High-efficiency Photocatalysts Research Articles

Efficient photocatalytic removal of ciprofloxacin through in-situ growth of g-C3N4 on the surface of clinoptilolite

Natural mineral clinoptilolite has many advantages such as porous structure, stability, low price, environmental protection, and simple modification process, making it an ideal choice for wastewater treatment materials. Loading photocatalysts on the surface of zeolite can effectively exert adsorption degradation synergy in wastewater treatment, improve pollutant removal and mineralization capabilities, and further reduce the harm of wastewater to the environment. In this work, g-C3N4 was in-situ grown on the surface of clinoptilolite using a one-step calcination method for efficient photocatalytic removal of the pollutant ciprofloxacin from water. In-situ growth of g-C3N4 on clinoptilolite enables the catalyst to have strong adsorption capacity for pollutants. At the same time, the large specific surface area and extended photo-generated carrier lifetime make the composite photocatalyst exhibit excellent visible light adsorption degradation ability. The CN/CLI-60 with the best photocatalytic performance showed a removal rate of over 90 % of ciprofloxacin within 60 min, much higher than pure g-C3N4 and clinoptilolite. In addition, the pH value, pollutant concentration, catalyst quantity, and cycle stability have all been investigated to evaluate the practical application potential of this catalyst. This work can provide industrial guidance for the rational design of low-cost and high-efficiency photocatalysts using natural clinoptilolite.

Boosting intimate contact and charge transfer between carotenoid dye and Ti3C2Tx MXene for photocatalytic hydrogen production

Developing efficient heterojunction photocatalysts with improved light-harvesting capacity and high charge carrier separation rates for photocatalytic hydrogen production remains a challenge in the field of energy conversion. In this study, we synthesized two-dimensional Ti3C2Tx nanosheets through HF etching of Ti3AlC2 and combined them with carotenoid dyes (Car) with different structural characteristics using a solvent spontaneous volatilization method to construct novel Car@Ti3C2Tx Schottky heterojunctions. The intimate interface contacts between the two-dimensional Ti3C2Tx MXene and Car enhanced the light-harvesting capacity of the photocatalysts and promoted charge separation rates. The optimal sample, Car-3@Ti3C2Tx nanocomposite, exhibited excellent photocatalytic activity of 84.4 µmol h−1 g−1 for H2 production under visible light illumination. This work demonstrates the potential of earth-abundant organic Car dyes in constructing high-efficiency and low-cost photocatalysts for hydrogen production.

Fe-TiO2-x/TiO2 S-scheme homojunction for efficient photocatalytic CO2 reduction

CO2-to-high value-added chemicals via a photocatalytic route is of interest but strangled by the low efficiency. Herein, a novel Fe-TiO2-x/TiO2 S-scheme homojunction was designed and constructed by using a facile surface modification approach whereby oxygen vacancy (OV) and Fe introducing on the TiO2 nanorod surface. The as-synthesized Fe-TiO2-x/TiO2 S-scheme homojunction exhibits positive properties on promoting photocatalytic CO2 reduction: i) the nanorod structure provides numerous active sites and a radical charge transfer path; ii) the doped Fe and OV not only synergistically enhance light utilization but also promote CO2 adsorption; iii) the Fe-TiO2-x/TiO2 S-scheme homojunction benefits photoexcited charge separation and retains stronger redox capacity. Thanks to those good characters, the Fe-TiO2-x/TiO2 homojunction exhibits superior CO2 reduction performances with optimized CO/CH4 generation rates of 122/22 μmol g-1h−1 which exceed those of pure TiO2 by more than 9.4/7.3 folds and most currently reported catalytic systems. This manuscript develops a facile and universal approach to synthesize well-defined homojunction and may inspire the construction of other more high-efficiency photocatalysts toward CO2 reduction and beyond.

