Photocatalytic H2 Production Research Articles

Modulating the Microenvironments of Robust Metal Hydrogen‐Bonded Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution

AbstractHydrogen‐bonded organic frameworks (HOFs) are outstanding candidates for photocatalytic hydrogen evolution. However, most of reported HOFs suffer from poor stability and photocatalytic activity in the absence of Pt cocatalyst. Herein, a series of metal HOFs (Co2‐HOF‐X, X=COOMe, Br, tBu and OMe) have been rationally constructed based on dinuclear cobalt complexes, which exhibit exceptional stability in the presence of strong acid (12 M HCl) and strong base (5 M NaOH) for at least 10 days. More impressively, by varying the ‐X groups of the dinuclear cobalt complexes, the microenvironment of Co2‐HOF‐X can be modulated, giving rise to obviously different photocatalytic H2 production rates, following the −X group sequence of −COOMe>−Br>−tBu>−OMe. The optimized Co2‐HOF‐COOMe shows H2 generation rate up to 12.8 mmol g−1 h−1 in the absence of any additional noble‐metal photosensitizers and cocatalysts, which is superior to most reported Pt‐assisted photocatalytic systems. Experiments and theoretical calculations reveal that the −X groups grafted on Co2‐HOF‐X possess different electron‐withdrawing ability, thus regulating the electronic structures of Co catalytic centres and proton activation barrier for H2 production, and leading to the distinctly different photocatalytic activity.

Optimizing Photocatalytic H2 Production by Introduction of Pyrazinyls to WRCs and a New tris-Rhenium Photosensitizer.

The replacement of pyridyl by pyrazinyl in ligands of polypyridyl-based cobalt water reducing catalysts (WRC) shifts reduction potentials anodically. Together with a new, trinuclear ReI photosensitizer, these WRCs show strongly improved photocatalytic performances in turnover numbers (TONs) and maximal H2 evolution rate. Depending on the catalyst structure, up to 65 kTONs at 1 μM WRC concentration were reached. Under electrocatalytic conditions in both DMF and H2O, one of the reported WRCs displays remarkable stability, producing H2 steadily over 21 and 14 d, respectively.

Constructing cascade electric fields and sulfur vacancies in Ni3S4/NiS2/v-Zn3In2S6 photocatalyst for efficient degradation of contaminants and H2 production

The increasing environmental pollution and looming energy crisis necessitate the development of advanced photocatalysts that demonstrate efficient separation and transfer of the photo-generated holes and electrons, as well as multiple functions to address the above issues. Herein, a bifunctional Ni3S4/NiS2/v-Zn3In2S6 photocatalyst has been constructed to degrade environmental hormones and antibiotics with simultaneous H2 production. Sulfur vacancies have been engineered in the Zn3In2S6 from a kinetic point of view to accelerate the separation of photogenerated charge carriers and act as active sites. Ni3S4 and NiS2 are introduced to construct cascade electric fields with Zn3In2S6 via ohmic junctions for spatially separated charge carriers and reduced hydrogen evolution potential. As a result, the composite exhibits enhanced photocatalytic H2 production and efficient degradation of bisphenol A, norfloxacin, and tetracycline, respectively. Specifically, the degradation pathways of BPA have been investigated based on Fukui calculations and liquid chromatography-mass spectrometry techniques. This work may shed new light on the design and construction of dual-function photocatalysts for wastewater treatment and H2 production.

A Schottky/Z-Scheme Hybrid for Augmented Photocatalytic H2 and H2O2 Production.

