Hydrogen production from dry reforming of methane, using CO2 previously chemisorbed in the Li6Zn1-xNixO4 solid solution.

Li6ZnO4 was chemically modified by nickel addition, in order to develop different compositions of the solid solution Li6Zn1-xNixO4. These materials were evaluated bifunctionally; analyzing their CO2 capture performances, as well as on their catalytic properties for H2 production via dry reforming of methane (DRM). The crystal structures of Li6Zn1-xNixO4 solid solution samples were determined through X-ray diffraction, which confirmed the integration of nickel ions up to a concentration around 20 mol%, meanwhile beyond this value, a secondary phase was detected. These results were supported by XPS and TEM analyses. Then, dynamic and isothermal thermogravimetric analyses of CO2 capture revealed that Li6Zn1-xNixO4 solid solution samples exhibited good CO2 chemisorption efficiencies, similarly to the pristine Li6ZnO4 chemisorption trends observed. Moreover, a kinetic analysis of CO2 isothermal chemisorptions, using the Avrami-Erofeev model, evidenced an increment of the constant rates as a function of the Ni content. Since Ni2+ ions incorporation did not reduce the CO2 capture efficiency and kinetics, the catalytic properties of these materials were evaluated in the DRM process. Results demonstrated that nickel ions favored hydrogen (H2) production over the pristine Li6ZnO4 phase, despite a second H2 production reaction was determined, methane decomposition. Thereby, Li6Zn1-xNixO4 ceramics can be employed as bifunctional materials.

In-situ construction of N-doped Zn0.6Cd0.4S/oxygen vacancy-rich WO3 Z-scheme heterojunction compound for boosting photocatalytic hydrogen production.

Photocatalytic water splitting technology for H2 production represents a promising and sustainable approach to clean energy generation. In this study, a high concentration of oxygen vacancies was introduced into tungsten trioxide (WO3) to create a vacancy-rich layer. This modified WO3 (WO3-x) was then combined with N-doped Zn0.6Cd0.4S through a hydrothermal synthesis, resulting in the formation of a Z-scheme heterojunction composite aimed at enhancing photocatalytic performance. Under visible light, the H2 production activity of the composite reached an impressive 8.52 mmol·g-1 without adding co-catalyst Pt. This corresponds to enhancements of 7.82 and 4.39 times the production yield of pure ZCS and ZCSN, respectively. However, the hydrogen production increased to 21.98 mmol·g-1 when Pt was added as a co-catalyst. Furthermore, an array of characterizations were employed to elucidate the presence of oxygen vacancies and the establishment of the Z-scheme heterojunction. This structural enhancement significantly facilitates the utilization of photo-generated electrons while effectively preventing photo-corrosion of ZCSN, thus improving material stability. Our study provides a new scheme for the incorporation of oxygen-rich vacancy and the construction of Z-scheme heterojunction, demonstrating a synergistic effect that greatly advances photocatalytic performance.

Stable Cu/Cu2O/CuN3@NC Catalysts for Aqueous Phase Reforming of Methanol.

Aqueous-phase reforming of methanol represents a promising avenue for hydrogen (H2) production. However, developing highly efficient and low-cost nonprecious catalysts remains challenging. Here, we report the synthesis of Cu-based catalysts with Cu, Cu2O, and CuN3 nanoparticles anchored on the nitrogen-doped carbon, forming Cu0/Cu+/Cu-N3 active sites. This catalyst achieves a H2 production rate of 140.1 µmol/gcat/s at 210 °C, which is several times to 2 orders of magnitude higher than that of Cu-, Ni-, even Pt-based catalysts, demonstrating excellent long-term stability over 350 h at 210 °C. A mechanism investigation reveals that the Cu-N3 site facilitates water dissociation into *OH and improves *CO and *OH conversion, leading to enhanced CO conversion and H2 production kinetics.

The Dependence of NiMo/Cu Catalyst Composition on Its Catalytic Activity in Sodium Borohydride Hydrolysis Reactions.