High-efficiency photocatalyst based on Au nanoparticles loaded on defective ZnO nanorods

Optimizing the semiconductor-metal interaction is the key to developing metal single-atom cocatalysts with 100 % metal atom utilization and unique electronic properties. Metal atom sites are exclusively coordinated with semiconductor, featuring a chemical-bond-driven tunable interaction. Here vacancy defect-rich ZnO nanorods (NRs) are fabricated by a facile hydrothermal approach. Au nanoparticles (NPs) are preferentially anchored on surface zinc vacancy sites of ZnO NRs in an ultra-low concentration (10−4 mol/L) of HAuCL4 solution. The Au/ZnO nanohybrids exhibit an excellent photocatalytic activity toward removal of Rhodamine B and levofloxacin. Combining ferromagnetism and valence-band XPS spectra analysis, it is demonstrated that the strong interaction of surface vacancy defects in ZnO and Au generates a distinct upshift of the valence band edge, resulting from the antibonding interaction between O 2p and Au 5d orbitals which significantly weakens the Au–O bonds. This facilitates the release of the lattice oxygen and thus generates more oxygen vacancies. The remarkable photoactivity of defective Au/ZnO is due to the synergistic interaction between the intrinsic oxygen vacancy and Au. Optimizing the hybridization of transition metal d and O 2p states at the atomic scale can induce more active-sites, improve atomic utilization efficiency and thus provide a new approach for enhancing photoactivity.

Construction of an Electron Capture and Transfer Center for Highly Efficient and Selective Solar-Light-Driven CO2 Conversion.

Exploring high-efficiency photocatalysts for selective CO2 reduction is still challenging because of the limited charge separation and surface reactions. In this study, a noble-metal-free metallic VSe2 nanosheet was incorporated on g-C3N4 to serve as an electron capture and transfer center, activating surface active sites for highly efficient and selective CO2 photoreduction. Quasi in situ X-ray photoelectron spectroscopy (XPS), soft X-ray absorption spectroscopy (sXAS), and femtosecond transient absorption spectroscopy (fs-TAS) unveiled that VSe2 could capture electrons, which are further transferred to the surface for activating active sites. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations revealed a kinetically feasible process for the formation of a key intermediate and confirmed the favorable production of CO on the VSe2/PCN (protonated C3N4) photocatalyst. As an outcome, the optimized VSe2/PCN composite achieved 97% selectivity for solar-light-driven CO2 conversion to CO with a high rate of 16.3 μmol·g-1·h-1, without any sacrificial reagent or photosensitizer. This work offers new insights into the photocatalyst design toward highly efficient and selective CO2 conversion.

Construction of Bi2O3−x/NiAl-LDH S-scheme heterojunction for boosting photothermal-assisted photocatalytic CO2 reduction

In this study, a new type of 2D/2D Bi2O3−x/NiAl-LDH (BO/NA-LDH) S-scheme photocatalyst was prepared by combining NiAl-LDH with Bi2O3−x by wet chemical deposition for obtaining efficient photothermal-assisted photocatalytic reduction of CO2 under simulated sunlight irradiation. In particular, the as-prepared optimal 50-BO/NA-LDH sample exhibited the CO production yield of 83.55 ± 2.76 μmol/g/h, which was 9 and 27 times that of BO (9.32 ± 0.62 μmol/g/h) and NA-LDH (3.09 ± 0.38 μmol/g/h), respectively. The enhancement of photothermal-assisted activity over the 50-BO/NA-LDH system was mainly attributed to the coupling of the photothermal conversion performance of Bi2O3−x and improving the migration efficiency of interface carriers of S-scheme heterojunction and 2D/2D structure. This study presents a promising strategy for the development of high-efficient photothermal-assisted photocatalysts.

Enhanced performance of attapulgite-supported g-C3N4 for photocatalytic CO2 reduction

As a new type of non-metallic semiconductor photocatalyst, g-C3N4 has great potential in photocatalytic CO2 reduction. However, due to the low catalytic activity, it is still far from industrial reality for such applications. Herein, this work introduces attapulgite (ATP) into the photocatalyst system of g-C3N4. Additionally, ATP/Au-CN was obtained through the photodeposition method. The photocatalytic reduction ability of the photocatalyst for CO2 is enhanced. The photoelectric tests show that loading of ATP can promote the separation and migration of photocarriers. Through BET testing, it was found that the alkaline pore structure on the surface of ATP not only captures CO2, but also increases the specific surface area of the composite. According to the experimental results, the possible photocatalytic mechanism was verified by in-situ diffuse reflection infrared Fourier transform (DRIFT) spectral analysis and DFT calculation. This work provides new guidance for the construction of high efficient photocatalyst systems using abundant ATP as a support.

