Photocatalytic Water Splitting Activity Research Articles

Computational study of hydrostatic pressure effect on MgSiO3 perovskite oxide for photocatalytic water splitting application

Despite the challenges of developing efficient photocatalysts for water splitting, we demonstrate that MgSiO3 perovskite oxide, under applied external stress, significantly enhances photocatalytic activity. The use of earth-abundant and low-cost photocatalysts for high-efficiency photocatalytic water splitting is extremely important. Using density functional (DFT) calculations, we present increased photocatalytic water splitting activity of MgSiO3 perovskite oxide by applying external stress. Our findings indicate that raising the concentrations of pressure can lower the lattice constants and volume of MgSiO3. An anisotropic elastic material with high stiffness that changes from brittle to ductile at high pressure (10–30 GPa). It is stable under various circumstances owing to its high Debye temperature, thermal conductivity, and melting temperature, all of which are thermodynamic properties. MgSiO₃ is an indirect bandgap (Γ →R) p-type semiconductor with a band gap energy is 2.627 eV at 0 GPa. However, the band gap energies increase as enhanced stress is confirmed by its electronic characteristics, making it appropriate for photocatalytic water-splitting applications. Strong anisotropy, effective light absorption, and reflective properties were revealed by optical investigations, which bode well for photocatalytic applications. Moreover, the optical conductivity suggests its potential for light amplification by showing a gain behavior in the visible light region. Crucially, because of its advantageous band-edge placements, MgSiO₃ shows great promise for photocatalytic water-splitting applications. This work paves the path for more investigation into effective water-splitting technologies by demonstrating the multidimensional properties and novel and inventive nature of MgSiO3 under high pressure, as well as by demonstrating its feasibility for a variety of photocatalytic applications.

All-solid-state red phosphorus/RGO/WO3 Z-scheme heterostructure for photocatalytic overall water splitting

Red phosphorus’s (Red P) photocatalytic overall water splitting activity is limited by rapid charge recombination. In this case, Red P/RGO/WO3, an all-solid-state Z-scheme heterostructure, was created by simply dispersing, mixing, and heating Red P, WO3, and graphene oxide (GO). Among them, Reduced GO (RGO) facilitated the Z-scheme charge transmission between Red P and WO3. Achieving the space separation between electrons stored in Red P’s conduction band and holes accumulated in WO3′s valence band would prolong the lifespan of photogenerated carriers and increase their redox capacity, which will increase photocatalytic activity. When exposed to visible light, Red P/RGO/WO3 demonstrated an effective overall water splitting activity, producing 287.00 μmol h−1 g−1 of H2, which is around 2.5 times more than Red P. This study constructs Z-scheme heterostructures as a possible means of enhancing Red P’s photocatalytic overall water splitting activity.

Ultrafine Rhodium-Chromium Mixed-Oxide Cocatalyst with Facet-Selective Loading for Excellent Photocatalytic Water Splitting.

The development of water-splitting photocatalysts capable of generating green hydrogen (H2) from water and sunlight is crucial for achieving carbon neutrality. Further enhancement of the photocatalytic water-splitting activity is essential to realizing this objective. Photocatalysts with specific exposed crystal facets can facilitate efficient charge separation of electrons/holes, thereby achieving high activity for water splitting. However, there have been no reports of ultrafine (∼1 nm) cocatalysts being loaded onto specific crystal facets of photocatalysts, despite cocatalysts being the actual reaction sites for water splitting. This study establishes a novel method for achieving facet-selective loading of ultrafine H2-evolution cocatalysts onto the {100} facets, which are the H2-evolution facets, of a strontium titanate photocatalyst. The resulting photocatalyst exhibits the highest apparent quantum yield achieved to date for strontium titanate. This research holds the potential to further improve various types of advanced photocatalysts and is expected to accelerate the transition to carbon neutrality.