The production of high-purity hydrogen from hydrogen storage materials with further direct use of generated hydrogen in fuel cells is still a relevant research field. For this purpose, nickel-molybdenum-plated copper catalysts (NiMo/Cu), comprising between 1 and 20 wt.% molybdenum, as catalytic materials for hydrogen generation, were prepared using a low-cost, straightforward electroless metal deposition method by using citrate plating baths containing Ni2+-Mo6+ ions as a metal source and morpholine borane as a reducing agent. The catalytic activity of the prepared NiMo/Cu catalysts toward alkaline sodium borohydride (NaBH4) hydrolysis increased with the increase in the content of molybdenum present in the catalysts. The hydrogen generation rate of 6.48 L min-1 gcat-1 was achieved by employing NiMo/Cu comprising 20 wt.% at a temperature of 343 K and a calculated activation energy of 60.49 kJ mol-1 with remarkable stability, retaining 94% of its initial catalytic activity for NaBH4 hydrolysis following the completion of the fifth cycle. The synergetic effect between nickel and molybdenum, in addition to the formation of solid-state solutions between metals, promoted the hydrogen generation reaction.

Limosilactobacillus Regulating Microbial Communities to Overcome the Hydrolysis Bottleneck with Efficient One-Step Co-Production of H2 and CH4.

The efficient co-production of H2 and CH4 via anaerobic digestion (AD) requires separate stages, as it cannot yet be achieved in one step. Lactic acid bacteria (LAB) (Limosilactobacillus) release H2 and acetate by enhancing hydrolysis, potentially increasing CH4 production with simultaneous H2 accumulation. This study investigated the enhanced effect of one-step co-production of H2 and CH4 in AD by LAB and elucidated its enhancement mechanisms. The results showed that 236.3 times increase in H2 production and 7.1 times increase in CH4 production are achieved, resulting in profits of 469.39 USD. Model substrates lignocellulosic straw, sodium acetate, and H2 confirmes LAB work on the hydrolysis stage and subsequent sustainable volatile fatty acid production during the first 6 days of AD. In this stage, the enrichment of Limosilactobacillus carrying bglB and xynB, the glycolysis pathway, and the high activity of protease, acetate kinase, and [FeFe] hydrogenase, jointly achieved rapid acetate and H2 accumulation, driving hydrogenotrophic methanogenesis dominated. From day 7 to 24, with enriched Methanosarcina, and increased methenyltetrahydromethanopterin hydrogenase activity, continuously produced acetate led to the mainly acetoclastic methanogenesis shift from hydrogenotrophic methanogenesis. The power generation capacity of LAB-enhanced AD is 333.33 times that of China's 24,000 m3 biogas plant.

Rationally designed CaTiO3/Mn0.5Cd0.5S/Ni3C S-scheme/Schottky integrated heterojunction for efficient photocatalytic H2 evolution.

Developing effective photocatalysts to achieve stable and efficient solar-induced hydrogen production remains a significant challenge due to rapid photocarrier recombination and sluggish hydrogen evolution kinetics. Here, a multi-interfacial engineering strategy involving the decoration of metallic Ni3C onto CaTiO3/Mn0.5Cd0.5S was proposed to create an S-scheme/Schottky hybrid heterostructure with multiple carrier transport paths for effective photocatalytic H2 production. Exploiting the synergy between S-scheme heterojunction and Schottky barrier, the engineered ternary CaTiO3/Mn0.5Cd0.5S/Ni3C hybrid heterojunction exhibits outstanding photostability and significantly enhanced hydrogen evolution activity of 79.1 mmol g-1 h-1, which was about 4.55, 3.22 and 2.59 times greater than Mn0.5Cd0.5S, Mn0.5Cd0.5S/Ni3C, and CaTiO3/Mn0.5Cd0.5S, respectively. By creating an S-scheme heterojunction between CaTiO3 and Mn0.5Cd0.5S, accompanied by a robust internal electric field (IEF), spatial charge separation can be effectively accelerated while ensuring the simultaneous preservation of highly active electrons and holes. Meanwhile, Ni3C nanoparticles, acting as a Schottky-junction H2 generation cocatalyst, can efficiently trap the photoinduced electrons to establish multiple charge transfer channels and supply ample active sites for photoreduction reaction, thereby further optimizing the hydrogen generation kinetics. The integration of a Schottky barrier and S-scheme heterojunction in this research is expected to offer new perspectives for designing other highly effective hybrid catalysts for solar-to-hydrogen fuel conversion.

Engineering ZnIn2S4 with efficient charge separation and utilization for synergistic accelerate dual-function photocatalysis.

