Efficient photoanode with a MoS2/TiO2/Au nanoparticle heterostructure for ultraviolet-visible photoelectrocatalysis.

Green energy technology is generally becoming one of hot issues that need to be solved due to the adverse effects on the environment of fossil fuels. One of the strategies being studied and developed by theorists and experimentalists is the use of photoelectrochemical (PEC) cells, which are emerging as a candidate to produce hydrogen from water splitting. However, creating photoelectrodes that meet the requirements for PEC water splitting has emerged as the primary obstacle in bringing this technology to commercial fruition. Here, we construct a heterostructure, which consists of MoS2/TiO2/Au nanoparticles (NPs) to overcome the drawbacks of the photoanode. Owing to the dependence on charge transfer, the bandgap of MoS2/TiO2and the utilization the Au NPs as a stimulant for charges separation of TiO2by localized surface plasmon resonances effect as well as the increase of hot electron injection to cathode, leading to photocatalytic activities are improved. The results have recorded a significant increase in the photocurrent density from 2.3µAcm-2of TiO2to approximately 16.3µAcm-2of MoS2/TiO2/Au NPs. This work unveils a promising route to enhance the visible light adsorption and charge transfer in photo-electrode of the PEC cells by combining two-dimensional materials with metal NPs.

Electrocatalytic Coupling of Nitrate and Formaldehyde for Hexamethylenetetramine Synthesis via C-N Bond Construction and Ring Formation.

Hexamethylenetetramine (HMTA) is extensively used in the defense industry, medicines, food, plastics, rubber, and other applications. Traditional organic synthesis of HMTA relies on ammonia derived from the Haber process at high temperatures and pressures. In contrast, electrochemical methods enable a safe and green one-pot synthesis of HMTA from waste NO3-. However, HMTA synthesis through the electrochemical method is challenging owing to the complex reaction pathways involving C-N bond construction and ring formation. In this study, HMTA was efficiently synthesized over electrochemical oxidation-derived copper (e-OD-Cu), with a yield of 76.8% and a Faradaic efficiency of 74.9% at -0.30 VRHE. The catalytic mechanism and reaction pathway of HMTA synthesis on e-OD-Cu were investigated through a series of in situ characterization methods and density-functional theory calculations. The results demonstrated that the electrocatalytic synthesis of HMTA involved a tandem electrochemical-chemical reaction. Additionally, the results indicated that the presence of Cu vacancies enhanced substrate adsorption and inhibited the further hydrogenation of C═N. Overall, this study provides an electrocatalytic method for HMTA synthesis and an electrochemical strategy for constructing multiple C-N bonds.

Polyacrylate modified Cu electrode for selective electrochemical CO2 reduction towards multicarbon products.

Highly selective production of value-added multicarbon (C2+) products via electrochemical CO2 reduction reaction (eCO2RR) on polycrystalline copper (Cu) remains challenging. Herein, the facile surface modification using poly (α-ethyl cyanoacrylate) (PECA) is presented to greatly enhance the C2+ selectivity for eCO2RR over polycrystalline Cu, with Faradaic efficiency (FE) towards C2+ products increased from 30.1% for the Cu electrode to 72.6% for the obtained Cu-PECA electrode at -1.1 V vs. reversible hydrogen electrode (RHE). Given the well-determined FEs towards C2+ products, the partial current densities for C2+ production could be estimated to be -145.4 mA cm-2 for the Cu-PECA electrode at -0.9 V vs. RHE in a homemade flow cell. In-situ spectral characterizations and theoretical calculations reveal that PECA featured with electron-accepting -C≡N and -COOR groups decorated onto the Cu electrode could inhibit the adsorption of *H intermediates and stabilize the *CO intermediates, given the redistributed interfacial electron density and the raised energy level of d-band center (Ed) of Cu active sites, thus facilitating the C-C coupling and then the C2+ selective production. This study is believed to be guidable to the modification of electrocatalysts and electrodes with polymers to steer the surface adsorption behaviors of reaction intermediates to realize practical eCO2RR towards value-added C2+ products with high activity and selectivity.

Main Group SnN4O Single Sites with Optimized Charge Distribution for Boosting the Oxygen Reduction Reaction.

