Highest Hydrogen Evolution Rate Research Articles

Bimetallic MOF-Derived Sulfides with Heterojunction Interfaces Synthesized for Photocatalytic Hydrogen Evolution

The synthesis of highly efficient and stable CdS composites without noble metals has become a hotspot in the photocatalytic field. Although NiS is an ideal candidate, it remains a challenge to optimize the combination of NiS and CdS to improve the photocatalytic activity for hydrogen evolution. Herein, we have successfully synthesized a CdS@NiS photocatalyst using bimetallic metal–organic frameworks (MOFs) as the precursor. The formation of bimetallic Cd/Ni-MOFs can lead to well-contacted heterogeneous interfaces between CdS and NiS at the nanoscale, efficiently promoting the separation of photogenerated carriers and boosting electron interface transfer. The obtained results demonstrated that CdS@NiS exhibits a high photocatalytic hydrogen evolution rate of 42.7 mmol·g–1·h–1, and the corresponding apparent quantum yield reaches 13.23% at 450 nm, superior to those obtained using the traditional simple physical mixing methods. This work provides a promising strategy for the design of new photocatalysts for hydrogen evolution.

Design and fabrication of C–Mn0.5Cd0.5S/Cu3P ternary heterojunction catalyst for photocatalytic hydrogen evolution

Photocatalytic hydrogen evolution from water splitting is a promising strategy to solve the energy demand of human beings. Here, we first designed a C–Mn0.5Cd0.5S/Cu3P ternary heterojunction catalyst for photocatalytic hydrogen production. The results show that the combination of C and Cu3P can effectively improve the photocatalytic activity of Mn0.5Cd0.5S. C–Mn0.5Cd0.5S loading with 5 wt% Cu3P exhibits the highest hydrogen evolution rate (44.1 mmol g−1 h−1), which is 3.2 and 2.8 times higher than that of pure Mn0.5Cd0.5S (13.7 mmol g−1 h−1) and Mn0.5Cd0.5S/3 wt%Pt (15.6 mmol g−1 h−1), respectively. In addition, it shows a high hydrogen evolution rate (19.6 mmol g−1 h−1) under visible light (≥420 nm) irritation and the apparent quantum efficiency (AQE) is detected to be 3.2% at 420 nm. The enhanced photocatalytic activity can be attributed to the good conductivity of C and the formation of p-n heterojunction, which is beneficial for light harvesting and the separation and transportation of charge carriers. Besides, a possible mechanism is proposed. This work provides an effective way to improve the photocatalytic activity of Mn0.5Cd0.5S by using non noble metal co-catalysts.

Interfacial chemical bond and internal electric field modulated Z-scheme Sv-ZnIn2S4/MoSe2 photocatalyst for efficient hydrogen evolution

Construction of Z-scheme heterostructure is of great significance for realizing efficient photocatalytic water splitting. However, the conscious modulation of Z-scheme charge transfer is still a great challenge. Herein, interfacial Mo-S bond and internal electric field modulated Z-scheme heterostructure composed by sulfur vacancies-rich ZnIn2S4 and MoSe2 was rationally fabricated for efficient photocatalytic hydrogen evolution. Systematic investigations reveal that Mo-S bond and internal electric field induce the Z-scheme charge transfer mechanism as confirmed by the surface photovoltage spectra, DMPO spin-trapping electron paramagnetic resonance spectra and density functional theory calculations. Under the intense synergy among the Mo-S bond, internal electric field and S-vacancies, the optimized photocatalyst exhibits high hydrogen evolution rate of 63.21 mmol∙g−1·h−1 with an apparent quantum yield of 76.48% at 420 nm monochromatic light, which is about 18.8-fold of the pristine ZIS. This work affords a useful inspiration on consciously modulating Z-scheme charge transfer by atomic-level interface control and internal electric field to signally promote the photocatalytic performance.

