Photocatalytic Activity For Hydrogen Generation Research Articles

W–N heteroatom-interface in melon carbon nitride/N-doped tungsten oxide Z-Scheme photocatalyst toward improved photocatalytic hydrogen generation activity

The construction of heterointerface in photocatalyst is an efficient approach to boost the separation and utilization efficiency of charge carriers, which is challenging and crucial in photocatalysis. Here, the construction of melon-structured carbon nitride/N-doped WO3 (MCN/NWx) heterojunction photocatalyst was achieved by a method of prealcoholysis combined with thermal polymerization, where N-doping of WO3 was achieved in-situ in the formation of heterojunction. The promoted charge separation efficiency was realized through the charge transfer from the conduction band of N-doped WO3 to the valence band of the MCN. Density functional theory calculation results showed that the formation of the W–N heteroatom-interface led to the increase of density of states at the heterointerface and decrease of the band gap. The MCN/NWx nanocomposite featured a metallic band structure of the nanocomposite photocatalysts, resulting in the enhanced photocatalytic activity. The photocatalytic hydrogen evolution activity of the MCN/NW2 was enhanced about 2.5 times than that of MCN. This research provides a novel insight into the construction of a novel heteroatom-junction that boosts the separation efficiency of charge carriers, and thereby improves the photocatalytic activity.

Pt nanoclusters modified porous g-C3N4 nanosheets to significantly enhance hydrogen production by photocatalytic water reforming of methanol

For the use of green hydrogen energy, it is crucial to have efficient photocatalytic activity for hydrogen generation by water reforming of methanol under mild conditions. Much attention has been paid to g-C3N4 as a promising photocatalyst for the generation of hydrogen. To improve the separation of photogenerated charge, porous nanosheet g-C3N4 was modified with Pt nanoclusters (Pt/g-C3N4) through impregnation and following photo-induced reduction. This catalyst showed excellent photocatalytic activity of water reforming of methanol for hydrogen production with a 17.12 mmol·g−1·h−1 rate at room temperature, which was 311 times higher than that of the unmodified g-C3N4. The strong interactions of Pt–N in Pt/g-C3N4 constructed effective electron transfer channels to promote the separation of photo-generated electrons and holes effectively. In addition, in-situ infrared spectroscopy was used to investigate the intermediates of the hydrogen production reaction, which proved that methanol and water eventually turn into H2 and CO2via formaldehyde and formate. This study provides insights for understanding the photocatalytic hydrogen production in the water reforming of methanol.

Triazine- and porphyrin-based donor-acceptor microporous conjugated polymers for enhanced photocatalytic hydrogen production activity

Donor-acceptor type conjugated microporous polymers (D-A CMPs) have recently gained popularity as active components for photocatalytic hydrogen evolution from water due to their ability to separate the photoinduced holes and electrons efficiently and vastly absorb visible light. However, creating a novel CMP photocatalyst with high photoconversion efficiency is still difficult. Porphyrins and triazines exhibit intriguing electrical and optical features. We present here the directed synthesis and photocatalytic activity in hydrogen generation of two donor-acceptor isostructural triazine- and porphyrin-based conjugated microporous polymers (H-Por-TPT and Zn-Por-TPT CMPs). Our data demonstrate that both CMPs have extremely high specific surface areas (around 650 m2 g−1) and thermal stabilities (Td10: equal to 629 °C with char yields equal to 76.18 wt%). Introducing a Zn atom into a porphyrin ring profoundly influences its optoelectronic properties and photocatalytic efficiency for hydrogen generation from water. Zn-Por-TPT CMP has one of the highest reported values for a D-A CMP, with a photocatalytic hydrogen evolution rate of 11450 μmol g−1 h−1 when exposed to visible light. In addition, the Zn-Por-TPT CMP is notable not just for increasing the rate of hydrogen generation but also for improving photocatalysis stability during prolonged irradiation for roughly 30 h. These CMPs may prove useful as organic photocatalysts in future photocatalytic H2 production from water applications.