Transition metal single-atom catalysts (SACs) have been regarded as possible alternatives to platinum-based materials due to their satisfactory performance of the oxygen reduction reaction (ORR). By contrast, main-group metal elements are rarely studied due to their unfavorable surface and electronic states. Herein, a main-group Sn-based SAC with penta-coordinated and asymmetric first-shell ligands is reported as an efficient and robust ORR catalyst. The introduction of the vertical oxygen atom breaks the symmetric charge balance, modulating the binding strength to oxygen intermediates and decreasing the energy barrier for the ORR process. As expected, the prepared Sn SAC exhibits outstanding ORR activity with a high half-wave potential of 0.912 V (vs RHE) and an excellent mass activity of 13.1 A mgSn-1 at 0.850 V (vs RHE), which surpasses that of commercial Pt/C and most reported transition-metal-based SACs. Additionally, the reported Sn SAC shows excellent ORR stability due to the strong interaction between Sn sites and the carbon support with oxygen atom as the bridge. The excellent ORR performance of Sn SAC was also proven by both liquid- and solid-state zinc-air battery (ZAB) measurements, indicating its great potential in practical applications.

Ultra-Low-Potential Methanol Oxidation on Single-Ir-Atom Catalyst.

Methanol oxidation plays a central role to implement sustainable energy economy, which is restricted by the sluggish reaction kinetics due to the multi-electron transfer process accompanied by numerous sequential intermediate. In this study, an efficient cascade methanol oxidation reaction is catalyzed by single-Ir-atom catalyst at ultra-low potential (<0.1 V) with the promotion of the thermal and electrochemical integration in a high temperature polymer electrolyte membrane electrolyzer. At the elevated temperature, the electron deficient Ir site with higher methanol affinity could spontaneous catalyze the CH3OH dehydrogenation to CO under the voltage, then the generated CO and H2 was electrochemically oxidized to CO2 and proton. However, the methanol cannot thermally decompose with the voltage absence, which confirm the indispensable of the coupling of thermal and electrochemical integration for the methanol oxidation. By assembling the methanol oxidation reaction with hydrogen evolution reaction with single-Ir-atom catalysts in the anode chamber, a max hydrogen production rate reaches 18 mol gIr -1 h-1, which is much greater than that of Ir nanoparticles and commercial Pt/C. This study also demonstrated the electrochemical methanol oxidation activity of the single atom catalysts, which broadens the renewable energy devices and the catalyst design by an integration concept.

Accelerating Oxygen Electrocatalysis Kinetics on Metal-Organic Frameworks via Bond Length Optimization.

Metal-organic frameworks (MOFs) have been developed as an ideal platform for exploration of the relationship between intrinsic structure and catalytic activity, but the limited catalytic activity and stability has hampered their practical use in water splitting. Herein, we develop a bond length adjustment strategy for optimizing naphthalene-based MOFs that synthesized by acid etching Co-naphthalenedicarboxylic acid-based MOFs (donated as AE-CoNDA) to serve as efficient catalyst for water splitting. AE-CoNDA exhibits a low overpotential of 260 mV to reach 10 mA cm-2 and a small Tafel slope of 62 mV dec-1 with excellent stability over 100 h. After integrated AE-CoNDA onto BiVO4, photocurrent density of 4.3 mA cm-2 is achieved at 1.23 V. Experimental investigations demonstrate that the stretched Co-O bond length was found to optimize the orbitals hybridization of Co 3d and O 2p, which accounts for the fast kinetics and high activity. Theoretical calculations reveal that the stretched Co-O bond length strengthens the adsorption of oxygen-contained intermediates at the Co active sites for highly efficient water splitting.

Determining Quasi-Equilibrium Electron and Hole Distributions of Plasmonic Photocatalysts Using Photomodulated X-ray Absorption Spectroscopy.

Most photocatalytic and photovoltaic devices operate under broadband, constant illumination. Electron and hole dynamics in these devices, however, are usually measured by using ultrafast pulsed lasers in a narrow wavelength range. In this work, we use excited-state X-ray theory originally developed for transient X-ray experiments to study steady-state photomodulated X-ray spectra. We use this method to attempt to extract electron and hole distributions from spectra collected at a nontime-resolved synchrotron beamline. A set of plasmonic metal core-shell nanoparticles is designed as the control experiment because they can systematically isolate photothermal, hot electron, and thermalized electron-hole pairs in a TiO2 shell. Steady-state changes in the Ti L2,3 edge are measured with and without continuous-wave illumination of the nanoparticle's localized surface plasmon resonance. The results suggest that within error the quasi-equilibrium carrier distribution can be determined even from relatively noisy data with mixed excited-state phenomena. Just as importantly, the theoretical analysis of noisy data is used to provide guidelines for the beamline development of photomodulated steady-state spectroscopy.