Solar driven photocatalytic hydrogen evolution using graphitic-carbon nitride/NSGQDs heterostructures

The evolution of hydrogen by splitting water and sunlight renders a promising approach to produce scalable and sustainable carbon-free green energy. In this aspect, development of semiconductor heterostructure photocatalyst can spatially separate photogenerated electron-hole at the heterojunction interface and inhibit charge recombination to synergistically enhance photocatalytic performance. Herein, for the first time, we have designed exfoliated graphitic-carbon nitride (g-CN)/N, S co-doped graphene quantum dots (NSGQDs) heterostructure grown by one pot pyrolysis process. NSGQDs create strong π-π interactions with g-CN to construct an effective heterostructure and thus act as a efficient photosensitiser. We have made extensive investigations to understand the nature of g-CN/NSGQDs heterostructure, like optical and electrochemical properties and its shows improved charge transfer kinetics with reduced recombination. As a result, g-CN/NSGQDs heterostructure has achieved significantly high hydrogen evolution rate (HER) of 5.24 mmol h−1 g−1 under sunlight and with the apparent quantum yield (AQY) of 23.2%.

Phosphorus vapor assisted preparation of P-doped ultrathin hollow g-C3N4 sphere for efficient solar-to-hydrogen conversion

The design and synthesis of g-C3N4 with favourable physical-chemical architecture are important factors in influencing its photoactivity. Herein, a phosphorus (P) vapor assisted synthetic strategy was employed to fabricate the P-doped hollow g-C3N4 photocatalysts with ultrathin shell structure (< 25 nm in thickness). The doping of P and the compression of shell thickness of the hollow g-C3N4 were induced simultaneously by the P vapor during the heating process. The as-prepared P-doped ultrathin hollow g-C3N4 sphere (P/UH-CNS) photocatalysts exhibited enlarged surface area and light responsive range, and improved charge transportation efficiency by suppressing the charge recombination and self-trapping within g-C3N4. These resulted in a high photocatalytic hydrogen evolution rate of 9653 μmol h−1 g−1. The charge dynamics in this P/UH-CNS system was revealed in detail by using the ultrafast time-resolved spectroscopy.

Boosting the Photocatalytic Hydrogen Evolution Activity for D-π-A Conjugated Microporous Polymers by Statistical Copolymerization.

Recently, great progress has been achieved in the design and preparation of conjugated organic polymer photocatalysts for hydrogen generation. However, it is still challenging to develop an organic polymer photocatalyst with high photoconversion efficiency. Rational structure design of organic polymer photocatalysts holds the key point to realize high photocatalytic performance. Herein, a series of donor-π-acceptor (D-π-A) conjugated organic copolymer photocatalysts is developed using statistical copolymerization by tuning the feed molar ratio of pyrene (donor) to dibenzothiophene-S,S-dioxide (acceptor) units. It reveals that the photocatalytic activity of the resulting copolymers is significantly dependent on the molar ratio of donor to acceptor, which efficiently changes the polymer structure and component. When the monomer feed ratio is 25:75, the random copolymer PyBS-3 of 10mg with Pt cocatalyst shows a high hydrogen evolution rate of 1.05mmol h-1 under UV/Vis light irradiation using ascorbic acid as the hole-scavenger, and an external quantum efficiency of 29.3% at 420nm, which represents the state-of-the-art of organic polymer photocatalysts. This work demonstrates that statistical copolymerization is an efficient strategy to optimize the polymer structure for improving the photocatalytic activity of conjugated organic polymer catalysts.

Investigating the effect of Nd3+ dopant and the formation of g-C3N4/BiOI heterostructure on the microstructural, optical and photoelectrocatalytic properties of g-C3N4

A two-step thermal poly-condensation and hydrothermal method is used to prepare noble metal-free nano-heterostructure of neodymium (Nd)-doped graphitic carbon nitride (g-C3N4) and bismuth oxyiodide (BiOI). The synthesised Nd- doped g-C3N4/BiOI heterostructure shows high electron-hole separation. Moreover, a fast charge transport at the heterojunction is noted and further leads to low charge recombination rate. Consequently, the synthesised heterostructure overcomes the high charge recombination rate of g-C3N4. This work reports the effect of Nd- doping and the formed heterojunction on the structural, optical, electrical conductivity and photoelectrochemical (PEC) properties of the heterostructure. Moreover, introducing Nd dopant into g-C3N4 enhances visible light absorption of g-C3N4. The optimal hetero-nanostructure (5.0 wt% Nd doped g-C3N4/BiOI) shows high photocurrent density (15.50 mA/cm2) and hydrogen evolution rate (288 μmol h−1 cm−2) under visible light (λ ≥ 420 nm) illumination when compared to other wt.% of Nd doped g-C3N4 and heterostructure. Additionally, the low emission features obtained from the photoluminescence studies and the heterojunction visually observed by HRTEM strongly emphasise that the formation of heterostructure leads to low recombination of charge carriers. Doping and forming heterostructure is shown to be an effective, controllable and an optimal approach to improve the PEC water splitting performance of g-C3N4.