MoC nanoparticles embedded in superior thin g-C3N4 nanosheets for efficient photocatalytic activity

Photogenerated charge carrier transfer efficiency in graphitic carbon nitride (g-C3N4) based heterostructures depended strongly on the interface nature. In this paper, MoC nanoparticles less than 5 nm were implanted in superior thin g-C3N4 nanosheets to create high charge carrier separation and transfer efficiency. Cubic MoC in N-doped graphitic carbon was first fabricated using dicyandiamide and ammonium molybdate tetrahydrate at 800 °C. The MoC nanoparticles were homogeneously implanted in g-C3N4 nanosheets by further thermal polymerization of bulk g-C3N4 prepared using melamine and MoC/C composites to create a Schottky junction which was confirmed by band gap analysis and free radical capture test. Melamine and dicyandiamide also play important role to create highly efficient catalysts. The MoC nanoparticles revealed fine crystallinity. A well-developed interface between MoC and g-C3N4 was observed. Because of high conductivity of MoC, well-developed interface, and co-catalyst role of MoC, the MoC/g-C3N4 junction exhibited ideal photocatalytic activity for dye degradation and water splitting. The kinetic constant rate of Rhodamine B degradation using a MoC/g-C3N4 sample created by optimized conditions was 0.061 min−1 which was 8.7 times of that of pristine g-C3N4 nanosheets. In the case of without co-catalyst addition, the photocatalytic hydrogen generation rate using this composite sample was 233.0 μmol g−1 h−1 which was 15.2 times of that of initial g-C3N4 nanosheets. These results supply an efficient approach for the first time to homogeneously distribute small cubic MoC nanoparticles in superior thin g-C3N4 nanosheets to construct heterostructures and greatly reduce photogenerated charge carrier recombination.

Induced Manipulation of Atomically Dispersed Cobalt through S Vacancy for Photocatalytic Water Splitting: Asymmetric Coordination and Dynamic Evolution.

It is still a challenge to construct single-atom level reduction and oxidation sites in single-component photocatalyst by manipulating coordination configuration for photocatalytic water splitting. Herein, the atomically dispersed asymmetric configuration of six-coordinated Co-S2O4 (two exposed S atoms, two OH groups, and two Co─O─Zn bonds) suspending on ZnIn2S4 nanosheets verified by combining experimental analysis with theoretical calculation, is applied into photocatalytic water splitting. The Co-S2O4 site immobilized by Vs acts as oxidation sites to guide electrons transferring to neighboring independent S atom, achieving efficient separation of reduction and oxidation sites. It is worth mentioning that stabilized Co-S2O4 configuration show dynamic structure evolution to highly active Co-S1O4 configuration (one exposed S atom, one OH group, and three Co─O─Zn bonds) in reaction, which lowers energy barrier of transition state for H2O activization. Ultimately, the optimized photocatalyst exhibits excellent photocatalytic activity for water splitting (H2: 80.13 µmol g-1 h-1, O2: 37.81 µmol g-1 h-1) and outstanding stability than that of multicomponent photocatalysts due to dynamic and reversible evolution between stable Co-S2O4 configuration and active Co-S1O4 configuration. This work demonstrates new cognitions on immobilized strategy through vacancy inducing, manipulating coordination configuration, and dynamic evolution mechanism of single-atom level catalytic site in photocatalytic water splitting.

(Invited) Controlled Synthesis of Cocatalyst-Semiconductor Hybrid Nanomaterials for Photocatalytic Water Splitting