The prodigious employment of fossil fuels to conquer the global energy demand is becoming a dreadful threat to the human society. This predicament is appealing for a potent photocatalyst that can generate alternate energy sources via solar to chemical energy conversion. With this interest, we have fabricated a ternary heterostructure of Ti3C2 nanosheet modified g-C3N4/Bi2O3 (MCNRBO) Z-scheme photocatalyst through self-assembly process. The morphological analysis clearly evidenced the close interfacial interaction between g-C3N4 nanorod, Bi2O3 and Ti3C2 nanosheets. The oxygen vacancy created on Bi2O3 surface, as suggested by XPS and EPR analysis, supported the Z-scheme heterojunction formation between g-C3N4 nanorod and Bi2O3 nanosheets. The collaborative effect of Z-scheme and Schottky junction significantly reduced charge transfer resistance promoting separation efficiency of excitons as indicated from PL and EIS analysis. The potential of MCNRBO towards photocatalytic application was investigated by H2O2 and H2 evolution reaction. A superior photocatalytic H2O2 and H2 production rate for MCNRBO is observed, which are respectively around 5 and 18 folds higher as compared to pristine CNR nanorod. The present work encourages for the development of a noble, eco-benign and immensely efficient dual heterojunction based photocatalyst, which can acts as saviour of human society from energy crisis.

Constructing magnetically propelled piezoelectric and pyroelectric bifunctional micromotors to boost the photocatalytic H2 production involving biomass reforming

Biomass-assisted photocatalytic water splitting for hydrogen (H2) production has attracted widespread interest, which is important for the development of green H2 energy and the high value-added utilization of biomass. Although photothermal utilization can improve solar energy conversion efficiency, the elevated temperature also enhances the likelihood of electron-hole collisions. Herein, magnetically propelled PVDF/Fe3O4@g-C3N4 spiral micromotors were constructed to easily foster the synergistic coupling of piezoelectric and pyroelectric effects, which is beneficial to enhance the directional migration of photogenerated carriers at high temperatures. With both piezo- and pyroelectric effects, the biomass glucose involved H2 production rate on PVDF/Fe3O4@g-C3N4 spiral micromotors is 42.3 μmol/h, representing a significant increase of 31.9 times compared to water splitting without these effects, and the average apparent quantum yield at ordinary pressure can reach 12.6 %. Furthermore, photoluminescence and variable-temperature electrochemistry demonstrate that the piezo-pyroelectric coupling can accelerate the separation of carriers. Meanwhile, COMSOL simulations and KPFM tests show that the built-in electric field of the sample is enhanced under the piezo-pyroelectric effect. The spiral micromotors can easily realize the synergism of piezoelectric and pyroelectric effects, which provides an effective strategy to enhance the built-in electric field and thereby improve the performance of photocatalytic H2 evolution involving biomass reforming.

Engineering of LiTaO3 Nanoparticles by Flame Spray Pyrolysis: Understanding In Situ Li-Incorporation into the Ta2O5 Lattice.

Lithium tantalate (LiTaO3) perovskite finds wide use in pyroelectric detectors, optical waveguides and piezoelectric transducers, stemming from its good mechanical and chemical stability and optical transparency. Herein, we present a method for synthesis of LiTaO3 nanoparticles using a scalable Flame Spray Pyrolysis (FSP) technology, that allows the formation of LiTaO3 nanomaterials in a single step. Raman, XRD and TEM studies allow for comprehension of the formation mechanism of the LiTaO3 nanophases, with particular emphasis on the penetration of Li atoms into the Ta-oxide lattice. We show that, control of the High-Temperature Particle Residence Time (HTPRT) in the FSP flame, is the key-parameter that allows successful penetration of the -otherwise amorphous- Li phase into the Ta2O5 nanophase. In this way, via control of the HTPRT in the FSP process, we synthesized a series of nanostructured LiTaO3 particles of varying phase composition from {amorphous Li/Ta2O5/LiTaO3} to {pure LiTaO3, 15-25 nm}. Finally, the photophysical activity of the FSP-made LiTaO3 was validated for photocatalytic H2 production from H2O. These data are discussed in conjunction with the role of the phase composition of the LiTaO3 nanoparticles. More generally, the present work allows a better understanding of the mechanism of ABO3 perovskite formation that requires the incorporation of two cations, A and B, into the nanolattice.

