Regulation of the photogenerated carrier transfer process during photoelectrochemical water splitting:A review

Photoelectrochemical(PEC)water splitting is considered as an ideal technology to produce hydrogen.Photogenerated carrier migration is one of the most important roles in the whole process of PEC water splitting.It includes bulk transfer inside of the photoelectrode and the exchange at the solid-liquid interface.The energy barriers during the migration process lead to the dramatic recombination of photogenerated hot carrier and the reducing of their redox capacity.Thus,an applied bias voltage should be provided to overcome these energy barriers,which brings the additional loss of energy.Plentiful researches indicate that some methods for the regulation of photogenerated hot carrier,such as p-n junction,unique transfer nanochannel,tandem nanostructure and Z-Scheme transfer structure et al.,show great potential to achieve high-efficient PEC water overall splitting without any applied bias voltage.Up to now,many reviews have summarized and analyzed the methods to enhance the PEC or photocatalysis water splitting from the perspectives of materials,nanostructures and surface modification etc.However,few of them focus on the topic of photogenerated carrier transfer regulation,which is an important and urgent developing technique.For this reason,this review focuses on the regulation of photogenerated carriers generated by the photoelectrodes and summarizes different advanced methods for photogenerated carrier regulation developed in recent years.Some comments and outlooks are also provided at the end of this review.

Construction of charge transfer chain in Bi_(12)TiO_(20)-Bi_(4)Ti_(3)O_(12)/α-Bi_(2)O_(3)composites to accelerate photogenerated charge separation

Photogenerated charge separation and transfer is one of the bottleneck steps in photocatalysis,and efficient charge separation strategies are strongly desired.Here,mimicking the electron transport chain in natural photosynthesis,we report the design and fabrication of a charge transfer chain using bismuth-based semiconductor as a proof-of-concept.In view of the thermodynamic energy band positions and structural similarity based on the density functional theory(DFT)analysis,heterostructured combination ofα-Bi_(2)O_(3),perovskite-like Bi_(4)Ti_(3)O_(12),and sillenite Bi12TiO20 was designed for fabrication of charge transfer chain.By tuning the molar ratio of Bi and Ti precursors,the Bi_(4)Ti_(3)O_(12)and Bi12TiO20 particles were formed on the surface ofα-Bi_(2)O_(3)by an insitu transformation process,giving rise to Bi_(12)TiO_(20)-Bi_(4)Ti_(3)O_(12)/α-Bi_(2)O_(3)composites with charge transfer chain.We propose that the effective charge transfer is accomplished amongα-Bi_(2)O_(3),Bi12TiO20,and Bi_(4)Ti_(3)O_(12),which significantly improves the photogenerated charge separation and transfer,as indicated by photoluminescene,time-resolved photoluminescene,and electrochemical impedance spectra results.As expected,the Bi_(12)TiO_(20)-Bi_(4)Ti_(3)O_(12)/α-Bi_(2)O_(3)shows the superior photocatalytic activity for the degradation of environmental pollutants with high concentration.Even for the refractory pollutants like 4-chlorophenol,the optimal Bi_(12)TiO_(20)-Bi_(4)Ti_(3)O_(12)/α-Bi_(2)O_(3)composite shows 28 times higher than that ofα-Bi_(2)O_(3)for photocatalytic degradation,verifying the superiority of photogenerated charge transfer chain in photocatalysis.This work demonstrates the feasibility of the charge transfer chain strategy to boost the photogenerated charge separation,which is of great significance for designing energy and environmental-related materials in heterogonous photocatalysis.

Synergetic effect of graphene and Co(OH)2 as cocatalysts of TiO2 nanotubes for enhanced photogenerated cathodic protection

A layer of graphene(GR)particles was successfully deposited at the interface between Co(OH)2 nanoparticles and TiO2 nanotubes,aiming to improve the photoelectrochemical performance of the large-bandgap semiconductor TiO2.The obtained Co(OH)2/GR/TiO2 was extensively characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),UV–vis absorption spectra and photoluminescence(PL)emission spectra.Electrochemical impedance spectra,photogenerated potential-time(E-t),photocurrent density-time(i-t)and i-E curves and open circuit potential(OCP)curves were measured to investigate the photoelectrochemical activities and photogenerated cathodic protection properties.The results revealed that Co(OH)2/GR/TiO2 exhibits excellent photoelectrochemical and photogenerated cathodic performance due to synergistic effect between Co(OH)2 and graphene.Co(OH)2 and graphene co-modified TiO2 photoanode could provide an effective protection for 304 stainless steel(304 SS)in 3.5 wt%Na Cl solution for 12 h,which would be promising for future practical applications in the field of marine corrosion protection.