With the escalating global demand for energy, mitigating anthropogenic climate change necessitates the pursuit of carbon-neutral energy sources to diminish reliance on fossil fuels. Utilizing particulate photocatalysts for solar-light-driven water splitting presents a promising and sustainable paradigm for the large-scale production of storable and clean H2 fuel. To improve the solar energy conversion efficiency, coupling the photocatalysts with cocatalysts is a broadly adopted approach not only to facilitate charge separation and transport but also to serve as reaction sites and accelerate water-splitting reactions. Recent breakthroughs in colloidal synthesis enable the fabrication of advanced nanoparticles with precise control over size and composition. Colloidal NPs represent ideal cocatalyst candidates due to their capacity to provide numerous active sites and facilitate uninterrupted light absorption by the semiconductor. Here, we introduce our approach to synthesize cocatalyst-semiconductor hybrids as efficient photocatalysts, including the alloying of platinum group metal nanoparticle cocatalysts and the control of single-atom cocatalyst locations on semiconductor nanoparticles.Platinum group metals exhibit high efficiency as cocatalysts in the hydrogen evolution reaction, attributed to their favorable catalytic and electronic properties. Bimetallic alloy systems, in general, can considerably modulate their electronic structures, resulting in exceptional physicochemical properties surpassing those of their monometallic counterparts. Herein, we synthesized PtRu solid-solution alloy nanoparticles as high-performance H2 evolution reaction cocatalysts. The rational integration of PtRu nanoparticles with Al-doped SrTiO3 photocatalyst through liquid-phase adsorption and successive two-step annealing ensure the uniform deposition of PtRu alloy nanoparticles with a solid-solution structure. The bimetallic synergy between Pt and Ru induces higher electrocatalytic activity for the hydrogen evolution reaction and a superior electron-capturing property than its Pt counterpart. Modification of Al-doped SrTiO3 with PtRu alloy nanoparticles, CrOx, and CoOOH results in efficient photocatalytic overall water-splitting activity with an apparent quantum yield of 65% at 365 nm. This work introduces a framework to elucidate catalytic trends, offering rational design guidance for the development of bimetallic solid-solution nanoparticles as highly active cocatalysts for overall water splitting.Single-atom cocatalysts dispersed on semiconductor materials exhibit outstanding heterogeneous catalytic properties through the interactions between the single atoms and the photocatalyst. The nature of these interactions depends on whether the single atoms are located on the surface or within the interior of the photocatalyst. In this work, the location-selective placement of single atoms is achieved by carefully adjusting experimental procedure. Using CdSe nanoplatelets as a support, applying different Pt precursor complexes, solvent, and workup process resulted in location selective deposition of Pt atoms outside/inside CdSe nanoplatelet support. In photocatalytic hydrogen evolution reaction, the surface-adsorbed single Pt atoms exhibit higher stability than the substituted ones. This study provides a viable strategy for the structurally precise synthesis and design of single-atom catalysts.

Interfacial B-O bonding modulated S-scheme B-doped N-deficient C3N4/O-doped-C3N5 for efficient photocatalytic overall water splitting

Photocatalytic overall pure water splitting is a promising method for generating green hydrogen energy under mild conditions. However, this process is often hindered by sluggish electron-hole separation and transport. To address this, a step-scheme (S-scheme) B-doped N-deficient C3N4/O-doped C3N5 (BN-C3N4/O-C3N5) heterojunction with interfacial B-O bonds has been constructed. Utilizing Pt and Co(OH)2 as co-catalysts, BN-C3N4/O-C3N5 S-scheme heterojunction demonstrates significantly enhanced photocatalytic activity for overall pure water splitting under visible light, achieving H2 and O2 evolution rates of 40.12 and 19.62 µmol/h, respectively. Systematic characterizations and experiments revealed the performance-enhancing effects of the enhanced built-in electric field and the interfacial B-O bonding. Firstly, the strengthened built-in electric field provides sufficient force for rapid interfacial electron transport. Secondly, by reducing the transport energy barrier and transfer distance, the interfacial B-O bonds facilitate rapid recombination of electrons and holes with relatively low redox potential via the S-scheme charge-transfer route, leaving the high-potential electrons and holes available for H+ reduction and OH− oxidation reactions. Overall, the photocatalytic efficiency of BN-C3N4/O-C3N5 S-scheme heterojunction was significantly improved, making it a promising approach for green hydrogen production through overall pure water splitting.

Photocatalytic water splitting over K6M10.8O30 (M = Ta, Nb) with a partially filled tetragonal tungsten bronze structure

Abstract K6M10.8O30 (M = Ta, Nb) with partially filled C sites in a tetragonal tungsten bronze structure represented as the general formula (A1)4(A2)2C4M10O30 shows photocatalytic activity for water splitting under UV light irradiation upon loading with suitable cocatalysts. An apparent quantum yield of the optimized NiO(0.2 wt%)-loaded K6Ta10.8O30 for water splitting is 13% at 248 nm.