Electrostatic Self-Assembly of CdS Quantum Dots with Co9S8 Hollow Nanotubes for Enhanced Visible Light Photocatalytic H2 Production.

CdS quantum dots (CdS QDs) are regarded as a promising photocatalyst due to their remarkable response to visible light and suitable placement of conduction bands and valence bands. However, the problem of photocorrosion severely restricts their application. Herein, the CdS QDs-Co9S8 hollow nanotube composite photocatalyst has been successfully prepared by loading Co9S8 nanotubes onto CdS QDs through an electrostatic self-assembly method. The experimental results show that the introduction of Co9S8 cocatalyst can form a stable structure with CdS QDs, and can effectively avoid the photocorrosion of CdS QDs. Compared with blank CdS QDs, the CdS QDs-Co9S8 composite exhibits obviously better photocatalytic hydrogen evolution performance. In particular, CdS QDs loaded with 30% Co9S8 (CdS QDs-30%Co9S8) demonstrate the best photocatalytic performance, and the H2 production rate reaches 9642.7 μmol·g-1·h-1, which is 60.3 times that of the blank CdS QDs. A series of characterizations confirm that the growth of CdS QDs on Co9S8 nanotubes effectively facilitates the separation and migration of photogenerated carriers, thereby improving the photocatalytic hydrogen production properties of the composite. We expect that this work will facilitate the rational design of CdS-based photocatalysts, thereby enabling the development of more low-cost, high-efficiency and high-stability composites for photocatalysis.

One step co-deposition of Ni0.96S and Ag2S on TiO2 nanosheets for enhanced photocatalytic H2 generation with superior stability

Introduction of co-catalysts to construct heterojunctions is one of the important strategies to improve the photocatalytic hydrogen production activity of semiconductor catalysts. Here, Ni0.96S and Ag2S co-decorated TiO2 composites were prepared by a simple one-step solvothermal method, whose photocatalytic H2 production activities were evaluated and related H2 evolution mechanism was explored. The 5%Ni0.96S-8%Ag2S/TiO2 ternary composite exhibited much enhanced photocatalytic activity with the photocatalytic hydrogen evolution rate (HER) of 23.67 mmol·h−1·g−1, which is 131.5 fold higher than that of the pure TiO2. Even higher HER, 29.45 mmol·h−1·g−1, was obtained in the presence of 40 mL glycerol. The photocatalytic HERs of the 5%Ni0.96S-8%Ag2S/TiO2 catalyst under visible light (λ > 420 nm) and simulated solar light (AM1.5) were 353.78 and 935.24 µmol·h−1·g−1, respectively. The apparent quantum efficiency (365 nm) is as high as 13.9%. Remarkably, the catalyst exhibited excellent photocatalytic cycling stability and durability, beneficial to practice applications. The improved photocatalytic activity of the composite can be attributed to much improved charge carrier transfer/separation, optimized energy band structure and enhanced visible light absorption caused by synergistic effect of Ni0.96S and Ag2S.

Synergistic effect of NiO-loaded gold NPs modified exfoliated graphitic carbon nitride (E-gC3N4) with the role of hot electrons and hole scavengers for boosting solar hydrogen production