Novel Tetradentate Phosphonate Ligand Based Bioinspired Co-Metal–Organic Frameworks: Robust Electrocatalyst for the Hydrogen Evolution Reaction in Different Mediums

The limited stock of classical nonrenewable energy sources has motivated researchers to explore efficient strategies for sustainable and renewable energy production. Hydrogen production via electrochemical water splitting is one of the key solutions that can meet this demand. Today 3d transition metal based nanomaterials offer a huge opportunity in the hydrogen evolution reaction (HER) via electrochemical water splitting. Herein, we report an easy and convenient synthesis route for designing the novel tetradentate phosphonate ligand based metal–organic framework (MOF, H8L-Co-crystal). The material has been characterized by single crystal X-ray diffraction (SXRD), powder XRD, thermogravimetric analysis, scanning electron microscopy, and Fourier transform infrared spectroscopy, and explored in the HER from various mediums including seawater. This single crystal belongs to the monoclinic phase having C2/c space group, with unit cell parameters a = 29.364(8) (Å), b = 12.204(4) (Å), c = 9.925(3) (Å), α = 90° = γ, β = 97.405° (CCDC no. 1922964) and the unit cell volume = 3527.04 Å3. The material H8L-Co-crystal shows very good catalytic activity towards H2 evolution with a low overpotential of 243 mV at a current density 10 mA/cm2 as well as a low Tafel slope of 102 mV/dec in acidic medium, which is comparable to commercial HER catalysts, and one of the best among non-postsynthetically modified MOFs. The electrochemical active surface area (ECSA) data have been measured to explain the high hydrogen evolution rate in different mediums. Density functional theory (DFT) study based on first-principle calculations provides a very useful understanding about the structure–catalytic property relationship and reveals the role of surface active sites toward electrochemical HER.

In2Se3/CdS nanocomposites as high efficiency photocatalysts for hydrogen production under visible light irradiation

Hydrogen energy is an important clean energy. Using visible light to produce hydrogen by semiconductor photocatalysts is one of the current research hotspots. In this work, In2Se3/CdS nanocomposite photocatalysts with different mass content of CdS are prepared. The In2Se3/CdS photocatalyst with 85.25% CdS mass content exhibits the optimal photocatalytic hydrogen evolution activity (1.632 mmol g−1 h−1), which is much higher than that of CdS (0.715 mmol g−1 h−1) and In2Se3 (trace). Moreover, the In2Se3/CdS photocatalyst still maintains a high hydrogen evolution rate after five cycles. The high photocatalytic activity and stability of the In2Se3/CdS nanocomposite is due to the formation of heterojunction between In2Se3 and CdS. The existence of heterojunction is confirmed by high resolution transmission electron microscopy image and X-ray photoelectron spectra. Theoretical calculations and experimental results indicate that the electron transfer route at the heterojunction is step-scheme. The step-scheme helps the separation of photogenerated electrons and holes, and maximize the hydrogen evolution activity. This work provides a high efficiency step-scheme photocatalyst for hydrogen production.

Enhanced Photocatalytic Performance of Donor–Acceptor-Type Polymers Based on a Thiophene-Contained Polycyclic Aromatic Unit

Donor–acceptor (D–A)-type photocatalysts containing the polycyclic aromatic donor (BTT-CPP) and nonpolycyclic aromatic donor (TTB-CPP) are designed and synthesized. Their physicochemical properties are thoroughly investigated. The photocatalytic hydrogen generation experiments show that both polymers exhibit distinct photocatalytic performance. BTT-CPP displays an attractive hydrogen evolution rate (HER) of 37,866 μmol g–¹ h–¹ without further addition of the metal co-catalyst, one of the highest values reported for organic photocatalysts. The optimal HER of TTB-CPP is 8466 μmol g–¹ h–¹. These results highlight the important role of the donor unit on the performance of D–A-type photocatalysts and demonstrate that thiophene-contained polycyclic aromatic unit BTT is an excellent donor unit for high HER photocatalysts.