Interface Regulation of Bi3TiNbO9/Rh Photocatalysts by Introducing Ultrathin Heterolayer to Enhance Overall Water Splitting

AbstractAurivillius compounds‐based photocatalysts have attracted extensive interest largely due to their ferroelectric properties and modifiable characteristics arising from the alternate stacking of structural units. However, the interfacial Schottky barrier between such semiconducting compounds as light absorbers and metallic cocatalysts for hydrogen evolution restrains the transfer of photogenerated electrons, resulting in low photocatalytic overall water splitting activity and stability. Here, an anions‐induced surface structure transformation strategy is employed to modulate the interface structure between Bi3TiNbO9 as a typical Aurivillius compound and the cocatalyst Rh by in situ growing ultrathin Bi2MoO6 heterolayer on the surface of Bi3TiNbO9 nanosheets. The introduction of Bi2MoO6 heterolayer lowers the energy barrier near the Bi3TiNbO9 surface, which can facilitate the transfer of the photogenerated electrons from bulk to surface and thus the reduction of Rh cocatalyst for highly active hydrogen production. Compared with the Bi3TiNbO9‐Rh photocatalyst, the proportion of low‐valence metallic Rh0 in Bi2MoO6 heterolayer‐modified Bi3TiNbO9‐Rh (Bi3TiNbO9‐Bi2MoO6‐Rh) is improved by 7.76%, giving rise to a photocatalytic overall water splitting activity enhancement by a factor of 4.74. This strategy emphasizes the importance of interface regulation in promoting the transfer of photogenerated charge carriers in Aurivillius‐type photocatalysts, providing an effective pathway for designing and fabricating high‐performance photocatalysts.

Boosting solar-light photocatalytic activity of Ni2P-decorated ZnCr2O4 nanofibers for H2 evolution and tetracycline elimination

Photocatalysis is a promising route to convert solar light into chemical energy for H2 evolution and pollutants degradation. Hence, Ni2P decorated ZnCr2O4 (Ni2P/ZnCr2O4) nanofibers were prepared for boosting solar-light induced water splitting and tetracycline hydrochloride (TCH) degradation. For comparison to ZnCr2O4 nanofibers, Ni2P/ZnCr2O4 composites exhibited the better photocatalytic activities for water splitting and TCH removal. Owing to the co-catalytic effect of Ni2P for the efficient photon capture, the charge carriers were rapidly separated and migrated at the interface between Ni2P and oxygen-defected ZnCr2O4. H2 evolution rate of optimal C–Ni2P/ZnCr2O4 with a nominal Ni2P content of 9.0 wt% was 575.89 μmol g−1 h−1, and its apparent quantum yield at 420 nm was 15.25 %, while its H2 evolution decreased from 2815.13 to 2602.51 μmol g−1 after fifth cycle. In addition, the removal efficiency of C–Ni2P/ZnCr2O4 was 93.68 % within 90 min, and declined to 88.76 % after five cycles for solar-light driven degradation of 50 mg L−1 TCH solution. The deactivation of C–Ni2P/ZnCr2O4 was due to the photo-corrosion for the change in valence states of compositions.

Research Progress of β-Ketoenamine-Linked Covalent Organic Frameworks for Photocatalytic Hydrogen Evolution

β-Ketoamide covalent organic frameworks (COFs), also named Tp-COFs, are considered to be a milestone material in the history of photocatalysts because of their excellent visible-light absorption, high crystallinity, ultra-high stability and structural diversity. In recent years, a large number of Tp-COFs and their composites have been successfully constructed based on molecular or composite engineering strategies, and exhibited splendid photocatalytic water splitting activity. In comparison with a composite strategy, the molecular engineering technique effectively avoids interface problems by designing and preparing frameworks at the molecular level. Therefore, it is necessary to timely summarize the construction of Tp-COF photocatalysts based on the molecular engineering strategy, so as to provide some theoretical basis and enlightenment for the subsequent development of high-performance Tp-COFs. Finally, the shortcomings and challenges of this technique and personal views on the further development of Tp-COFs are presented.