2D/2D heterojunction of MgAlTi-LDH/g-C3N4 with oxygen vacancy engineering for enhanced photocatalytic activities under natural sunlight

Semiconductor photocatalysis is an ideal method for wastewater treatment. However, the rapid recombination of photogenerated electron-hole pairs limits the improvement of photocatalytic efficiency. Constructing heterostructures by different energy band-matched semiconductors and surface defect engineering are considered as effective strategies to inhibit the recombination of photogenerated electron-hole pairs. Herein, a novel MgAlTi-LDH/g-C3N4 heterojunction was fabricated by in-situ growth of oxygen vacancy rich MgAlTi-LDH on ultrathin g-C3N4 nanosheets first time for the degradation of methylene blue (MB) under natural sunlight. The optical absorption properties, crystalline phase, microstructure, and morphological analysis of the fabricated materials are subsequently characterized by XRD, FT-IR, UV–vis DRS, TEM, BET and XPS. Owing to Ti-doping, oxygen vacancy rich MgAlTi-LDH exhibited superior photocatalytic activity for MB degradation, which was 5.5 times of that of MgAl-LDH. Furthermore, MgAlTi-LDH/g-C3N4 heterostructures showed a higher photocatalytic activity under visible light irradiation, which was 5.9, 4.9, and 3.2 times of that of MgAl-LDH, MgAlTi-LDH and g-C3N4, respectively. Upon natural sunlight irradiation, MgAlTi-LDH/g-C3N4 can degrade 95 % of MB after 130 min of irradiation. The improvement of photocatalytic activity of MgAlTi-LDH/g-C3N4 was attributed to the synergistic effect of MgAlTi-LDH and g-C3N4, surface oxygen vacancies, and heterostructure interface. This work promotes a new strategy to synthesize high-efficiency photocatalysts for the removal of organic pollutants from wastewater by constructing heterojunctions with surface defects.

Application of Silicon Nanowires

Abstract:: Silicon Nanowires (SiNWs), a novel category of nanomaterials, exhibit several outstanding properties, including superior transistor performance, quantum tunneling effects, and remarkable electrical and optical capabilities. These properties are expected to contribute significantly to the development of future nanodevices, such as sensors and optoelectronic components. The potential for device miniaturization with SiNWs is based on their ease of monocrystallization. This leads to a reduced rate of hole-electron complexes and their extensive specific surface area that promotes boundary effects, thereby diminishing conductivity. Characterized by unique structural attributes, SiNWs hold promise for a wide range of applications in various sectors. To date, multiple methods have been established for SiNW fabrication, including solgel, electrochemical, laser ablation, chemical vapor deposition, and thermal vapor deposition techniques. Subsequently, the focus has shifted to the application of SiNWs in electronics, energy, and biomedicine. SiNWs are instrumental in producing high-performance electronic devices, such as field-effect transistors, sensors, and memory units. They also exhibit outstanding photovoltaic properties, making them suitable for high-efficiency solar cell and photocatalyst production. Additionally, SiNWs are poised to make significant contributions to biomedicine, particularly in biosensors, drug delivery systems, and tissue engineering materials. This article provides a concise review of the current status of SiNWs in electronics, sensing devices, and solar cell applications, and their roles in high-performance transistors, biosensors, and solar cells. It concludes with an exploration of the challenges and prospects for SiNWs. In summary, the unique attributes of SiNWs establish them as a versatile nanomaterial with broad applicability. This review offers a comprehensive overview of SiNW research and theoretical insights that may guide similar studies. The insights into recent SiNW research presented here are intended to inform future applications and investigations involving these nanomaterials.