TiO2–x@C/MoO2 Schottky junction: Rational design and efficient charge separation for promoted photocatalytic performance

Limited solar light harvesting, sluggish charge transfer kinetics, and inferior affinity for adsorbed hydrogen species (H*) severely restrict the photocatalytic hydrogen generation activity of TiO2 photocatalysts. Herein, we present a novel TiO2–x@C/MoO2 Schottky junction prepared via a simple one-step in situ phase-transition-regulation strategy. Crucially, the abundant oxygen vacancies in TiO2–x@C/MoO2 narrow the bandgap and introduce defects to improve the photoresponse. The strongly bonded carbon layer not only serves as a fast charge-transport channel to improve the interlayer charge transfer efficiency but also protects oxygen vacancies from oxidation. Moreover, the Schottky barrier effectively impairs the recombination of electrons and holes and promotes the utilization of photogenerated electrons. Furthermore, the MoO2 cocatalyst optimizes the Gibbs free energy for H2 evolution. As a result of the favorable synergy, the resulting TiO2–x@C/MoO2 presents a significantly enhanced photocatalytic H2 production rate of 506 μmol g−1 h−1 compared to those of TiO2–x and TiO2–x@C (125.5- and 15.8-times larger, respectively). Moreover, outstanding stability over 27 h was achieved because of the protection provided by the surface carbon layer. This ingenious design and facile synthetic strategy offer exciting avenues for the design of strongly coupled Schottky junction photocatalysts for efficient solar-to-chemical conversions.

Single-Atom Sn-Loaded Exfoliated Layered Titanate Shows Photocatalytic Activity in Hydrogen Generation.

Single-Atom Sn-Loaded Exfoliated Layered Titanate Shows Photocatalytic Activity in Hydrogen Generation.

Increasing the Photocatalytic Hydrogen Generation Activity of CdS Nanorods by Introducing Interfacial and Polarization Electric Fields.

Cadmium sulfide (CdS) is a photocatalyst widely used for efficient H2 production under visible light irradiation, due to its narrow bandgap and suitable conduction band position. However, the fast recombination of carriers results in their low utilization. In order to improve photocatalytic hydrogen production, it reports the successful introduction of metallic Cd and S vacancies on CdS nanorods (CdS NRs) by a facile in situ chemical reduction method, using a thermal treatment process. This procedure generates interfacial and polarization electric fields, that significantly improve the photocatalytic hydrogen production performance of CdS NRs in sodium sulfide and sodium sulfite aqueous solutions, under visible light irradiation (λ>420nm). The introduction of these electric fields is believed to improve charge separation and facilitate faster interfacial charge migration, resulting in a significantly optimized catalyst, with a photocatalytic hydrogen evolution rate of up to 10.6mmol-1 g-1 h-1 with apparent quantum efficiency (AQE) of 12.1% (420nm), which is 8.5 times higher than that of CdS. This work provides a useful method to introduce metallic and S vacancies on metal sulfide photocatalysts to build local polarization and interfacial electric fields for high-performance photocatalytic H2 production.

Constructing CdIn2S4/ZnS type-I band alignment heterojunctions by decorating CdIn2S4 on ZnS microspheres for efficient photocatalytic H2 evolution

In this study, a series of promising binary hybrid heterojunction CdIn2S4/ZnS (CIS/ZnS) were constructed via a facile hydrothermal method. Credible characterization methods including powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV–vis diffuse reflectance spectra (DRS) were carried out to investigate the physicochemical properties the as-obtained photocatalysts. Photocatalytic water splitting for hydrogen evolution was performed to evaluate the photocatalytic activity of the photocatalyst. The results indicate that the light-harvesting ability could be markedly enhanced by decorating CdIn2S4 on ZnS microspheres. Compared with the pristine CdIn2S4 and ZnS, the hybrid photocatalysts present more efficient photocatalytic hydrogen production performance. Among composite photocatalysts, the 5% CIS/ZnS sample manifests the highest photocatalytic hydrogen production rate of 10.80 mmol g−1 h−1, which is 2.6 and 5.4 times higher than that of ZnS and CdIn2S4, respectively. Moreover, a type-I band alignment mechanism was prudently put forward to interpret the photocatalytic hydrogen generation activity. The boosted photocatalytic hydrogen evolution activities of CIS/ZnS can be attributed to the enhanced light-harvesting ability, efficient separation and transfer of the photo-induced charge carriers, and inhibition of electrons and holes recombination of binary hybrid CIS/ZnS photocatalysts.