Dual Function of Naphthalenediimide Supramolecular Photocatalyst with Giant Internal Electric Field for Efficient Hydrogen and Oxygen Evolution.

Organic supramolecular photocatalysts have garnered widespread attention due to their adjustable structure and exceptional photocatalytic activity. Herein, a novel bis-dicarboxyphenyl-substituent naphthalenediimide self-assembly supramolecular photocatalyst (SA-NDI-BCOOH) with efficient dual-functional photocatalytic performance is successfully constructed. The large molecular dipole moment and short-range ordered stacking structure of SA-NDI-BCOOH synergistically create a giant internal electric field (IEF), resulting in a remarkable 6.7-fold increase in its charge separation efficiency. Additionally, the tetracarboxylic structure of SA-NDI-BCOOH greatly enhances its hydrophilicity. Thus, SA-NDI-BCOOH demonstrates efficient dual-functional activity for photocatalytic hydrogen and oxygen evolution, with rates of 372.8 and 3.8µmol h-1, respectively. Meanwhile, a notable apparent quantum efficiency of 10.86% at 400nm for hydrogen evolution is achieved, prominently surpassing many reported supramolecular photocatalysts. More importantly, with the help of dual co-catalysts, it exhibits photocatalytic overall water splitting activity with H2 and O2 evolution rates of 3.2 and 1.6µmol h-1. Briefly, this work sheds light on enhancing the IEF by controlling the molecular polarity and stacking structure to dramatically improve the photocatalytic performance of supramolecular materials.

Tailoring photocatalytic water splitting activity of boron-thiophene polymer through pore size engineering.

Taking into account the electron-rich and visible light response of thiophene, first-principles calculations have been carried out to explore the photocatalytic activity of donor-acceptor polymers incorporating thiophene and boron. Honeycomb-kagome boron-thiophene (BTP) polymers with varying numbers of thiophene units and fixed B center atoms are direct bandgap semiconductors with tunable bandgaps ranging from 2.41 to 1.88eV and show high absorption coefficients under the ultraviolet and visible regions of the solar spectrum. Fine-tuning the band edges of the BTP polymer is efficiently achieved by adjusting the pore size through the manipulation of thiophene units between the B centers. This manipulation, achieved without excessive chemical functionalization, facilitates the generation of an appropriate quantity of photoexcited electrons and/or holes to straddle the redox potential of the water. Our study demonstrates that two units between B centers of thiophene in BTP polymers enable overall photocatalytic water splitting, whereas BTP polymers with larger pores solely promote photocatalytic hydrogen reduction. Moreover, the thermodynamics of hydrogen and oxygen reduction reactions either proceed spontaneously or need small additional external biases. Our findings provide the rationale for designing metal-free and single-material polymer photocatalysts based on thiophene, specifically for achieving efficient overall water splitting.

Crystal Facet Engineering on SrTiO3 Enhances Photocatalytic Overall Water Splitting.

Single-crystal semiconductor-based photocatalysts exposing unique crystallographic facets show promising applications in energy and environmental technologies; however, crystal facet engineering through solid-state synthesis for photocatalytic overall water splitting is still challenging. Herein, we develop a novel crystal facet engineering strategy through solid-state recrystallization to synthesize uniform SrTiO3 single crystals exposing tailored {111} facets. The presynthesized low-crystalline SrTiO3 precursors enable the formation of well-defined single crystals through kinetically improved crystal structure transformation during solid-state recrystallization process. By employing subtle Al3+ ions as surface morphology modulators, the crystal surface orientation can be precisely tuned to a controlled percentage of {111} facets. The photocatalytic overall water splitting activity increases with the exposure percentage of {111} facets. Owing to the outstanding crystallinity and favorable anisotropic surface structure, the SrTiO3 single crystals with 36.6% of {111} facets lead to a 3-fold enhancement of photocatalytic hydrogen evolution rates up to 1.55 mmol·h-1 in a stoichiometric ratio of 2:1 than thermodynamically stable SrTiO3 enclosed with isotropic {100} facets.