The photocatalytic hydrogen production capabilities of a well-designed NiO–Au loaded exfoliated graphitic carbon nitride (E-gC3N4) were evaluated after it was synthesized in a straightforward, template-free, single-step process. This study delves into the synergistic impact of utilizing exfoliated g-C3N4 (E-gC3N4) loaded with NiO to trap electrons and plasmonic Au to elevate solar-driven H2 evolution through the surface plasmon resonance effect. Using 2 % NiO/E-gC3N4 and 0.3 % Au/E-gC3N4 samples, the H2 yield of 2620 and 2725 μmol g−1, were obtained, which were 25 and 26 folds higher than using bulk g-C3N4, respectively. The highest photocatalytic H2 production of 4750 μmol g−1 was obtained with 1 % NiO-0.3 % Au/E-gC3N4, which was 1.74, 1.81 and 45.24-fold more than it was produced with 0.3 % Au/E-gC3N4, 2 % NiO/E-gC3N4 and bulk g-C3N4 samples, respectively. Increased visible light absorption and charge production due to the SPR effect of Au and efficient charge separation due to NiO co-catalyst led to an increase in H2 generation. The composite was also stable for the consecutive four cycles, in which continuous H2 evolution was obtained. This novel strategy offers promise for synthesizing effective composites for visible-light-driven H2 evolution.

InVO4-Decorated Ti3C2 MXene for Efficient Photocatalytic Hydrogen Evolution.

The generation of hydrogen through photocatalysis is a fascinating technology for addressing environmental concerns and the energy crisis. Nevertheless, the quest for cost-effective, stable, and efficient photocatalysts in the realm of energy conversion remains a significant challenge. Herein, we designed novel InVO4/Ti3C2 MXene (IVTC) heterostructures by employing acid etching to produce Ti3C2 MXene with an accordion-like morphology, using the hydrothermal technique for the production of orthorhombic InVO4 nanoparticles (NPs), and integrating them through a self-assembly approach. Both field-emission scanning electron microscopy and HRTEM analyses revealed a consistent distribution of InVO4 NPs with an average size of 43.4 nm on both surfaces and between the sheets of Ti3C2 MXene. The intimate interface between the Ti3C2 MXene nanosheet and InVO4 suppressed carrier recombination and promoted charge transfer, thereby boosting photocatalytic H2 production. Under visible light exposure, the rate of hydrogen evolution is enhanced in IVTC heterostructures containing an optimized 10% loading of InVO4, exhibiting over a 3-fold increase compared to pristine InVO4 NPs, maintaining efficiency across four cycles. This research presents a promising method for designing and creating high-efficiency heterostructures possessing excellent visible-light-driven photocatalytic activity for H2 evolution.

Oxygen deficient BaTiO3 loading sub-nm PtOx for photocatalytic biological wastewater splitting to green hydrogen production

Efficient photocatalytic production of H2 from wastewater rather than pure water is a dual solution to address environmental and energy crises. However, the rapid recombination of photo induced charges in photocatalysts and the inevitable electron consumption caused by organic pollutants pose significant challenges to bifunctional photocatalysis. In this study, we designed an amorphous PtOx supported BaTiO3 single catalyst (named BTPOv-0.09) characterized by oxygen vacancies. This catalyst provides Pt-O-Ti3+ charge separation sites and can effectively generate H2 (1891 μmol · g−1 · h−1), while oxidizing pefloxacin (rate constant k = 0.0485 min−1). It is worth noting that the catalytic performance of BTPOv-0.09 significantly exceeds that of the original BaTiO3, exhibiting 49 and 39 times higher H2 production activity and rate constants (BaTiO3, k = 0.00119 min−1). BTPOv-0.09 exhibits significant H2 production activity in various types of wastewater, highlighting its versatility and promising role in wastewater treatment and renewable energy production.

Investigation of ZnO@CdS nanocomposite with amplified photocatalytic H2 production under visible light irradiation