The influence of the size of a one-faced metallic head in Janus nanoparticles as a co-catalyst on the photocatalytic efficiency of hydrogen evolution under vis light irradiation

Janus nanoparticles (NPs) consisting of MoOxSy nanospheres and silver (Ag) head, successfully developed by a simple, controlled method were in the first time they were applied as a co-catalysts in photocatalytic hydrogen generation reaction under vis light irradiation (λ > 420 nm). The MoOxSy-Ag as a co-catalysts were deposited on the obtained ZnIn2S4 microspheres (ZIS) using physical absorption method. The influence of the size of a one-faced metallic head (Ag) in JNPs as a co-catalyst on the photocatalytic efficiency of hydrogen evolution has been investigated. Sample 2.5-Ag-MoOxSy@ZIS with the co-catalyst with the smallest head in the range of about 61–71 nm was characterized by 34 times higher photocatalytic hydrogen generation activity compared to pure ZIS. JNPs as a co-catalyst are characterized as asymmetric structure and precisely adjusted interface and thus, they influence on a very good electron mobility in hybrid metal-semiconductor nanostructures. JNPs can be a new alternativity to metal co-catalysts used in a photocatalytic hydrogen production reaction.

Covalent Functionalization of CdSe Quantum Dot Films with Molecular [FeFe] Hydrogenase Mimics for Light-Driven Hydrogen Evolution.

CdSe quantum dots (QDs) combined with [FeFe] hydrogenase mimics as molecular catalytic reaction centers based on earth-abundant elements have demonstrated promising activity for photocatalytic hydrogen generation. Direct linking of the [FeFe] hydrogenase mimics to the QD surface is expected to establish a close contact between the [FeFe] hydrogenase mimics and the light-harvesting QDs, supporting the transfer and accumulation of several electrons needed to drive hydrogen evolution. In this work, we report on the functionalization of QDs immobilized in a thin-film architecture on a substrate with [FeFe] hydrogenase mimics by covalent linking via carboxylate groups as the anchoring functionality. The functionalization was monitored via UV/vis, photoluminescence, IR, and X-ray photoelectron spectroscopy and quantified via micro-X-ray fluorescence spectrometry. The activity of the functionalized thin film was demonstrated, and turn-over numbers in the range of 360-580 (short linkers) and 130-160 (long linkers) were achieved. This work presents a proof-of-concept study, showing the potential of thin-film architectures of immobilized QDs as a platform for light-driven hydrogen evolution without the need for intricate surface modifications to ensure colloidal stability in aqueous environments.

Carbon-based nanomaterials: Characteristics, dimensions, advances and challenges in enhancing photocatalytic hydrogen production

The majority of research in the carbon-based nanomaterials (CNMs) field has concentrated on the classification and synthesis of CNMs, with relatively few studies focusing on CNMs’ roles in photocatalytic hydrogen production. CNMs have proven their potential as an effective addition to the appeal of photocatalytic hydrogen evolution because of their superior chemical and physical properties. This paper explores the recent advancements in photocatalytic hydrogen (H2) production utilizing CNMs. As evidenced in the literature, carbon quantum dot (CQD)-sensitized titanium dioxide (TiO2) can demonstrate to have a photocatalytic hydrogen generation activity of 472 mol g−1 h−1 and 1458 mol g−1 h−1 without and with loading metal co-catalyst (Pt). The optimum catalyst, 0.4 CQD/CdS, contributes to the highest H2 production rate of 309 mmol g−1 h−1 (apparent quantum yield of 32.6%), which is 1.5 times greater than that of bare CdS. This would significantly accelerate the hydrogen production process. There are still challenges to reaching maximum photocatalytic hydrogen production, including low hydrogen storage. The overall price of hydrogen produced via photocatalysis is also higher because of the energy needed to store the hydrogen. Even though the problem is not directly related to the usage of CNMs, this restriction generates uncertainty and limits commercial investment. Given the rising demand for energy and the trend toward green power, it is recommended that extensive industrial uses of photocatalytic hydrogen produced by employing CNMs be investigated for better and more sustainable energy frameworks.

Single-Atom Sn-Loaded Exfoliated Layered Titanate Revealing Enhanced Photocatalytic Activity in Hydrogen Generation.

Green H2 generation through layered materials plays a significant role among a wide variety of materials owing to their high theoretical surface area and distinctive features in (photo)catalysis. Layered titanates (LTs) are a class of these materials, but they suffer from large bandgaps and a layers' stacked form. We first address the successful exfoliation of bulk LT to exfoliated few-layer sheets via long-term dilute HCl treatment at room temperature without any organic exfoliating agents. Then, we demonstrate a substantial photocatalytic activity enhancement through the loading of Sn single atoms on exfoliated LTs (K0.8Ti1.73Li0.27O4). Comprehensive analysis, including time-resolved photoluminescence spectroscopy, revealed the modification of electronic and physical properties of the exfoliated layered titanate for better solar photocatalysis. Upon treating the exfoliated titanate in SnCl2 solution, a Sn single atom was successfully loaded on the exfoliated titanate, which was characterized by spectroscopic and microscopic techniques, including aberration-corrected transmission electron microscopy. The exfoliated titanate with an optimal Sn loading exhibited a good photocatalytic H2 evolution from water containing methanol and from ammonia borane (AB) dehydrogenation, which was not only enhanced from the pristine LT, but higher than conventional TiO2-based photocatalysts like Au-loaded P25.