Significantly influenced photocatalytic performance for H_(2)O_(2)generation over ultrathin g-C_(3)N_(4)through regulating the migration orientation of photogenerated charge carriers

H_(2)O_(2)has been widely applied in the fields of chemical synthesis,medical sterilization,pollutant removal,etc.,due to its strong oxidizing property and the avoidable secondary pollution.Despite of the enhanced performance for H_(2)O_(2)generation over g-C_(3)N_(4)semiconductors through promoting the separation of photo-generated charge carriers,the effect of migration orientation of charge carriers is still ambiguous.For this emotion,surface modification of g-C_(3)N_(4)was employed to adjust the migration orientation of charge carriers,in order to investigate systematically its effect on the performance of H_(2)O_(2)generation.It was found that ultrathin g-C_(3)N_(4)(UCN)modified by boron nitride(BN),as an effective hole-attract agent,demonstrated a significantly enhanced performance.Particularly,for the optimum UCN/BN-40%catalyst,4.0-fold higher yield of H_(2)O_(2)was obtained in comparison with the pristine UCN.As comparison,UCN modified by carbon dust demonstrated a completely opposite tendency.The remarkably improved performance over UCN/BN was ascribed to the fact that more photo-generated electrons were remained inside of triazine structure of g-C_(3)N_(4),leading to the formation of larger amount of 1,4-endoxide.It is anticipated that our work could provide new insights for the design of photocatalyst with significantly improved performance for H_(2)O_(2)generation.

Co3O4 Decorated Ti/TiO_(2) Nanotubes for Photogenerated Cathodic Protection of 304 Stainless Steel

The Co_(3)O_(4) decorated TiO_(2) nanotube arrays(NTAs)coatings are fabricated by the combination of anodization and impregnating methods.It is found that the introduction of Co_(3)O_(4) can reduce the diffraction intensity of(101)plane of the TiO_(2) and accelerate the separation of photogenerated electron/hole pairs.In addition,the open circuit potential(OCP)and the corrosion potential of 304 stainless steel(304SS)with or without Co_(3)O_(4) decorated TiO_(2) NTAs were measured under visible light,which indicated the 304SS coupled with Co_(3)O_(4) decorated TiO_(2) NTAs had better anticorrosion performance than that of the 304SS or the 304SS coupled with pure TiO_(2) NTAs.The enhancement of the cathodic protection performance of the Co_(3)O_(4) decorated TiO_(2) NTAs can be ascribed to the matched energy levels and strong interaction between Co_(3)O_(4) and TiO_(2) NTAs,and the improvement of light absorption.

An optical tweezer-based microdroplet imaging technology

Microspheres can break the diffraction limit and magnify nano-structure imaging,and with its advantages of low cost and label-free operation,microsphere-assisted imaging has become an irreplaceable tool in the life sciences and for precision measurements.However,the tiny size and limited imaging field of traditional solid microspheres cause difficulties when imaging large sample areas.Alternatively,droplets have similar properties to those of microspheres,with large surface curvature and refractive-index difference from the surrounding environment,and they can also serve as lenses to focus light for observation and imaging.Previous work has shown that droplets with controllable size can be generated using an optical tweezer system and can be driven by optical traps to move precisely like solid microspheres.Here,a novel microdroplet-assisted imaging technology based on optical tweezers is proposed that better integrates the generation,manipulation,and utilization of droplets.

Enhanced photocataly tic activity of TiO_2 by surface fluorination in degradation of organic cationic compound

Experiments were carried out to investigate the influence of TiO2 surface fluorination on the photodegradation of a representative organic cationic compound, Methylene Blue （MB）. The eleetropositive MB shows poor adsorption on TiO2 surface; its degradation performs a HO. radical-mediated mechanism. In the F-modified system, the kinetic reaction rate enlarged more than 2.5 fold that was attributed mainly to the accumulating adsorption of MB and the increased photogenerated hole available on the F-modified TiO2 surface.