Optimizing construction of fern-like Co3O4@Ni3Fe-LDH p-n heterojunction for boosting photo-assisted-electronic N2 reduction into NH3 and DFT calculation

Herein, a fern-like p-n heterojunction by anchoring Ni3Fe-LDH nanoplates onto Co3O4 nanoneedles have been optionally constructed. Essentially, p-n heterojunction ensured to induce strong built-in electric field, and inherit interfacial electron redistribution. Based on their compatible and well-matched electronic band structures, a staggered type-II photo-generated electron/holes transfer pathway have been elaborated by density functional theory calculation (DFT), in situ irradiation X-ray photoelectron spectroscopy (XPS), and fluorescent decay. This band bending and charge migrating module conferred the architecture with strong redox ability, sufficient exciton dissociation, and admirable optoelectronic characteristics. Moreover, the heterostructure acquired broad absorption spectrum to exhibit outperforming photocatalytic effect. Totally, this electron redistribution at the hierarchical interface, a type-II scheme charge-transfer pathway and the oxygen defects would lead to high efficiency in solar light assisted N2 reduction. Typically, Co@Ni3Fe-2 catalyst exhibited the highest NH3 production rate of 16.15 μg h−1 mgcat.−1 and Faraday efficiency (FE) of 31.57% at −0.6 V vs. RHE in 0.1 M Na2SO4 solution. Fortunately, with light exposure, the NH3 production rate and FE could increase by 27.9% and 18.1% than that under dark. This work would provide a plausible attitude towards the design of high efficient photocatalyst for artificial photosynthesis with multi-functionalized coupling effect.

Constructing a Titanium Silicon Molecular Sieve-Based Z-Scheme Heterojunction with Enhanced Photocatalytic Activity.

Titanium silicon molecular sieve (TS-1) is an oxidation catalyst that possesses a long lifetime of charge transfer excited state, high Ti utilization efficiency, large specific surface area, and good adsorption property; therefore, TS-1 acts as a Ti-based photocatalyst candidate. In this work, TS-1 coupled Bi2MoO6 (TS-1/BMO) photocatalysts were fabricated via a facile hydrothermal route. Interestingly, the optimized TS-1/BMO-1.0 catalyst exhibited a decent photodegradation property toward tetracycline hydrochloride (85.49% in 120 min) under the irradiation of full spectrum light, which were 4.38 and 1.76 times compared to TS-1 and BMO, respectively. The enhanced photodegradation property of the TS-1/BMO-1.0 catalyst could be attributed to the reinforced light-harvesting capacity of the photocatalyst, high charge mobility, and suitable band structure for tetracycline hydrochloride degradation. In addition, the mechanism of photocatalytic degradation of tetracycline hydrochloride by the TS-1/BMO-1.0 catalyst was reasonably proposed based on the band structure, trapping, and ESR tests. This research provided feasible ideas for the design and construction of high-efficiency photocatalysts for contaminant degradation.

Polyelectrolyte modified black phosphorus/titania nanosheet heterojunction enhanced photocatalysis: Synergistic enhancement effect of interface affinity and electron transport channel

The instability and high electron-hole recombination have limited the application of black phosphorus (BP) as an excellent photocatalyst. To address these challenges, poly dimethyl diallyl ammonium chloride (PDDA), poly (allylamine hydrochloride) (PAH), and polyethyleneimine (PEI) are introduced to the functionalization of BP (F-BP), which can not only enhance its stability, but also boost the carrier transfer. Furthermore, a high-performance heterojunction photocatalyst is fabricated using F-BP and titania nanosheets (TNs) via a layer-by-layer self-assembly approach. The experimental outcomes unequivocally indicate that F-BP exhibits fast charge migration compared to BP. The density functional theory (DFT), in situ Kelvin-probe force microscopy (KPFM) and other advanced characterization techniques collectively unfold that PDDA modified BP can notably boost separation and propagation of charges, along with an enhanced carrier abundance. In summary, this novel strategy of using polyelectrolytes to enhance the electron transfer and the stability of BP permits immense potential in building next-generation BP-based high efficiency photocatalysts.