Combining photocatalytic reduction with organic synthetic oxidation in the same photocatalytic redox system can effectively utilize photoexcited electrons and holes from solar to chemical energy. Here, we stabilized 0D Au clusters on the substrate surface of Zn vacancies modified 2D ZnIn2S4 (ZIS-V) nanosheets by chemically bonding Au-S interaction, forming surfactant functionalized Au/ZIS-V photocatalyst, which can not only synergistic accelerate the selective oxidation of phenylcarbinol to value-added products coupled with clean energy hydrogen production but also further drive photocatalytic CO2-to-CO conversion. An internal electric field of Au/ZIS-V ohmic junction and Zn vacancies synchronously promote the photoexcited charge carrier separation and transfer to optimized active sites for redox reactions. Compared with CO2 reduction in water and the pristine ZnIn2S4, the reaction thermodynamics and kinetics of CO2 reduction over the Au/ZIS-V were simultaneously improved about 11.09 and 45.51 times, respectively. Moreover, the photocatalytic redox mechanisms were also profoundly studied by 13CO2 isotope tracing tests, in situ electron paramagnetic resonance (in situ EPR), in situ X-ray photoelectron spectroscopy (in situ XPS), in situ diffuse reflection infrared Fourier transform spectroscopy (in situ DRIFTS) and density functional theory (DFT) characterizations, etc. These results demonstrate the advantages of vacancies coupled with metal clusters in the synergetic enhancement of photocatalytic redox performance and have great potential applications in a wide range of environments and energy.

Highly efficient visible light active iron oxide-based photocatalysts for both hydrogen production and dye degradation.

Photocatalysis is essential for wastewater cleanup and clean energy, and in this current study, we have synthesized nanomaterials (iron oxide-based) for photocatalytic pollution degradation and hydrogen production. The performance of aluminium oxide/ferric oxide (Al2O3/Fe2O3), samarium oxide/ferric oxide (Sm2O3/Fe2O3) and yttrium oxide/ferric oxide (Y2O3/Fe2O3) were compared for the production of hydrogen (H2) and degradation of dye under natural sunlight. Various characterisation equipment was used to characterize these photocatalysts' structure, morphology, elemental content, binding energy and band gap. The hydrogen recovery efficiency of iron oxide-based photocatalysts from sulphide-containing wastewater is assessed. Y2O3/Fe2O3 has shown the highest hydrogen production of 340 mL/h. The influence of operating factors such as sulphide ion concentration, catalyst quantity, and photocatalyst photolytic solution volume on hydrogen production is studied. The optimal values were 0.25 M, 0.2 g/L, and 1L, respectively. The developed photocatalyst passed multiple cycles of stability testing. Fe2O3 has shown the highest Rhodamine B (RhB) dye degradation efficiency of 94% under visible light.

Pollutant degradation and hydrogen production of landfill leachate membrane concentrates via aqueous phase reforming.

Membrane filtration is a mainstream method for landfill leachate treatment, leaving the landfill leachate membrane concentrates (LLMCs) a high-toxicity residue. Conventional LLMCs disposal technology shows specific challenges due to the low biodegradability, high inorganic salts, and high heavy metal ions content of LLMCs. Therefore, it is necessary to degrade LLMCs with a more suitable technology. In this study, a special method was proposed to convert some organic chemicals into valuable compounds by aqueous phase reforming (APR). Ni-based catalysts (Ni//La2O3, Ni/CeO2, Ni/MgO, and Ni/Al2O3) were prepared to investigate the effect of different supports on the APR of LLMCs. APR performed outstanding characteristics in the decrease of chemical oxygen demand (COD) and total organic carbon (TOC), the degradation of macromolecules, and the removal of heavy metal ions in the aqueous phase. In addition, H2 was generated which is beneficial for energy compensating during the APR process. The best-performing catalyst (Ni/Al2O3) was selected to investigate the effects of reaction temperature, reaction time, and catalyst addition on product distribution. The optimal H2 selectivity (44.71%) and H2 production (11.63 mmol/g COD) were obtained at 250 °C with 2 g Ni/Al2O3 usage for 1 h. This paper provided a new perspective on the disposal of LLMCs, which will degrade pollutants efficiently.

Light-Driven H2 Production in Chlamydomonas reinhardtii: Lessons from Engineering of Photosynthesis.