Fabrication of heterostructured Pd-porphyrin MOFs/ZnIn2S4composites to boost photocatalytic hydrogen evolution under visible light irradiation

The Pd-PMOFs@ZIS heterostructures exhibit prominently enhanced photocatalytic hydrogen generation activity.

WO3–x/PbS/Au Ternary Heterojunction Nanostructures for Visible-Light-Driven Photocatalytic Hydrogen Generation

The design of photocatalyst with excellent light-harvesting and charge-separation abilities is quite important for high-performance photocatalysis. Herein, narrow-bandgap PbS, wide-bandgap WO3–x, and Au nanoparticles were combined to form a plasmon-mediated Z-scheme nanostructure for the first time. Particularly, PbS nanoparticles were deposited on oxygen-abundant WO3–x nanobricks, then Au nanoparticles were grown on the hybrids to form WO3–x/PbS/Au ternary nanostructures. Because of the cooperation of wide and narrow bandgaps as well as the oxygen vacancies and plasmon, the ternary hybrids displayed wide light absorption ranging from ultraviolet to near-infrared region. Meanwhile, the energy band arrangement of PbS and WO3–x provides a direct Z-scheme pathway and built-in electric field for charge transfer and separation. As a result, WO3–x/PbS hybrids displayed a large enhancement on photocatalytic hydrogen generation activity compared with the components under visible light irradiation, which is 9.2 and 9.8 times of WO3–x and PbS, respectively. Furthermore, the WO3–x/PbS/Au ternary hybrids showed the best photocatalytic performance that is 21.8 and 2.4 times of WO3–x and WO3–x/PbS hybrids. Meanwhile, the ternary photocatalysts possessed prominent apparent quantum efficiency under near-infrared light irradiation. The prominent photocatalytic performance can be attributed to the broadband light absorption, enhanced specific surface area, efficient charge transfer and separation induced by the oxygen-vacancy and plasmon-mediated Z-scheme band energy structure.

Enhanced photocatalytic hydrogen evolution from reduced graphene oxide-defect rich TiO2-x nanocomposites

Solar-driven photocatalytic hydrogen generation by splitting water molecules requires an efficient visible light active photocatalyst. This work reports an improved hydrogen evolution activity of visible light active TiO2-x photocatalyst by introducing reduced graphene oxide via an eco-friendly and cost-effective hydrothermal method. This process facilitates graphene oxide reduction and incorporates intrinsic defects in TiO2 lattice at a one-pot reaction process. The characteristic studies reveal that RGO/TiO2-x nanocomposites were sufficiently durable and efficient for photocatalytic hydrogen generation under the visible light spectrum. The altered band gap of TiO2-x rationally promotes the visible light absorption, and the RGO sheets present in the composites suppresses the electron-hole recombination, which accelerates the charge transfer. Hence, the noble metal-free RGO/TiO2-x photocatalyst exhibited hydrogen production with a rate of 13.6 mmol h−1g−1cat. under solar illumination. The appreciable photocatalytic hydrogen generation activity of 947.2 μmol h−1g−1cat with 117 μAcm−2 photocurrent density was observed under visible light (>450 nm).

Engineering multifunctional carbon black interface over Mn0.5Cd0.5S nanoparticles/CuS nanotubes heterojunction for boosting photocatalytic hydrogen generation activity