Synergy of oxygen vacancies, Lewis acid sites, and interfacial chemical bonds on ZnSnO3/AgI for photodegradation of tetracycline

Chemically bonded Z-scheme ZnSnO3/AgI composites rich in oxygen vacancies (OVs) and Lewis acid sites were prepared successfully and showed excellent photocatalytic activities. Especially, ZnAg-2 degraded 96.1% tetracycline under visible light irradiation for 15 min. OVs contributed to Lewis acid sites production and interfacial chemical bonds formation through weakening the metal−O bonding. Lewis acid sites favored the adsorption of electron-rich tetracycline. Interfacial chemical bonds together with Z-scheme structure accelerated electron transfer and retained the high redox ability of ZnSnO3 and AgI. OVs contributed to singlet oxygen (1O2) production through facilitating the energy transfer from triplet exciton to O2. ZnSnO3/AgI composites possess good reusability and show great practical application potential. Based on ROSs generation and photoreduction experiment, the photocatalytic mechanism of the ZnAg composites was proposed. The possible degradation pathway was deduced and the biological toxicity was evaluated based on detected degradation intermediates. This work highlights the significant roles of OVs, Lewis acid sites, and chemical bonding in improving the photocatalytic activity of Z-scheme composites and provides new insight into designing high efficient photocatalysts.

Fabrication of p-n Heterostructured Photocatalysts with Triazine-Based Covalent Organic Framework and CuInS2 for High-Efficiency CO2 Reduction.

The application of covalent organic frameworks (COFs) for the photocatalytic reduction of CO2 is mostly limited by severe charge recombination and low sunlight utilization. Herein, a triazine-based COF with an electron-rich and large π-conjugated system (TCOF) was employed as a building block and integrated with CuInS2 (CIS) to construct a noble-metal-free and high-efficiency photocatalyst for CO2 reduction. The in situ growth of CIS nanosheets on TCOF creates a p-n heterojunction, named CIS@TCOF. Compared with TCOF, the CIS@TCOF heterostructure exhibits a dramatically boosted photocatalytic performance in the reduction of CO2. The produced HCOOH yield over 10 wt % CIS@TCOF can be up to 171.2 μmol g-1 h-1 under visible light irradiation with good reproducibility, which is about 3 times as high as that over TCOF. Further in-depth studies indicate that the introduction of CIS not only enhances the visible light utilization but also restrains the recombination of photogenerated electron-hole pairs efficiently and facilitates the photoinduced charge transfer via the p-n heterojunction system due to the unique structural and compositional features. This research shows the great potential of COFs as efficient photocatalytic carbon fixation materials and provides a versatile route to construct semiconductor-COF heterostructures for photocatalysis.

Multiflower-like ReS2/NiAl-LDH Heterojunction for Visible-Light-Driven Photocatalytic CO2 Reduction.

The development of high-efficiency heterojunction photocatalysts has been recognized as an effective approach to facilitate photocatalytic CO2 reduction. In this research, we successfully synthesized a novel multiflower-like ReS2/NiAl-LDH heterojunction through a hydrothermal method. Remarkably, when exposed to visible-light irradiation, 2-ReS2/NiAl-LDH demonstrated an exceptional CO production rate of 272.26 μmol·g-1·h-1, which was 4.0 and 10.8 times higher than that of pristine NiAl-LDH and ReS2. The intertwined structure of ReS2 and NiAl-LDH promoted the efficient transfer and separation of photogenerated carriers, thereby significantly enhancing the photocatalytic CO2 reduction capabilities of the ReS2/NiAl-LDH. Furthermore, the carrier transfer pathway for the 2-ReS2/NiAl-LDH heterojunction was elucidated, suggesting a type II scheme mechanism, as evidenced by photochemical deposition experiments. The findings of this study offer valuable insights and pave the way for future research in the design and construction of LDH-based and ReS2-based heterojunctions for efficient photocatalytic CO2 reduction.