Researchers are trying to develop an efficient solar-powered catalytic water splitting system to solve the energy dilemma and generate green hydrogen. In this study, ZnO@CdS nano-heterostructures were synthesized using sol-gel and co-precipitation techniques. The pristine ZnO, CdS, and their heterostructures were characterized through various characterization tools such as XRD, SAED, XPS, FTIR, EDX, SEM, FE-TEM, UV–vis, Mott-Schottky, GCG, EIS, and PL, to know the crystal structure, chemical state, elemental composition, morphology, band gap, scheme mechanism, hydrogen production and charge transfer resistance characteristics of the samples, respectively. The SEM, FE-TEM, confirm that CdS NPs are well decorated on hexagonal ZnO rods. The efficient H2 production of 587.86 μmolg−1 h−1 were measured for the optimized sample which is 3.91 times greater than pure ZnO rods and 3.22 times than CdS NPs. Strong photo-cyclic stability test was carried out for 20 h in four cycles while, PL spectroscopy confirms the suppressed charge recombination. All of the above characterization prove that (ZC-20) optimized sample, has a potential to be used as an efficient and stable photocatalyst for H2 production via photocatalytic water splitting.

Engineering Au-Pt atomic alloy cocatalysts for enhanced H2 production from photo-reforming of lignocellulosic biomass wastes

Harnessing solar energy to convert natural lignocellulosic biomass waste and water into clean fuel H2 at ambient conditions holds significant promise for sustainability. However, the efficiency of photocatalytic H2 production faces challenges due to inefficient charge separation, inadequate H2 evolution, and sluggish biomass oxidation process. Herein, we designed Au-Pt atomic alloy cocatalysts on g-C3N4 by decorating the surface of Au nanocrystals with minimal Pt atoms/clusters. The obtained bimetallic cocatalysts possess specific geometric and electronic configurations that play a pivotal role in expediting the separation of electron-hole pairs, spatially segregating the oxidation and reduction processes, and optimizing the H* adsorption strength. The optimal Au-Pt/g-C3N4 sample exhibited a H2 production rate of 1061.8 µmol/g/h, surpassing Pt/g-C3N4 by 6.8 times and Au/g-C3N4 by 14 times. Our research provides a straightforward, eco-friendly, and cost-effective method for converting biomass into H2, offering a promising avenue for sustainable energy production.

Constructing GO films/CdS nanoparticles/MoS2 nanosheets ternary nanojunction with enhanced photocatalytic hydrogen evolution activity

CdS, as a visible-light responsible photocatalyst, has gained considerable attentions for its relatively narrow bandgap and negative conduction band edge. However, its photocatalytic activity is hindered by challenges such as severe charge recombination, insufficient active sites and poor stability. In this work, a robust strategy is proposed to optimize the transfer channel for charge carriers and enhance the active sites by heterojunction and cocatalyst engineering. The well-designed GO/CdS/MoS2 shows remarkable durability (20 h without significant loss of H2 production rate) with a high photocatalytic H2 production rate of 1.45 mmol h−1g−1 (about 6.6-fold enhancement compared with CdS) at GO content of 0.1 wt% and MoS2 loading amount of 5.0 wt%. The bolstered H2 production rate is attributed to the augmented transfer channels of mass owing to the holey structure of GO, the enhanced active sites since the introduction of MoS2, and the unidirectional transfer of electrons from CdS to MoS2, which is ascribed to the built-in electric field in the CdS/MoS2 interface. Thanks to the directional transfer of holes from CdS to GO in the GO/CdS interface, the assemblage of holes in CdS is prevented, thus contributing to the amplified stability GO/CdS/MoS2. Our findings offer insights for the enhanced photocatalytic activity of CdS based photocatalysts, which may inspire the development of the heterostructure photocatalysts for solar-to-fuel conversion.

Facile fabrication of S-scheme MnCo2S4/ZnIn2S4 heterojunction for photocatalytic H2 evolution