Optical-induced dielectric tunability properties of DAST crystal in THz range

The optical-induced dielectric tunability properties of DAST crystal in THz range were experimentally demonstrated.The DAST crystal was grown by the spontaneous nucleation method(SNM) and characterized by infrared spectrum. With the optimum wavelength of the exciting optical field, the transmission spectra of the DAST crystal excited by 532 nm laser under different power were measured by terahertz time-domain spectroscopy(THz-TDS) at room temperature. The transmitted THz intensity reduction of 26 % was obtained at 0.68 THz when the optical field was up to 80 m W. Meanwhile,the variation of refractive index showed an approximate quadratic behavior with the exciting optical field, which was related to the internal space charge field of photorefractive phenomenon in the DAST crystal caused by the photogenerated carrier.A significant enhancement of 13.7 % for THz absorption coefficient occurred at 0.68 THz due to the photogenerated carrier absorption effect in the DAST crystal.

Exploring the mechanism of Ta_(3)N_(5)/KTaO_(3) photocatalyst for overall water splitting by first-principles calculations

The rational fabrication of heterostructures is one of efficient strategies for improving photocatalytic performance of semiconductor photocatalysts.Very recently,Domen and co-workers found that Ta_(3)N_(5) single crystals grown on the surface of KTaO_(3) can accomplish photocatalytic overall water splitting for the first time.In order to comprehend the underlying mechanism of this photocatalytic system,we have performed a systematic study based on density functional theory first-principles calculations.Ta_(3)N_(5)(010)/KTaO_(3)(110)slab models have been built according to experimental observations by considering two common terminations of KTaO_(3)(110)surface,named as Ta_(3)N_(5)/O_(2) and Ta_(3)N_(5)/KTaO.The formations of interfacial bonds are thermodynamically stable,showing a covalent interaction between two components of a heterostructure.Ta_(3)N_(5)/O_(2) has a higher mobility of photogenerated charge carriers and lower recombination rate of charge carriers than Ta_(3)N_(5)/KTaO.The light absorption of heterostructures displays the feature of KTaO_(3) in the short wavelength region and the characteristic of Ta_(3)N_(5) in the long wavelength region.The calculated band offsets show that Ta_(3)N_(5)/O_(2) and Ta_(3)N_(5)/KTaO have distinct Type-II band alignments,with Ta_(3)N_(5) as the accumulator of photoinduced electrons in the former and the collector of photogenerated holes in the latter,respectively.The difference in charge density and electrostatic potential between two components acts as a driving force to promote the transfer of electrons and holes to different domains of the interface,which is beneficial to extend the lifetime of photoinduced carriers.Our results demonstrate that the function of Ta_(3)N_(5) in Ta_(3)N_(5)/KTaO_(3) photocatalytic system is determined by the termination property of KTaO_(3)(110)surface,which provides a likely reason of the observed photocatalytic activity of overall water splitting achieved by Ta_(3)N_(5) synthesized by using KTaO_(3) as a precursor for the nitridation reaction.

Edge assisted epitaxy of CsPbBr_(3)nanoplates on Bi_(2)O_(2)Se nanosheets for enhanced photoresponse

Bi_(2)O_(2)Se has been proved to be a promising candidate for electronic and optoelectronic devices due to their unique physical properties.However,it is still a great challenge to construct the heterostructures with direct epitaxy of hetero semiconductor materials on Bi_(2)O_(2)Se nanosheets.Here,a two-step chemical vapor deposition(CVD)route was used to directly grow the CsPbBr_(3)nanoplate-Bi_(2)O_(2)Se nanosheet hetero structures.The CsPbBr_(3)nanoplates were selectively grown on the Bi_(2)O_(2)Se nanosheet along the edges,where the dangling bonds provide the nucleation sites.The epitaxial relationships between CsPbBr3 and Bi_(2)O_(2)Se were determined as[200]_(Bi_(2)O_(2)Se)‖[110]_(CsPbBr_(3))and[110]_(Bi_(2)O_(2)Se)‖[200]_(CsPbBr_(3))by transmission electron microscopy characterization.The photoluminescence(PL)results reveal that the formation of heterostructures results in the remarkable PL quenching due to the type-Ⅰband arrangement at CsPbBr_(3)/Bi_(2)O_(2)Se interface,which was confirmed by ultraviolet photoelectron spectroscopy(UPS)and Kelvin probe measurements,and makes the photogenerated carriers transfer from CsPbBr_(3)to Bi_(2)O_(2)Se.Importantly,the photodetectors based on the heterostructures exhibit a 4-time increase in the responsivity compared to those based on the pristine Bi_(2)O_(2)Se sheets,and the fast rise and decay time in microsecond.These results indicate that the direct epitaxy of the CsPbBr_(3)plates on the Bi_(2)O_(2)Se sheet may improve the optoelectronic performance of Bi_(2)O_(2)Se based devices.