Robust Co9S8@CdIn2S4 Cage for Efficient Photocatalytic H2 Evolution

We construct here a highly active and stable Co9S8@CdIn2S4 heterostructure for photocatalytic H2 evolution under visible light. In a hierarchical hollow construction with closely connected heterogeneous shells, two photoactive sulfide semiconductors are incorporated rationally. This unique architecture can efficiently allow photoinduced charges to be separated and transferred and provide a broad surface area and exposure of rich sites for photocatalytic redox reactions. The Co9S8@CdIn2S4 hierarchical hollow heterostructure shows enhanced light-harvesting ability and remarkable catalytic activity because of its distinctive structural and compositional advantages. The photocatalyst shows a high hydrogen evolution rate of 4604 μmol h–1 g–1 without any noble metal as a cocatalyst under 1.5 AM simulated light irradiation. In this work, using the two-dimensional ultrathin subunits with distinct structural and compositional benefits, we show how this material can be interfaced successfully to give intriguing photophysical properties.

Multi-component modeling and simulation of a new photoelectrochemical reactor design for clean hydrogen production

A novel photoelectrochemical cell design to make a unique reactor is developed and investigated to improve solar to hydrogen conversion efficiency and increase the hydrogen evolution rate. A dome-type photocathode and a circular disc anode are immersed in an alkaline electrolyte of potassium hydroxide in two cylindrical compartments. This new reactor design concerns utilizing the maximum sunlight during the daytime due to the dome shape and increasing the photocathode active area. Four different types of analyses and simulations, including energy, exergy, electrochemical and fluid flow, are performed to investigate the present hydrogen reactor performance using both Engineering Equation Solver and COMSOL software packages. Thermodynamic and electrochemical equations are solved, including mass, energy, entropy, and exergy balance equations, as well as the electrochemical equations. The proposed flow circulation shows a significant effect to avoid the hydrogen bubble coverage phenomenon. The influences of varying the illumined photocathode surface area, the solar irradiance flux, and the quantum efficiency are studied on the hydrogen evolution rate and the solar to hydrogen efficiency. The present hydrogen generation rate and the overall energy system efficiency are 42.1 μg/s, 4.9%, respectively, occurring at solar irradiance of 600 W/m2 and the illumined area of 840 cm2. The highest hydrogen evolution rate is 60.20 μg/s achieved at the illumined photocathode area of 1200 cm2. The maximum reactor energy efficiency found to be 6.52% occurred at a quantum efficiency of 20%, respectively. The study results further confirm that increasing the illuminated photocathode area increases the solar to hydrogen energy efficiency and the hydrogen production rates. Moreover, the hydrogen production rates increase with an increase in the solar irradiance.

Zinc sulfide quantum dots/zinc oxide nanospheres/bismuth-enriched bismuth oxyiodides as Z-scheme/type-II tandem heterojunctions for an efficient charge separation and boost solar-driven photocatalytic performance

A novel zinc sulfide quantum dot (ZnS QD)/zinc oxide (ZnO) nanosphere/bismuth-enriched bismuth oxyiodide (Bi4O5I2) tandem heterojunction photocatalyst is fabricated through two-step solvothermal, calcination and one-step hydrothermal strategies. The successfully constructed core-shell nanostructure can increase the interface area and the active sites of the composite photocatalysts. The formation of a Z-scheme/Type-II tandem heterojunction favors the transfer and spatial separation of charge carriers, in which Bi4O5I2 plays a bridging role to connect ZnO and ZnS. Simultaneously, the participation of Bi4O5I2 significantly shortens the band gap of the composite photocatalyst. This dual functional ZnO@Bi4O5I2/ZnS composite photocatalyst has a high photocatalytic hydrogen evolution rate of 578.4 µmol g−1h−1 and an excellent photocatalytic degradation efficiency for bisphenol A (BPA) and 2,4,5-trichlorophenol (TCP). In addition, cycling tests show that ZnO@Bi4O5I2/ZnS has a high stability, which is favorable for practical applications. This novel ZnO@Bi4O5I2/ZnS Z-scheme/Type-II tandem heterojunction photocatalyst will provide new ideas for the multichannel charge transfer of other highly efficient heterojunction photocatalysts.

In Situ Synthesis of Lead-Free Halide Perovskite Cs2AgBiBr6 Supported on Nitrogen-Doped Carbon for Efficient Hydrogen Evolution in Aqueous HBr Solution.