In this work, MnCo2S4 nano-particle and ZnIn2S4 nano-flower were synthesized via a facile hydrothermal method, respectively. The MnCo2S4/ZnIn2S4 heterojunction was subsequently fabricated using a physical solvent evaporation method. The photocatalytic H2 production rate over 10 wt. % MnCo2S4/ZnIn2S4 can reach 17.5 mmol·g−1·h−1 under the irradiation of a 300 W Xe lamp, with 20 % triethanolamine (TEOA) used as a sacrificial agent, which is 3.4 times and 54.6 times that of pure ZnIn2S4 (5.2 mmol·g−1·h−1) and MnCo2S4 (0.3 mmol·g−1·h−1). The improved performance can be attributed to the establishment of an S-scheme charge transfer pathway between MnCo2S4 and ZnIn2S4, which not only enhances charge separation but also preserves active electrons and holes. The formed heterojunction facilitates the broadening of the light absorption spectrum, enhance carriers generation, reduce charge transfer impedance, increase electrochemical activity surface area, and lower H2 evolution overpotential compared to individual components. The work offers a promising way for the development of stable and efficient sulfide heterojunction achieve efficent photocatalytic H2 evolution.

Dual S-scheme MoS2/ZnIn2S4/Graphene quantum dots ternary heterojunctions for highly efficient photocatalytic hydrogen evolution

The layered chalcogenide ZnIn2S4 (ZIS) exhibits photo-stability and a tunable band gap but is limited in photocatalytic applications, such as hydrogen (H2) production, due to rapid carrier recombination and slow charge separation. To overcome these limitations, we have synthesized a ternary MoS2/ZIS/graphene quantum dots (GQDs) heterojunction, wherein MoS2 and GQDs are strategically attached to ZIS interlaced nanoflakes, enhancing light absorption across the 500–1500 nm range. This heterojunction benefits from dual S-scheme interfaces between MoS2-ZIS and ZIS-GQDs, establishing directed internal electric fields (IEFs). These IEFs accelerate the transfer of photoinduced electrons from the conduction bands of MoS2 and GQDs to the valence band of ZIS, promoting rapid recombination with holes and facilitating efficient catalytic reactions with plentiful photoinduced electrons stemmed from the conduction band of ZIS. As a result, the photocatalytic H2 production rate of the MoS2/ZIS/GQDs heterojunction is measured at 21.63 mmol h−1 g−1, marking an increase of 36.7 times over pure ZIS. This research provides valuable insights into designing novel heterojunctions for improved charge separation and transfer for solar energy conversion applications.

Photoredox Cascade Catalysts for Solar Hydrogen Production from Sustainable Hydrogen Sources.

Visible-light-driven photocatalytic hydrogen (H2) production has been extensively studied as a clean and sustainable energy resource. Although sacrificial electron donors (SEDs) are commonly used to evaluate photocatalytic activity, their irreversible decomposition forces charge separation, which disrupts the inherent dual productivity of photocatalysis, that is, the formation of both the reduction and oxidation products. To achieve highly efficient photoinduced charge separation without SED decomposition, the layer-by-layer assembly of redox-active photosensitizing dyes and electron mediators through Zr4+-phosphonate bonds has been extensively studied as an artificial mimic of the electron transport chain in natural photosynthesis. This concept paper presents an overview of photoredox cascade catalytic (PRCC) systems comprising multiple Ru(II)-trisbipyridine-type dyes and mediator layers on Pt-loaded TiO2 nanoparticles for H2 production from redox reversible electron donors (RREDs). The PRCC structure-activity relationship for photocatalytic H2 production is briefly discussed in terms of layer thickness, surface structure and modification, and cooperativity with molecular oxidation catalysts. Finally, new insights into the design of efficient dual-production photocatalysts based on the PRCC structure are presented.

Boosting visible-light-driven photocatalytic H2 production by optimizing surface hydrogen desorption of NiS/CdS–P photocatalyst

