptor and an electron-pool, promotes charge separation and electron storage, which leads to a better suppression in charge recombination and enhancement in charge injection for ZnTPPtpyRubpyPHFTiO2. Therefore, ZnTPPtpyRubpyPHFTiO2 demonstrates a significantly improved catalytic activity in the illumination condition with a much higher TOF value compared to that of ZnTPPtpyRubpyTiO2.