CARRIER PHOTOGENERATION IN POLY(N-VINYL-CARBAZOLE)-BASED PHOTOCONDUCTIVE THIN-FILM DEVICES

In this paper, photoexcitation processes in the bilayer devices based on inorganic materials and poly（N-vinylcarbazole） （PVK） were investigated. In order to clarify the roles of inorganic materials in photoconductive properties of bilayer devices, TiO2 and ZnS were chosen to combine with PVK. A model for generation of photocurrent （Iph） in single layer device of PVK was obtained. It is deduced that the recombination rate constant （Pcomb） and the ionization rate constant （y） ofexcitons should be considered as the most important factors for Iph. For inorganic materials （TiO2 or ZnS）/PVK bilayer devices, in reverse bias of-4 V, the photocurrent of 115 mA/cm^2 in the TiO2/PVK device was observed, but the photocurrent in the ZnS/PVK device was only 10 mA/cma under the illumination light of 340 nm and the light intensity of 14.2 mW/cm^2. The weaker photocurrent is attributed to the absorption of ZnS within UV region and the energy offset at the interface between PVK and ZnS, which impedes the transport of charge carriers.

Effect of Self-Assembled Monolayers on the Performance of Organic Photovoltaic Cells

The improvement of the performance of organic photovoltaic cells (OPVCs) and the photogeneration process in these devices may occur via multiple mechanisms depending on their structure and/or architecture. For this purpose we investigate how self-assembled monolayers of thiol molecules (C12H25SH and 3T(CH2)6SH) and benzoic acid molecules (ABA and NBA) affect the efficiency and the photogeneration of free carriers in a sexithiophene based photovoltaic cells. Firstly, we provide the results of absorption spectra for samples with SAM of thiol that show there effect on orientation of 6T molecules on these structures and the organization degree of the thiol molecules on ITO substrate. Afterward, we describe from current vs. applied voltage after illumination, the enhancement of the performance of these cells. In the second, we study the effect of SAM of benzoic acids molecules on the photovoltaic behavior. A theoretical model is used for quantitative description of the open circuit voltage as a function of carrier’s generation rates at the electrodes. The results of I-V characterization under illumination show that open circuit voltage as well as short circuit current is dramatically affected by the dipolar layer. The orientation and the magnitude of dipole moment of benzoic acid molecules are the crucial factors that affect the organic photovoltaic parameters.

光电化学水分解中基于半导体的界面工程策略和载流子动力学表征技术的研究进展

为了缓解能源危机和环境问题,太阳能的应用受到了人们的广泛关注.光电化学水分解是一种极有前景的、可以将清洁可再生太阳能转化为清洁燃料的技术.提高能量转换效率无疑是光电化学水分解技术的关键.光生载流子的分离和转移速率是影响光电化学性能的主要因素之一.本综述简要介绍了一些界面工程策略以增强光阳极中光生载流子的分离和传输.此外,总结了近期在原位量化光生载流子传输动力学研究中的进展.我们的目的是帮助读者了解这一领域的最新发展,并为理解动态空穴转移提供一个独特的视角.最后,我们对发展微纳尺度电极界面光生载流子分离和转移动力学表征手段中面临的重大挑战和未来前景进行了展望.

Bio-inspired high-efficiency photosystem by synergistic effects of core-shell structured Au@CdS nanoparticles and their engineered location on{001}facets of SrTiO_(3)nanocrystals