Metal chalcogenides are regarded as favorable H2-evolution cocatalysts; however, they often exhibit unfavorable H desorption characteristics due to the strong affinity of nascent H and highly electronegative S sites, which significantly inhibit H2 generation. To address this issue, a general approach to electron-enriched control of sulfur-active sites is developed for weakening the strong interaction of S–H bonds. This is achieved through the formation of a nanostructured model composed of NiS/CdS–P, in which the surface phosphorus (P) atoms are incorporated in CdS NRs to create an imbalanced charge distribution and a localized built-in electric field in the crystal structure of CdS. In this situation, the built-in electric field not only separates the photogenerated electron hole pairs, but it also accelerates the photogenerated electrons from the CdS–P conduction band to the NiS surface for rapid hydrogen reduction rather than hydrogen adsorption. Photocatalytic tests show that the resultant NiS/CdS–P photocatalyst displays a significant H2-generation rate of 44.39 mmol g−1 h−1 and an apparent quantum efficiency of 41% at 420 nm. Valance band XPS analysis shows that CdS–P has a higher electron density than CdS, leading to the production of electron-rich Sδ− active centers. This better photocatalytic hydrogen generation might be due to the synergistic impact of tailoring the intrinsic built-in electric field for the acceleration of photogenerated charges by P-doping and the fabrication of a NiS cocatalyst for hydrogen reduction rather than hydrogen adsorption. The concept of optimizing the electron densities of active sites by morphology tailoring, with an extra built-in electric field, gives a method for rationally constructing artificial photocatalysts for solar power conversion.

Fabrication of Ni and Cd co-doped Zn ZIF-L photocatalyst for enhanced solar hydrogen evolution

Recently, photocatalytic H2 production has gained significant attention for its potential to generate clean and renewable energy. In this study, the enhancement of H2 production was examined by introducing various transition metal elements in Zn/Ni/Cd zeolitic imidazole frameworks photocatalysts (ZIF). The photocatalysts were synthesized using a precipitation method in water, resulting in the formation of ZIF-L structures. Increasing the Ni content leads to large particle sizes and typically reduced surface areas, owing to the increased possibility of coordination at the six coordination sites of Ni atoms. The trimetallic Zn/Ni/Cd ZIF at its optimum composition exhibits the highest absorbance and narrowest band gap, consequently yielding the highest average H2 production rate. To address unstable reproducibility from restricted electron transfer in the optimal sample, CdS is added to form a heterojunction and to achieve stable reproducibility. Consequently, improved H2 production is achieved by incorporating imidazole organic ligands into the co-doped trimetallic ZIF-L photocatalyst. Overall, in this study, the synthesis and optimization of ZIF composite photocatalysts are elucidated, providing insights into the design of efficient materials for sustainable energy production.

Thienyl-fused dibenzothiophene-S,S-dioxide based conjugated polymer toward highly efficient photocatalytic hydrogen production

Dibenzothiophene-S,S-dioxide (BTDO) is one of the cutting-edge electron-acceptor monomers for designing conjugated polymer based organic materials toward photocatalytic H2 production from water. Normally, structure design of BTDO containing donor-acceptor (D-A) polymer photocatalyst mainly focuses on screening electron-donor motifs, the importance of modification on BTDO molecular toward improving charge carrier separation and photocatalytic performance is always ignored. Herein, a novel thienyl-fused BTDO building block (BTDO-DT) is prepared and utilized to synthesize B-BTDO-DT polymer photocatalyst by Sonogashira-Hagihara cross-coupling polycondensation using 1,4-Diethynylbenzene (B) and BTDO-DT as monomers. Experimental and density functional theory (DFT) calculation results demonstrate that modification of BTDO by thiophene not only enlarges light absorption region and promotes photogenerated e−/h+ separation, but also decreases H atom adsorption free energy (ΔGH*) on oxygen atom in the OSO group. As a result, B-BTDO-DT exhibits an outstanding visible light induced photocatalytic H2 production rate of 156.6 μmol h−1 using 30 mg catalyst without Pt cocatalyst, which is 4.5 times higher than that of B-BTDO. And the H2 production rate of B-BTDO-DT is further improved to be 259.8 μmol h−1 with 2.0 wt% Pt as co-catalyst. The present work may open a new direction for the design of conjugated polymer based photocatalysts with high photocatalytic activities.