Te-vacancy defect triggering photocatalytic overall water splitting for MoTe2/GeN Z-scheme heterostructure

Developing proper semiconductor photocatalysts is urgently needed to solve energy and environmental crises. Especially, photocatalysts for water splitting with a Z-scheme mechanism are desirable materials. Herein, a two-dimensional VTe-MoTe2/GeN heterostructure (VTe-HS), including single Te vacancy, is theoretically proved to function as a direct Z-scheme photocatalyst with the wide light-harvesting range, the effective spatial separation for carriers, and the high catalytic activity for water splitting. An enhanced optical absorption coefficient of 105 cm−1 is observed and the absorption edge (∼1.0 eV) is red-shifted into the infrared light region. Separating photogenerated electron–hole pairs enhances the photocatalytic efficiency due to the staggered band alignment. Interlayer charge migration of about 0.154 electrons induces an intrinsic built-in electric field in the heterostructure, allowing forming the Z-scheme mechanism with a reduction potential of –4.01 eV and an oxidation potential of –7.13 eV. Gibbs free energies confirm that water redox reactions can proceed spontaneously under sunshine. Moreover, the Heyrovsky reaction is kinetically more favorable than the Tafel reaction because of a little energy barrier (0.071 eV). These features show that the VTe-HS is a desirable water-splitting photocatalyst, providing a valuable clue to constructing high-efficiency photocatalysts.

Marrying luminescent metal nanoclusters to C3N4 for efficient photocatalytic hydrogen peroxide production

Photocatalytic oxygen (O2) reduction has been considered a promising method for hydrogen peroxide (H2O2) production. However, the poor visible light harvesting and low-efficient separation and generation of charge carriers of conventional photocatalysts strongly limited their photocatalytic H2O2 generation performance. Herein, we design a highly efficient photocatalyst in this work by marrying luminescent gold-silver nanoclusters (AuAg NCs) to polyethyleneimine (PEI) modified C3N4 (C3N4-PEI). The key design in this work is the utilization of highly luminescent AuAg NCs as photosensitizers to promote the generation and separation of charge carriers of C3N4-PEI, thereby ultimately producing abundant e− for O2 reduction under visible light illumination (λ ≥ 400 nm). As a result, the as-designed photocatalyst (C3N4-PEI-AuAg NCs) exhibits excellent photocatalytic activity with an H2O2 production capability of 82 μM in pure water, which is 3.5 times higher than pristine C3N4 (23 μM). This interesting design provides a paradigm in developing other high-efficient photocatalysts for visible-light-driven H2O2 production.

Synergizing copolymerization and thermal induction for carbon nitride: Reinforcing photocatalytic performance and mechanism insight

Structure optimization of photocatalyst graphitic carbon nitride (CN) is still a key endeavor. CN nanosheets were prepared via a facile one-pot copolymerization process, incorporating electron-withdrawing groups 5-cyanopyrimidine (CPM) and melamine under calcination. The synergistic effect of molecular doping and thermal induction effectively modulates the intrinsic electronic and band structure of CN. The post-optimized sample (CNMCPM0.03–700) exhibits a higher reduction potential, reduced nanosheet thickness, stronger crystallinity, and enhanced electron-holes separation efficiency, compared to pristine CN (CNM). Notably, significant morphological and textural alterations were observed in the modified CNMCPMX-T samples. Consequently, a remarkable enhancement in visible-light photocatalytic H2 evolution and CO2 reduction performance was achieved. Specifically, the CNMCPM0.03–700 retained an H2 evolution rate of 166.4 µmol·h−1, which was 14.8-fold higher than that of CNM (11.3 µmol·h−1), along with a 31.6-fold increase in CO evolution efficiency. Molecular and textural engineering demonstrate their universal applicability for different comonomers. This study showcases the feasibility of synergizing thermal induction and copolymerization strategies for synthesizing high-efficiency CN-based photocatalysts with unique topology and structural precision.