Lead halide perovskites have shown great potential in photovoltaic and photocatalytic fields. However, the toxicity of lead impedes their wide application. Herein composites of lead-free halide perovskite Cs2AgBiBr6 supported on nitrogen-doped carbon (N-C) materials were synthesized successfully through a facile one-pot method for the first time. Without deposition of noble metals as the cocatalyst, the optimal composite Cs2AgBiBr6/N-C (Cs2AgBiBr6/N-C-140) exhibits outstanding photocatalytic performance with a high hydrogen evolution rate of 380 μmol g-1 h-1 under visible light irradiation (λ ≥ 420 nm), which is about 19 times faster than that of pure Cs2AgBiBr6 and 4 times faster than that of physically mixed Cs2AgBiBr6/N-C-140, respectively. The Cs2AgBiBr6/N-C-140 composite also displays high stability with no significant decrease after six cycles of repeated hydrogen evolution experiments. The addition of N-C with a high surface area helps to prevent aggregation of Cs2AgBiBr6 NPs and provides more pathways for the migration of photoinduced carriers. The nitrogen dopant can facilitate photoinduced electron transfer from Cs2AgBiBr6 to N-C to result in spatially separated electrons and holes with prolonged electron time and greatly enhance the photocatalytic performance. This study indicates that Cs2AgBiBr6-based perovskite materials are promising candidates for photocatalytic hydrogen evolution.

Completely Solar-Driven Photoelectrochemical Water Splitting Using a Neat Polythiophene Film

Summary π-Conjugated polymers are emerging as appealing photoelectrode materials for the photoelectrochemical hydrogen evolution reaction via water splitting, which has otherwise been extensively explored using inorganic semiconductors. Here, we report the performance of a pure organic semiconductor film as a catalyst for hydrogen production via visible light-driven water splitting. The neat and unsubstituted polythiophene film, characterized with a well-filled grain morphology of the crystalline polymer, is prepared by a facile polymerization method. The photovoltage of 1.38 V versus RHE at pH 12 enables solar-driven one-electron-per-photon water splitting in combination with a traditional water-oxidation catalyst to produce hydrogen and oxygen separately. The high photoelectrocatalytic hydrogen evolution rate of 1.02 mol(H2) h−1 g−1 or 0.75 mA/cm2 at 0 V versus RHE is also achieved with high durability. This study may open a new window for π-conjugated polymers for ultimately sustainable hydrogen production.

Boosting Visible‐Light‐Driven H2 Evolution of Covalent Triazine Framework from Water by Modifying Ni(II) Pyrimidine‐2‐thiolate Cocatalyst

AbstractCovalent triazine frameworks (CTFs) have recently emerged as prospective photoactive materials coupled with Pt or Pd cocatalyst for the hydrogen evolution. Herein, we report visible‐light driven hydrogen generation catalyzed by heterogeneous systems combining CTF photosensitizers and a noble‐metal‐free cocatalyst for the first time. CTF‐HC2 was doped with two‐dimensional Ni(II) pyrimidine‐2‐thiolate ([Ni(pymt)2]n) to yield a series of x‐[Ni(pymt)2]n/CTF‐HC2 (x=3, 6, 9, 12, 15, 18 and 24 wt %) composites. Illuminated with λ&gt;420 nm, [Ni(pymt)2]n/CTF‐HC2 materials display excellent photocatalytic performance for H2 generation from water. The highest hydrogen evolution rate is up to 3472 μmol h−1 g−1, which is 68 times of bare CTF‐HC2 (51 μmol h−1 g−1) and 1.16 times of CTF‐HC2 doped 2.0 wt % Pt (2991 μmol h−1 g−1). The efficient and recyclable heterogeneous photocatalytic H2 production from water under visible light has been established.

Triptycene-based discontinuously-conjugated covalent organic polymer photocatalysts for visible-light-driven hydrogen evolution from water