Natural photosynthesis,which provides a green and high-efficiency energy conversion path by spatial separation of photogenerated carriers through combined actions of molecules ingeniously arranged in an efficient solar nanospace,highlights the importance of rational nanostructure design to realize artificial high-efficiency photosystem.Inspired by these unique features,we constructed a high-efficiency ternary photosystem by selectively decorating the{001}facets of 18-facet SrTiO_(3)with Au@CdS photosensitizers via a green photo-assisted method.Benefiting from the dual-facilitated charge carriers transportation in core-shell structured Au@CdS heterojunction and well-faceted 18-facet SrTiO_(3)nanocrystal,such a photo-catalyst could realize the effective spatial separation of photogenerated electrons and holes.As expected,the 18-facet SrTiO_(3)/Au@CdS photocatalyst exhibits superior activity in visible-light-driven photocatalytic hydrogen evolution(4.61 mmol h^(−1)g^(−1)),166%improvement in comparison with randomly deposited Au@CdS(1.73 mmol h^(−1)g^(−1)).This work offers new insight into the development of green and high-efficiency photocatalytic systems based on the rational nanostructure design by crystal facet engineering.

In-situ construction of Z-scheme g-C_(3)N_(4)/WO_(3) composite with enhanced visible-light responsive performance for nitenpyram degradation

Developing an excellent photocatalysis system to remove pesticides from water is an urgent problem in current environment purification field.Herein,a Z-scheme WO_(3)/g-C_(3)N_(4) photocatalyst was prepared by a facile in-situ calcination method,and the photocatalytic activity was investigated for degradation of nitenpyram(NTP)under visible light.The optimal Z-scheme WO_(3)/g-C_(3)N_(4) photocatalyst displayed the highest rate constant(0.036 min-1),which is about 1.7 and 25 times higher than that of pure g-C_(3)N_(4) and WO_(3),respectively.The improvement of photocatalytic performance is attributed to fast transfer of photogene rated carriers in the Z-scheme structure,which are testified by electron spin resonance(ESR)experiments,photocurrent and electrochemical impedance spectra(EIS)measurements.Moreover,the effects of typical water environmental factors on the degradation NTP were systematically studied.And the possible degradation pathways of NTP were deduced by the intermediates detected by highperformance liquid chro matography-mass spectrometry(HPLC-MS).This work will not only contribute to understand the degradation mechanism of pesticides in real water environmental condition,but also promote the development of new technologies for pesticide pollution control as well as environmental remediation.

Achieving an electron transfer photochromic complex for switchable white-light emission

Tuning white-light emission via free radicals is still a challenge in molecular-based functional materials.Herein, a new photoactive Zn^(2+) oxalate-based chain containing a polypyridine ligand was designed and synthesized with remarkably bifunctional photochromism and photo-actuated greenish white-light emission after UV, sunlight or Xe lamp light irradiation at room temperature. The photo-actuated coloration process was induced by the photogeneration of stable radicals originated from intermolecular electron transfers from oxalate components to the protonated polypyridine units, as demonstrated by UV–vis, IR,electron spin resonance and X-ray photoelectron spectra and magnetic measurements. Importantly, the on/off greenish white light emission(WLE) could be reversibly switched by generation and elimination of radicals via light irradiation and heat treatment, providing a feasible strategy for designing photoswitchable light emission diodes materials.

Fabrication of Z-Scheme WO3/KNbO3 Photocatalyst with Enhanced Separation of Charge Carriers

Z-Schemc photocatalysts as a research locus pertomi strong redox capability and high photocatalytic peribnnance.WO3/KNbO3 photocatalysts were fabricated by ball milling method,and performed higlier photocatalytic activity in liquid degradation(rhodamine B,methylene blue and bisphenol A),compared with WO3 or KNbO3 monomer.This is due to that Z-scheme heterojunction is lonned between WO3 and KNbO3,and the holes photo-excited in valence band of KNbO?are quickly combined with the electrons in conduction band of WO3.The electrons accumulated in conduction band of KNbO3 show high reducibility,thereby reducing O2 to·O 2-,and the holes in valence band of WO3 show high oxidative to oxidize H2O to·OH,respectively.Furthermore,it is proved by means of electron spin resonaiice(ESR)spectra,terephthalic acid photolumiiiescence probing technique(TA・PL),and UV-Vis absorption spectra of nitroblue tetrazolium.This work indicates that the iabrication of Z-scheme structure can improve the photocatalytic activity by efficiently separating the photogenerated electrons and holes in the photocatalytic reaction system,which is helpful to deeply understand the migration mechanism of photoexcited cairier(band-band transfer and Z-scheme transfer)in heterojunction photocatalysts.