In the green alga Chlamydomonas reinhardtii, hydrogen production is catalyzed via the [FeFe]-hydrogenases HydA1 and HydA2. The electrons required for the catalysis are transferred from ferredoxin (FDX) towards the hydrogenases. In the light, ferredoxin receives its electrons from photosystem I (PSI) so that H2 production becomes a fully light-driven process. HydA1 and HydA2 are highly O2 sensitive; consequently, the formation of H2 occurs mainly under anoxic conditions. Yet, photo-H2 production is tightly coupled to the efficiency of photosynthetic electron transport and linked to the photosynthetic control via the Cyt b6f complex, the control of electron transfer at the level of photosystem II (PSII) and the structural remodeling of photosystem I (PSI). These processes also determine the efficiency of linear (LEF) and cyclic electron flow (CEF). The latter is competitive with H2 photoproduction. Additionally, the CBB cycle competes with H2 photoproduction. Consequently, an in-depth understanding of light-driven H2 production via photosynthetic electron transfer and its competition with CO2 fixation is essential for improving photo-H2 production. At the same time, the smart design of photo-H2 production schemes and photo-H2 bioreactors are challenges for efficient up-scaling of light-driven photo-H2 production.

Releasing Au Electrons to Mo Site for Weakened Mo─H Bond of Mo2C MXene Cocatalyst Toward Improved Photocatalytic H2 Production.

Mo2C MXene (Mo2CTx) is one of the most promising noble-metal-free cocatalysts for photocatalytic H2 production because of its excellent electron transport capacity and abundant Mo sites. However, Mo2CTx typically exhibits a strong Mo─Hads bond, resulting in that the produced H2 difficultly desorbs from the Mo surface for the limited activity. To effectively weaken the Mo─Hads bond, in this paper, a regulation strategy of electron donor Au releasing electrons to the d-orbitals of Mo sites in Mo2CTx is proposed. Herein, the Mo2CTx-Au/CdS photocatalysts are prepared through a two-step process, including the initial loading of Au nanoparticles on the Mo2CTx surface and the subsequent in situ growth of CdS onto the Mo2CTx-Au surface. Photocatalytic measurements indicate that the maximal H2-production rate of Mo2CTx-Au/CdS reaches up to 2799.44 µmol g-1 h-1, which is 30.99 and 3.60 times higher than that of CdS and Mo2CTx/CdS, respectively. Experimental and theoretical data corroborate that metallic Au can transfer free electrons to Mo2CTx to generate electron-enriched Moδ- sites, thus causing the increased antibonding-orbital occupancy state and the weakened Mo─Hads bond for the boosted H2-production efficiency. This research provides a promising approach for designing Mo2CTx-based cocatalysts by regulating the antibonding-orbital occupancy of Mo sites for improved photocatalytic performance.

Synergistic manipulation of sulfur vacancies and palladium doping of In2S3 for enhanced photocatalytic H2 production.

In this study, a simple one-pot synthesis process is employed to introduce Pd dopant and abundant S vacancies into In2S3 nanosheets. The optimized Pd-doped In2S3 photocatalyst, with abundant S vacancies, demonstrates a significant enhancement in photocatalytic hydrogen evolution. The joint modification of Pd doping and rich S vacancies on the band structure of In2S3 result in an improvement in both the light absorption capacity and proton reduction ability. It is worth noting that photogenerated electrons enriched by S vacancies can rapidly migrate to adjacent Pd atoms through an efficient transfer path constructed by Pd-S bond, effectively suppressing the charge recombination. Consequently, the dual-defective In2S3 shows an efficient photocatalytic H2 production rate of 58.4 ± 2.0 µmol·h-1. Additionally, further work has been conducted on other ternary metal sulfide, ZnIn2S4. Our findings provide a new insight into the development of highly efficient photocatalysts through synergistic defect engineering.

Tungsten-needle intensifies microwave-sustained plasma accelerating direct H2S conversion to H2.

Direct sustainable conversion of hydrogen sulfide (H2S) enables collaborative recovery of H and S resources via a metal-enhanced microwave plasma strategy, avoiding the hydrogen waste in the traditional Claus process. However, the metal size effect on microwave plasma property, the optimal process parameters, and the enhancement mechanism remain unclear in H2S conversion. Herein, the optimal tungsten needle (diameter: 1 mm, length: 60 mm, and tip angle: 10°) is experimentally proven for intensifying microwave discharge in multi-mode cavities. Theoretical calculations and plasma distribution reveal that the optimized tungsten needle achieves the ideal coupling with the microwave field, exhibiting extreme electric field augmentation around the needle tip. Tungsten-needle intensifies microwave-sustained plasma, realizing 40.2 % (90.1 %) conversion of 100 % (10 %) concentration H2S to H2 at a low microwave power of 300 W with a good stability of 30 hrs. Low power, large flow rate, and high H2S concentration are beneficial for improving energy efficiency. The excitation of microwave plasma is accompanied by a massive generation of highly energetic electrons. The direct high-energy electron-H2S collision contributes a lot to H2S splitting, especially for high-concentration H2S. In-situ optical emission spectroscopy confirms the vital S and H radicals in the plasma. The free radical reactions triggered by electron collisions are responsible for the production of H2 and S. This work opens an avenue to sustainable and low-carbon hydrogen production from the direct conversion and utilization of H2S.