Enhancement of photocatalytic activity for overall water splitting by inhibiting reverse reactions and photocorrosion of C3N4 via modified with TiO2 thin layer

Rapid H2 and O2 recombination on typical semiconductor photocatalysts and severe photocorrosion side reactions are two critical factors limiting the scale-up application of photocatalytic overall water splitting (OWS) in solar hydrogen generation with high efficiency and stability. In this work, we have developed a new strategy to enhance easy-corroded C3N4 stability by coating a thin TiO2 inert layer and have promoted the stability of the C3N4 catalyst significantly. In addition, this thin layer of TiO2 could suppress the H2 and O2 recombination effectively. TiO2@Pt/C3N4 catalyst showed 130% enhanced activity than that of the naked Pt/C3N4 in pure water (7.63 μmol g−1h−1) and satisfied stability without remarkable decay in the long-term test. The characterization results indicated the corrosion-led NO3− formation rate decreased about three times (1.06 ppm). Besides, a thin TiO2 layer-coated catalyst showed higher photocurrent, longer charge lifetime (6.60 ns), and less charge transfer resistance (27.48 kΩ). The calculation investigation results co-related with the characterization results well. A possible mechanism was proposed to promote photocatalytic OWS by blocking the reverse reaction and suppressing photocorrosion. This study provides new guidance for the design of stable and efficient C3N4-based catalysts for H2 generation via photocatalytic OWS.

Construction of NiS/MnCdS S-scheme heterojunction for efficient photocatalytic overall water splitting: Regulation of surface sulfur vacancy and energy band structure

The overall water splitting based on specific photocatalysts is one of the ultimate ways to solve the energy and environmental crisis facing humanity. Sulfide photocatalysts have greater potential in photocatalytic production of solar fuel. However, due to its easy photocorrosion phenomenon, it not effectively driving the water oxidation semi-reaction to produce oxygen, so how to use sulfide photocatalyst to decompose pure water to achieve stoichiometric reaction of H2/O2 production remains a quite challenging task. Herein, sulfur vacancies-rich MnCdS nanoparticles were modified with NiS nanosheets through the hydrothermal derivation method. Different concentration gradients of sulfur-vacancy in MnCdS nanoparticles (MnCdS-Vs-X) with tunable band structures were successful prepared by regulating the concentration of hydrazine hydrate, thus improves the efficiency of light energy utilization and charge separation and the existence of S defects was verified by transmission electron microscopy (TEM) and electron paramagnetic resonance (EPR). The density function theory (DFT) calculation bears out that the draw into of S vacancy adjusted the band structure of MnCdS. Moreover, the successful construction of an S-scheme heterojunction between NiS and MnCdS-Vs-3 has been strongly demonstrated by in-situ XPS and UPS, which promoted interfacial charge separation and further improved the photocatalytic hydrogen evolution efficiency. The as-obtained S-scheme 20 %NiS/MnCdS-Vs-3 heterojunction exhibit excellent visible-light H2 production activity of 4099.55 μmol g−1h−1, 6.75 times higher than pure MnCdS. Most importantly, the excellent and stable photocatalytic overall water splitting activity of H2-509.70 μmol g-1h−1/O2-254.90 μmol g-1h−1 were obtained over 20 % NiS/MnCdS-Vs-3, which further demonstrates the application value of NiS/MnCdS-Vs-3 photocatalysts. This work proposes new ideas for the application of S-vacancies and S-scheme heterojunction in addressing the stability issues associated with sulfide-based photocatalysts in photocatalytic water splitting.

Ba3SnGa10-xInxO20 (0 ≤ x ≤ 2): site-selective doping, band structure engineering and photocatalytic overall water splitting.