A method for modeling and deciphering the persistent photoconductance and long-term charge storage of ZnO nanorod arrays

The controllability of persistent photoconductance （PPC） and charge/energy storage of ZnO nanorod arrays （NRAs） were demonstrated experimentally by tuning the nanorod diameter. The dependency of the ZnO NRAs＇ photoelectric characteristics on the nanorod diameter suggests that the Debye length and photon penetration depth in ZnO could spatially partition a standalone nanorod into three different photoelectric functional regions （PFRs）. Theoretically, a series of rate functions was employed to describe the different extrinsic/intrinsic carrier photogeneration/recombination dynamic sub-processes occurring in the different PFRs, associated with oxygen chemisorption/photodesorption, oxygen vacancy photoionization, and electron trapping by photoionized oxygen vacancies. On the basis of the coupled contributions of these different dynamic sub-processes in the photoelectric properties of the ZnO NRAs, a thorough-process photoelectric dynamic model （TPDM） was proposed using the simultaneous rate functions. Through solving the rate functions, the corresponding analytical equations could be employed to simulate the time-resolved PPC spectra of the ZnO NRAs, and then the quantitative parameters extracted to decipher the PPC and charge/energy storage mechanisms in the ZnO NRAs. In this way, the TPDM model provided a numerical-analytical method to quantitatively evaluate the photoelectric properties of ZnO NRA-based devices. Additionally, the TPDM model revealed how the different photoinduced carrier dynamics in the different PFRs could play functional roles in different optoelectronic applications, e.g., photodetectors, photocatalysts, solar cells and optical nonvolatile memories, and thus it illuminated a practical approach for the design of ZnO NRA-based devices via optimization of the modularized spatial configuration of the PFRs.

Photo-degradation organic dyes by Sb-based organic-inorganic hybrid ferroelectrics

The organic-inorganic hybrid halide compounds have emerged as one of the most promising photoelectric material for their superior optoelectronic properties and hold great prospects for renewable energy substitutes and environmental protection as photocatalysis.Here,we report the optical properties of the Sb-based organic-inorganic hybrid ferroelectric materials:pyridine-4-aminium tetrachloroantimonate((C_(5)H_(7)N_(2))SbCl_(4),sample 1),piperidin-1-aminium tetrachloroantimonate((C_(5)H_(13)N_(2))SbCl_(4),sample 2)and tris(trimethylammonium)nonachlorodiantimonate(((CH_(3))_(3)NH)_(3)Sb_(2)Cl_(9),sample 3),which are a kind of exploited efficient photocatalysts.Samples 2 and 3 exhibit distinct photoelectric respond,which are mainly ascribed to their minor narrow band-gap compared with sample 1.For the ferroelectrics,the intrinsic of spontaneous polarization of sample 3 at room temperature is favourable for the separation of photogenerated electrons and holes within the photorespond process.Moreover,sample 3 shows the highest efficiency of photo-decomposed Rhodamine B(90.2%within 80 min)and Methyl Orange(MO)(97.4%within 50 min),thanks to the photo-excited electrons and holes promoting the formation of oxidative radical species during the photo-redox progress.These findings prove that the development of a novel Sbbased organic-inorganic hybrid halide compounds with good stability in the degradation of organic dyes paves a way to designing new photocatalyst.

Morphology-controlled porphyrin nanocrystals with enhanced photocatalytic hydrogen production

Molecular self-assembly is a natured-inspired strategy to integrate individual functional molecules into supramolecular nanostructured materials through noncovalent bond interactions for solar to fuel conversion.However,the design and engineering of the morphology,size,and orderly stacking of supramolecular nanostructures remain a great challenge.In this study,regular porphyrin nanocrystals with different orderly stacked structures are synthesized through noncovalent self-assembly of Pt(II)meso-tetra(4-carboxyphenyl)porphine(PtTCPP),using surfactants with different electronegativity.The synergy of noncovalent bond interactions between porphyrin molecules,and between porphyrin molecules and surfactants resulted in different molecular packing patterns.Due to the spatial ordering of PtTCPP molecules,the different nanocrystals exhibit both collective optical properties and morphology-dependent activities in photocatalytic hydrogen production.The measurements of the photodeposition of dual cocatalysts showed that the photogenerated electrons and holes selectively aggregated at different active sites,revealing separation pathways and directional transfer of photogenerated electrons and holes in the assemblies.This study provides a new strategy to exert rational control over porphyrin self-assembly nanocrystals for highly efficient water splitting.