Synergistic photocatalytic breakdown of azo dyes coupled with H2 generation via Cr-doped α-Fe2O3 nanoparticles.

This research addresses the scalable and inexpensive synthesis of α-Fe2O3via hydrothermal method without any precipitating agent as well as the enhancement of solar driven photocatalytic and H2 production through doping different chromium proportions. Competency of α-Fe2O3, both pure and doped with chromium, to function as photocatalyst was evaluated by its interaction with multiple dyes, which was real-time monitored utilizing (Internet of Things) IoT technique. By adding chromium, the rate of deterioration increased substantially from 15 to 94% for TB under sunlight in a remarkably brief 20 min by employing a very small amount of Cr0.8Fe1.2O3 (0.3 g/L), as evidenced by high degree of mineralization i.e. 85% and LC-HRMS. Also, the rapid breakdown of Trypan Blue (TB) was indicated by BOD5/COD ratio. Moreover, Cr-doped α-Fe2O3 displays excellent H2 production (~ 132 µmol h-1 g-1) as compared to α-Fe2O3. This work highlights the potential utilization of Cr-doped α-Fe2O3 for the purification of industrial waste water and green energy harvesting.

Organic Donor-Acceptor-Donor Trimers Nanoparticles Stabilized by Amphiphilic Block Copolymers for Photocatalytic Generation of H2.

Photocatalytic generation of H2 via water splitting emerges as a promising avenue for the next generation of green hydrogen due to its low carbon footprint. Herein, a versatile platform is designed to the preparation of functional π-conjugated organic nanoparticles dispersed in aqueous phase via mini-emulsification. Such particles are composed of donor-acceptor-donor (DAD) trimers prepared via Stille coupling, stabilized by amphiphilic block copolymers synthesized by reversible addition-fragmentation chain transfer polymerization. The hydrophilic segment of the block copolymers will not only provide colloidal stability, but also allow for precise control over the surface functionalization. Photocatalytic tests of the resulting particles for H2 production resulted in promising photocatalytic activity (≈0.6 mmol g-1 h-1). This activity is much enhanced compared to that of DAD trimers dispersed in the water phase without stabilization by the block copolymers.

Engineering bionanoreactor in bacteria for efficient hydrogen production.

Hydrogen production through water splitting is a vital strategy for renewable and sustainable clean energy. In this study, we developed an approach integrating nanomaterial engineering and synthetic biology to establish a bionanoreactor system for efficient hydrogen production. The periplasmic space (20 to 30 nm) of an electroactive bacterium, Shewanella oneidensis MR-1, was engineered to serve as a bionanoreactor to enhance the interaction between electrons and protons, catalyzed by hydrogenases for hydrogen generation. To optimize electron transfer, we used the microbially reduced graphene oxide (rGO) to coat the electrode, which improved the electron transfer from the electrode to the cells. Native MtrCAB protein complex on S. oneidensis and self-assembled iron sulfide (FeS) nanoparticles acted in tandem to facilitate electron transfer from an electrode to the periplasm. To enhance proton transport, S. oneidensis MR-1 was engineered to express Gloeobacter rhodopsin (GR) and the light-harvesting antenna canthaxanthin. This led to efficient proton pumping when exposed to light, resulting in a 35.6% increase in the rate of hydrogen production. The overexpression of native [FeFe]-hydrogenase further improved the hydrogen production rate by 56.8%. The bionanoreactor engineered in S. oneidensis MR-1 achieved a hydrogen yield of 80.4 µmol/mg protein/day with a Faraday efficiency of 80% at a potential of -0.75 V. This periplasmic bionanoreactor combines the strengths of both nanomaterial and biological components, providing an efficient approach for microbial electrosynthesis.

Charge self-regulation over in-plane two-dimensional/two-dimensional hetero-cocatalyst for robust photocatalytic hydrogen generation.