Novel H4Nb6O17/BiOCl heterojunction with oxygen defects for boosting photodegradation activity under simulated solar light

The development of green, thorough and high-efficiency photocatalysts for tetracycline hydrochloride (TCH) degradation is a hot spot in environmental and energy fields. In this work, the H+-restacked H4Nb6O17 nanotubes (RHNT) were incorporated with BiOCl plates to successfully construct RHNT/BiOCl (RTB) composites with the 1D/2D heterostructure, which was beneficial to the charge carrier separation. The introduction of oxygen vacancies in RTB composites could promote the effective separation of charge carriers and the generation of reactive active species. The performance of the as-synthesized samples was evaluated by TCH photodegradation under simulated solar light. Compared to RHNT and BiOCl, the RTB composites, with an optimal sample of RTB-7, showed the enhanced photocatalytic activity for TCH degradation. The characterization results revealed that the enhanced TCH photodegradation activity for RTB composites was due to the synergistic effect of heterojunction formation and oxygen vacancies. During TCH photodegradation for RTB-7, the active radical species were determined by the radical trapping experiments and EPR spectra. The possible TCH photodegradation pathways and mechanism over RTB-7 were explored based on the characterization results. This work offers an effective approach for the rational design and construction of 1D/2D heterostructured photocatalysts with a high efficiency.

Hetero-Motif Molecular Junction Photocatalysts: A New Frontier in Artificial Photosynthesis.

ConspectusTo cope with the increasingly global greenhouse effect and energy shortage, it is urgent to develop a feasible means to convert anthropogenic excess carbon dioxide (CO2) into energy resources. The photocatalytic CO2 reduction reaction (CO2RR) coupled with the water oxidation reaction (WOR), known as artificial photosynthesis, is a green, clean, and promoting strategy to deal with the above issues. Among the reported photocatalytic systems for CO2 reduction, the main challenge is to achieve WOR simultaneously due to the limited charge separation efficiency and complicated dynamic process. To address the problem, scientists have assembled two nanosemiconductor motifs for CO2RR and WOR into a heterojunction photocatalyst to realize artificial photosynthesis. However, it is difficult to clearly explore the corresponding catalytic mechanism and establish an accurate structure-activity relationship at the molecular level for their aperiodic distribution and complicated structural information. Standing on the shoulders of the heterojunction photocatalysts, a new-generation material, hetero-motif molecular junction (HMMJ) photocatalysts, has been developed and studied by our laboratory. A hetero-motif molecular junction is a class of crystalline materials with a well-defined and periodic structure, adjustable assembly mode, and semiconductor-like properties, which is composed of two predesigned motifs with oxidation and reduction, respectively, by coordination or covalent bonds. The intrinsic properties make these catalysts susceptible to functional modifications to improve light absorption and electrical conductivity. The small size and short distance of the motifs can greatly promote the efficiency of photogenerated electron-hole separation and migration. Based on these advantages, they can be used as potential excellent photocatalysts for artificial photosynthesis. Notably, the explicit structural information determined by single-crystal or powder X-ray diffraction can provide a visual platform to explore the reaction mechanism. More importantly, the connection number, spatial distance, interaction, and arrangement mode of the structural motifs can be well-designed to explore the detailed structure-activity relationship that can be hardly studied in nanoheterojunction photocatalyst systems. In this regard, HMMJ photocatalysts can be a new frontier in artificial photosynthesis and serve as an important bridge between molecular photocatalysts and solid photocatalysts. Thus, it is very important to summarize the state-of-the-art of the HMMJ photocatalysts used for artificial photosynthesis and to give in-depth insight to promote future development.In this Account, we have summarized the recent advances in artificial photosynthesis using HMMJ photocatalysts, mainly focusing on the results in our lab. We present an overview of current knowledge about developed photocatalytic systems for artificial photosynthesis, introduce the design schemes of the HMMJ photocatalysts and their unique advantages as compared to other photocatalysts, summarize the construction strategies of HMMJ photocatalysts and their application in artificial photosynthesis, and explain why hetero-motif molecular junctions can be promising photocatalysts and show that they provide a powerful platform for studying photocatalysis. The structure-activity relationship and charge separation dynamics are illustrated. Finally, we bring our outlook on present challenges and future development of HMMJ photocatalysts and their potential application prospects on other photocatalytic reaction systems. We believe that this Account will afford important insights for the construction of high-efficiency photocatalysts and guidance for the development of more photocatalytic systems in an atom-economic, environmentally friendly, and sustainable way.