Developing new photocatalysts and deciphering the structure-property relationship are always the central topics in photocatalysis. In this study, a new photocatalyst Ba3SnGa10O20 containing two d10 metal cations was prepared by a high temperature solid state reaction, and its crystal structure was investigated by Rietveld refinements of monochromatic X-ray powder diffraction data for the first time. There are 2 Ba, 4 metal cations and 6 O independent atoms in a unit cell. Sn4+ and Ga3+ co-occupy the octahedral cavities named M1 and M2 sites, and the other two metal sites are fully occupied by Ga3+. Rational In3+-to-Ga3+ substitution was performed to reduce the potential of the conduction band minimum and enhance the light absorption ability, which was indeed confirmed using UV-vis diffuse reflectance spectra and Mott-Schottky plots for Ba3SnGa10-xInxO20 (0 ≤ x ≤ 2). Interestingly, In3+ exhibits site selective doping at M1 and M2 sites exclusively. With the light absorption ability enhanced, the photocatalytic overall water splitting activity was also improved, i.e. the photocatalytic H2 generation rate was 1.7(1) μmol h-1 for Ba3SnGa10O20, and the optimal catalyst Ba3SnGa8.5In1.5O20 loaded with 1.0 wt% Pd exhibited the H2 generation rate of 27.5(4) μmol h-1 and the apparent quantum yield at 254 nm was estimated to be 2.28% in pure water.

LaVO4 with alkali metal doping for enhanced photocatalytic water splitting

The photocatalytic water-splitting activity of Na–LaVO4 is enhanced due to the extended visible-light response and improved charge separation.

Full‐Spectrum Responsive Naphthalimide/Perylene Diimide with a Giant Internal Electric Field for Photocatalytic Overall Water Splitting

AbstractThe co‐assembly naphthalimide/perylene diimide (NDINH/PDINH) supramolecular photocatalysts were successfully synthesized via a rapid solution dispersion method. A giant internal electric field (IEF) in co‐assembly structure was built by the larger local dipole. NDINH coated on PDINH could reduce the reflected electric field over PDINH to improve its responsive activity to ultraviolet light. Resultantly, an efficient full‐spectrum photocatalytic overall water splitting activity with H2 and O2 evolution rate of 317.2 and 154.8 μmol g−1 h−1 for NDINH/PDINH together with optimized O2 evolution rate with 2.61 mmol g−1 h−1 using AgNO3 as a sacrificial reagent were achieved. Meanwhile, its solar‐to‐hydrogen efficiency was enhanced to 0.13 %. The enhanced photocatalytic activity was primarily attributed to the IEF between NDINH and PDINH, significantly accelerating transfer and separation of photogenerated carriers. Additionally, a direct Z‐Scheme pathway of carriers contributed to a high redox potential. The strategy provided a new perspective for the design of supramolecular photocatalysts.

Full-Spectrum Responsive Naphthalimide/Perylene Diimide with a Giant Internal Electric Field for Photocatalytic Overall Water Splitting.

The co-assembly naphthalimide/perylene diimide (NDINH/PDINH) supramolecular photocatalysts were successfully synthesized via a rapid solution dispersion method. A giant internal electric field (IEF) in co-assembly structure was built by the larger local dipole. NDINH coated on PDINH could reduce the reflected electric field over PDINH to improve its responsive activity to ultraviolet light. Resultantly, an efficient full-spectrum photocatalytic overall water splitting activity with H2 and O2 evolution rate of 317.2 and 154.8 μmol g-1 h-1 for NDINH/PDINH together with optimized O2 evolution rate with 2.61 mmol g-1 h-1 using AgNO3 as a sacrificial reagent were achieved. Meanwhile, its solar-to-hydrogen efficiency was enhanced to 0.13 %. The enhanced photocatalytic activity was primarily attributed to the IEF between NDINH and PDINH, significantly accelerating transfer and separation of photogenerated carriers. Additionally, a direct Z-Scheme pathway of carriers contributed to a high redox potential. The strategy provided a new perspective for the design of supramolecular photocatalysts.