Developing exceptionally robust and cost-effective cocatalysts to suppress charge recombination and reduce the reaction energy barrier remains an enormous challenge for producing high-valued and storable hydrogen fuel from photocatalytic water splitting. Herein, novel Mn0.5Cd0.5S nanoparticles modified with multifunctional carbon black (CB) nanowires and CuS nanotubes as dual cocatalysts were fabricated via sonochemical loading, and subsequent in-situ deposition routes. In this ternary hierarchical architecture, both CB nanowires and CuS nanotubes can serve as normal electron cocatalysts to markedly promote the hydrogen generation performance by lowering the thermodynamic overpotential for hydrogen evolution. Moreover, due to the high electrical conductivity, the multifunctional CB material can also function as a bridge to effectively capture and transmit the photoexcited electrons from Mn0.5Cd0.5S to CuS with outstanding electrocatalytic hydrogen evolution activity, thus maximizing the carrier separation and H2-evolution reaction kinetics. Interestingly, the cooperative effects between CB and CuS dual cocatalysts are also helpful for improving the oxidation capacity of photoexcited holes by lowering the valence band position of Mn0.5Cd0.5S, which further accelerates the electron-hole separation. As a result, the constructed Mn0.5Cd0.5S/CB/CuS hierarchical multiheterojunction catalyst shows the superior hydrogen generation efficiency of 819.9 μmol h−1 and excellent stability under simulated solar light irradiation.

Manganese phosphorous trifulfide nanosheets and nitrogen doped carbon dot composites with manganese vacancies for a greatly enhanced hydrogen evolution

As a novel chalcogenide photocatalyst, MnPS3 suffered from limited visible light absorption, high photogenerated electron-hole recombination, and low hole oxidation capability due to its high valence band (VB) potential. In this work, the novel MnPS3 nanosheets-Nitrogen-doped carbon dots (NCDs) composites were fabricated by immobilizing NCDs with terminal amine groups on Na+ intercalated MnPS3 nanosheets for a greatly enhanced photocatalytic hydrogen production activity. MnPS3 nanosheets of 400 nm with Mn2+ vacancies are produced in high yield by NaCl intercalation and subsequent exfoliation in N-methylpyrrolidone (NMP). NCDs with 5 nm are evenly loaded on the surface of MnPS3 nanosheets of 400 nm via strong chemical interactions of ammonium sulfate salts formed at the interface. The MnPS3-NCDs composites exhibit enhanced light absorption at 500–600 nm, reduced charge recombination and notably promoted photocatalytic activity in relative to neat MnPS3 nanosheets. MnPS3-NCDs composite with the NCDs content of 16.5% possessed the highest photocatalytic hydrogen evolution rate of 339.63 μmol·g−1·h−1 with good cycling stability, which is 9.17 times that of exfoliated MnPS3 nanosheets. The type-II MnPS3-NCDs heterojunction is conducive to the efficient interfacial carrier transport and the significantly improved photocatalytic hydrogen generation activity. Our work confirmed that the non-toxic MnPS3 could possess photocatalytic performance comparable to CdS, which will be promising to become an attractive visible-light driven photocatalyst in environmental purification and energy applications.

Tailoring Plasmonic Bimetallic Nanocatalysts Toward Sunlight‐Driven H2 Production

AbstractHybrid nanoparticles combining plasmonic and catalytic components have recently gained interest for their potential use in sunlight‐to‐chemical energy conversion. However, a deep understanding of the structure–performance that maximizes the use of the incoming energy remains elusive. Here, a suite of Au and Pd based nanostructures in core–shell and core‐satellites configurations are designed and their photocatalytic activity for Hydrogen (H2) generation under sunlight illumination is tested. Formic acid is employed as H2 source. Core‐satellite systems show a higher enhancement of the reaction upon illumination, compared to core–shell ones. Electromagnetic simulations reveal that a key difference between both configurations is the excitation of highly localized and asymmetric electric fields in the gap between both materials. In this scheme, the core Au particle acts as an antenna, efficiently capturing visible light via the excitation of localized plasmon resonances, while the surrounding Pd satellites transduce the locally‐enhanced electric field into catalytic activity. These findings advance the understanding of plasmon‐driven photocatalysis, and provide an important benchmark to guide the design of the next generation of plasmonic bimetallic nanostructures.

A novel Dy3+ modified Zn2Ti3O8 nanoparticles for efficient hydrogen production photocatalysis