The rationally designing and constructing atomic-level heterointerface of two-dimensional (2D) chalcogenides is highly desirable to overcome the sluggish H2O-activation process toward efficient solar-driven hydrogen evolution. Herein, a novel in-plane 2D/2D molybdenum disulfide-rhenium disulfide (ReS2-MoS2) heterostructure is well-designed to induce the charge self-regulation of active site by forming electron-enriched Re(4-δ)+ and electron-deficient S(2-δ)- sites, thus collectively facilitating the activation of adsorbed H2O molecules and its subsequent H2 evolution. Furthermore, the obtained in-plane heterogenous ReS2-MoS2 nanosheet can powerfully transfer photoexcited electrons to inhibit photocarrier recombination as observed by advanced Kelvin probe measurement (KPFM), in-situ X-ray photoelectron spectroscopy (XPS) and femtosecond transient absorption spectroscopy (fs-TAS). As expected, the obtained ReS2-MoS2/TiO2 photocatalyst achieves an outperformed H2-generation rate of 6878.3 µmol h-1 g-1 with visualizing H2 bubbles in alkaline/neutral conditions. This work about in-plane 2D/2D heterostructure with strong free-electron interaction provides a promising strategy for designing novel and efficient catalysts for various applications.

Pyridinethiolate-Capped CdSe Quantum Dots for Red-Light-Driven H2 Production in Water.

The utilization of low-energy sunlight to produce renewable fuels is a subject of great interest. Here we report the first example of metal chalcogenide quantum dots (QDs) capped with a pyridinethiolate carboxylic acid (pyS-COOH) for red-light-driven H2 production in water. The precious-metal-free system is robust over 240 h, and achieves a turnover number (TON) of 43910±305 (vs Ni) with a rate of 31570±1690 µmol g-1 h-1 for hydrogen production. In contrast to the inactive QDs capped with other thiolate ligands, the CdSe-pyS-COOH QDs give a significantly higher singlet oxygen quantum yield [ΦΔ (1O2)] in solution.

The photocatalytic wastewater hydrogen production process with superior performance to the overall water splitting.

The utilization of a cost-free sacrificial agent is a novel approach to significantly enhance the efficiency of photocatalytic hydrogen (H2) production by water splitting. Wastewater contains various organic pollutants, which have the potential to be used as hole sacrificial agents to promote H2 production. Our studies on different pollutants reveals that not all pollutants can effectively promote H2 production. However, when using the same pollutants, not all photocatalysts achieved a higher H2 evolution rate than pure water. Only when the primary oxidizing active species of the photocatalyst are •OH radicals, which are generated by photogenerated holes, and when the pollutants are easily attacked and degraded by •OH radicals, can the production of H2 be effectively promoted. It is noteworthy that the porous brookite TiO2 photocatalyst exhibits a significantly higher H2 evolution rate in Reactive Red X-3B and Congo Red, reaching as high as 26.46 mmol⋅g-1⋅h-1 and 32.85 mmol⋅g-1 ⋅h-1, respectively, which is 2-3 times greater than that observed in pure water and is 10 times greater than most reported studies. The great significance of this work lies in the potential for efficient H2 production through the utilization of wastewater.

Triazine and Fused Thiophene-Based Donor-Acceptor Type Semiconducting Conjugated Polymer for Enhanced Visible-Light-Induced H2 Production.

Conjugated polymers have attracted significant attention in the field of photocatalysis due to their exceptional properties, including versatile optimization, cost-effectiveness, and structure stability. Herein, two conjugated porous polymers, PhIN-CPP and ThIN-CPP, based on triazines, were meticulously designed and successfully synthesized using benzene and thiophene as building blocks. Based on UV diffuse reflection spectra, the photonic band gaps of PhIN-CPP and ThIN-CPP were calculated as 2.05 eV and 1.79 eV. The PhIN-CPP exhibited a high hydrogen evolution rate (HER) of 5359.92 µmol·g-1·h-1, which is 10 times higher than that of Thin-CPP (538.49 µmol·g-1·h-1). The remarkable disparity in the photocatalytic performance can be primarily ascribed to alterations in the band structure of the polymers, which includes its more stable benzene units, fluffier structure, larger specific surface area, most pronounced absorption occurring in the visible region and highly extended conjugation with a high density of electrons. The ΔEST values for PhIN-CPP and ThIN-CPP were calculated as 0.79 eV and 0.80 eV, respectively, based on DFT and TD-DFT calculations, which revealed that the incorporation of triazine units in the as-prepared CMPs could enhance the charge transfer via S1 ↔ T1 and was beneficial to the photocatalytic decomposition of H2O. This study presents a novel concept for developing a hybrid system for preparation of H2 by photocatalysis with effectiveness, sustainability, and economy.