Effective photocatalytic systems that are capable of converting solar energy into chemical fuels have recently attracted significant attention. Covalent organic polymers (COPs) have been explored as promising photocatalysts for visible-light-driven hydrogen evolution from water. Herein, a series of triptycene (TP)-based discontinuously conjugated COP photocatalysts are described for the first-time using TP with monothiophene (MT), trithiophene (TT), dithiophene benzothiadiazole (DTBT), and diphenyl benzothiadiazole (DPBT), denoted as MT-TP, TT-TP, DTBT-TP, and DPBT-TP, respectively. Difference photophysical, morphological, and photocatalytic properties can be tuned by introducing different types of linkers of the TP-based COPs. DPBT-TP shows a significant enhancement of the hydrogen evolution rate (HER) in comparison to those using other polymer photocatalysts at identical conditions. The transmission electron microscopy/scanning electron microscopy data show that the tube-like polymer photocatalysts afford higher HERs than those observed with the particle-like polymer photocatalysts. This report describes the first demonstration that the polymer photocatalysts constructed by the disconuiously conjugated system (conjugation length: less than 5 aromatic rings) is sufficient for an efficient visible-light-driven hydrogen evolution. It provides an alternative material design strategy for polymer photocatalysts to achieve efficient visible light hydrogen evolution.

One step synthesis of self-doped F–Ta2O5 nanoshuttles photocatalyst and enhanced photocatalytic hydrogen evolution

Tantalic oxide (Ta2O5), as an excellent transition metal oxide photocatalyst, has been extensively studied on fluorination or self-doped for hydrogen production, while there is little research to combine the two modifications. In this work, surface fluorination self-doped Ta2O5 nanoshuttles (FTNSs) photocatalyst is synthesized successfully by a modified one-step hydrothermal method. The test results show the presence of surface fluorine ions, Ta4+ and oxygen vacancies in the sample. The FTNSs prepared by hydrothermal method under 180 °C for 24 h exhibits the highest hydrogen evolution rate (HER). The HER is 179.2 and 19.78 μmol h−1 g−1 in the absence of any co-catalyst under full-spectrum and simulated solar light, respectively, which is higher than that of the Ta2O5 nanoshuttles without fluoride and the commercial Ta2O5. The higher HER can attribute to the existence of F, Ta4+ and oxygen vacancies, which enhance the photogenerated carrier mobility and reduce the recombination.

Carbon Nitride-Perovskite Composites: Evaluation and Optimization of Photocatalytic Hydrogen Evolution in Saccharides Aqueous Solution

The application of hybrid photocatalysts made of carbon nitride and lead-free perovskites, namely DMASnBr3/g-C3N4 and PEA2SnBr4/g-C3N4, for the H2 evolution from saccharides aqueous solution is described. The novel composites were tested and compared in terms of hydrogen evolution rate (HER) under simulated solar light, using Pt as a reference co-catalyst, and glucose as a representative sacrificial biomass. The conditions were optimized to maximize H2 generation by a design of experiments involving catalyst amount, glucose concentration and Pt loading. For both materials, such parameters affected significantly H2 photogeneration, with the best performance observed using 0.5 g L−1 catalyst, 0.2 M glucose and 0.5 wt% Pt. Under optimized conditions, DMASnBr3/g-C3N4 showed a 5-fold higher HER compared to PEA2SnBr4/g-C3N4, i.e., 925 µmoles g−1 h−1 and 190 µmoles g−1 h−1, respectively (RSD ≤ 11%, n = 4). The former composite, which affords an HER 15-fold higher in aqueous glucose than in neat water, provided H2 also with no metal co-catalyst (around 140 µmoles g−1 h−1), and it was reusable for at least three photoreactions. Encouraging results were also collected by explorative tests on raw starch solution (around 150 µmoles g−1 h−1).

Neat Polythiophene Film: Their Very High Photoelectrochemical Performance Allowing Completely Solar-Driven Water-Splitting

π-Conjugated polymers are emerging as appealing photoelectrode materials for the photoelectrochemical hydrogen evolution reaction via water-splitting, which has otherwise been extensively explored using inorganic semiconductors. Herein we report the very high performance of a pure organic semiconductor film as a catalyst for hydrogen production via visible-light-driven water-splitting. The neat and unsubstituted polythiophene film, characterised with a well-filled grain morphology of the crystalline polymer, was prepared by a facile polymerisation method. The high photovoltage of 1.38 V vs. RHE at pH 12 enables solar-driven one-electron-per-photon water-splitting in combination with a traditional water-oxidation catalyst to produce hydrogen and oxygen separately. The very high photoelectrocatalytic hydrogen evolution rate of 1.02 mol(H2) h-1g-1 or 0.75 mA/cm2 at 0 V vs. RHE was also achieved with high durability. This study opens a new window for π-conjugated polymers for ultimately sustainable hydrogen production.