Novel Dy 3+ :Zn 2 Ti 3 O 8 (Dy 3+ :ZTO) nano-photocatalysts with different Dy 3+ concentrations were applied to enhance the photocatalytic hydrogen generation activity from sodium borohydride hydrolysis reaction. XRD and Raman measurements confirm the formation of cubic Zn 2 Ti 3 O 8 phase as a major phase in addition to minor TiO 2 phase. The analysis of XPS spectra shows the existence of lattice oxygen (LO) and non-lattice oxygen (NLO) where 0.07 mol Dy 3+ :ZTO has the highest percentage of NLO compared to the undoped photocatalyst. The energy gap value decreases with increasing doping concentrations (3.137 eV for 0.07 mol Dy 3+ :ZTO). The degree of disorder, represented by Urbach energy, has an optimum high value (0.169 eV) for 0.07 mol Dy 3+: ZTO. The photoluminescence studies revealed that Dy 3+ dopant can effectively separate the photogenerated electron/hole pairs in the ZTO. These photocatalysts have strong photocatalytic hydrogen generation. The most active nano-photocatalyst towards hydrogen generation was 0.07 mol Dy 3+ : ZTO (5.6 mmol/g). The highest photocatalytic activity for 0.07 mol Dy 3+ : ZTO are attributed to the lower recombination rate associated with the higher disorder and oxygen vacancies relative to the undoped photocatalyst. The stability and reusability of the most active photocatalyst were investigated. The results confirm that the developed photocatalyst has good durability in hydrogen generation reaction. The results, moreover, revealed that Dy 3+ : ZTO nano-photocatalyst is a promising nanomaterial in the field of energy production. Graphical illustration for the hydrogen generation. • Novel Dy 3+ :Zn 2 Ti 3 O 8 (Dy 3+ :ZTO) nano-photocatalysts were prepared. • Dy 3+ dopant can effectively separate the photogenerated carriers in the ZTO. • Dy 3+ :ZTO enhances the photocatalytic activity of hydrogen generation. • Catalyst reusability and stability of 0.07 mol Dy 3+ :ZTO was tested.

Bi@H-TiO2/B-C3N4 heterostructure for enhanced photocatalytic hydrogen generation activity under visible light

Herein, a ternary Bi@H-TiO2/B-C3N4 type II heterostructure is successfully designed and prepared via metal Bi as cocatalyst for photocatalytic H2 generation. As expected, under λ > 300 nm light, the highest photocatalytic hydrogen production rate (HPR) of Bi@H-TiO2/B-C3N4 is up to 223.08 μmol g−1 h−1. Excitingly, under visible light (λ > 400 nm), the highest HPR of Bi@H-TiO2/B-C3N4 is increased to 18.84 μmol g−1 h−1, which is about 67.3 times, 37.7 times and 6.8 times as high as that of H-TiO2, B-C3N4 and H-TiO2/B-C3N4 under the same conditions, respectively. Moreover, the electrochemical impedance spectroscopy and transient photocurrent tests manifest that the interface resistance of Bi@H-TiO2/B-C3N4 composite decreases and the photocurrent density increases after loading metal Bi. These results indicate that loading metal Bi as cocatalyst (providing more electron trapping sites) is beneficial to improve photocatalytic activity in the type II heterostructure composite. And the electron transfer directions (B-C3N4 → H-TiO2 → Bi or B-C3N4 → Bi) are proved by ultraviolet photoelectron spectroscopy test. Therefore, the Bi@H-TiO2/B-C3N4 photocatalyst with strong visible light absorption is expected to be a promising candidate in photocatalytic fields under visible light.

Meso‐Microporous Nanosheet‐Constructed 3DOM Perovskites for Remarkable Photocatalytic Hydrogen Production

AbstractThree‐dimensionally ordered macroporous (3DOM) structures have been widely utilized to largely enhance a photocatalytic activity. However, the common nanoparticles‐constructed 3DOM photocatalysts possess numerous grain boundaries, unavoidably leading to a fast recombination of photogenerated electrons and holes. Herein, for the first time, a hierarchically two‐dimensional (2D) meso‐microporous perovskite nanosheet‐constructed 3DOM CaTiO3 to significantly reduce the grain boundaries is designed and fabricated. Using carbon quantum dots (CQDs) as a metal‐free co‐catalyst, the 3DOM CQDs‐CaTiO3 exhibits an outstanding photocatalytic activity for hydrogen generation of 0.13 mmol h−1 (20 mg photocatalyst) with remarkable apparent quantum efficiency (QAY) of 14.55% at 365 nm monochromatic light. This unprecedented performance is endowed by the synergy of a macro‐meso‐microporosity architecture, a large surface area, enhanced light harvesting, and improved charge carriers separation and transport. Density functional theory calculations and finite difference time‐domain simulations further reveal the mechanism behind the enhanced separation of photogenerated electrons and holes. The present work demonstrates a trial on rationally designing meso‐microporous nanosheet‐constructed 3DOM perovskites for solar driven hydrogen production.