A Sustainable Route to Ruthenium Phosphide (RuP)/Ru Heterostructures with Electron-Shuttling of Interfacial Ru for Efficient Hydrogen Evolution.

Ruthenium (Ru) is a promising electrocatalyst for the hydrogen evolution reaction (HER), despite suffering from low activity in non-acidic conditions due to the high kinetic energy barrier of H2O dissociation. Herein, the synthesis of carbon nanosheet-supported RuP/Ru heterostructures (RuP/Ru@CNS) from a natural polysaccharide is reported and demonstrates its behavior as an effective HER electrocatalyst in non-acidic conditions. The RuP/Ru@CNS exhibits low overpotential (106 mV at 200 mA·cm-2) in alkaline electrolyte, exceeding most reported Ru-based electrocatalysts. The electron shuttling between Ru atoms at the RuP/Ru interface results in a lowered energy barrier for H2O dissociation by electron-deficient Ru atoms in the pure Ru phase, as well as optimized H* adsorption of electron-gaining Ru atoms in the neighboring RuP. A low H* spillover energy barrier between Ru atoms at the RuP/Ru interface further boosts HER kinetics. This study demonstrates a sustainable method for the fabrication of efficient Ru-based electrocatalysts and provides a more detailed understanding of interface effects in HER catalysis.

Novel Heterostructure-Based CoFe and Cobalt Oxysulfide Nanocubes for Effective Bifunctional Electrocatalytic Water and Urea Oxidation.

The development of effective oxygen evolution reaction (OER) and urea oxidation reaction (UOR) on heterostructure electrocatalysts with specific interfaces and characteristics provides a distinctive character. In this study, heterostructure nanocubes (NCs) comprising inner cobalt oxysulfide (CoOS) NCs and outer CoFe (CF) layered double hydroxide (LDH) are developed using a hydrothermal methodology. During the sulfidation process, the divalent sulfur ions (S2-) are released from the breakdown of the sulfur source and react with the Co-precursors on the surface leading to the transformation of CoOH nanorods into CoOS nanocubes. Further, X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) analyses reveal that the interactions at the interface of the CF@CoOS NCs significantly altered the electronic structure, thus enhancing the electrocatalytic performance. The optimal catalysts exhibited effective OER and UOR activities, the attained potentials are 1.51 and 1.36 V. This remarkable performance is attributable to the induction of electron transfer from the CoFe LDH to CoOS, which reduces the energy barrier of the intermediates for the OER and UOR. Furthermore, an alkaline water and urea two-cell electrolyzer assembled using CF@CoOS-2 NCs and Pt/C as the anode and cathode requires a cell voltage of 1.63 and 1.56 V along with a durability performance.

Vacancy-induced catalytic mechanism for alcohol electrooxidation on nickel-based electrocatalyst.

Owing to outstanding performances, nickel-based electrocatalysts are commonly used in electrochemical alcohol oxidation reactions (AORs), and the active phase is usually vacancy-rich nickel oxide/hydroxide (NiOx Hy ) species. However, researchers are not aware of the catalytic role of atom vacancy in AORs. Here, we study vacancy-induced catalytic mechanisms for AORs on NiOx Hy species. As to AORs on oxygen-vacancy-poor ß-Ni(OH)2 , the only redox mediator is electrooxidation-induced electrophilic lattice oxygen species, which can only catalyze the dehydrogenation process (e.g., the electrooxidation of primary alcohol to carboxylic acid) instead of the C-C bond cleavage. Hence, vicinal diol electrooxidation reaction involving the C-C bond cleavage is not feasible with oxygen-vacancy-poor ß-Ni(OH)2 . Only through oxygen vacancy-induced adsorbed oxygen-mediated mechanism, can oxygen-vacancy-rich NiOx Hy species catalyze the electrooxidation of vicinal diol to carboxylic acid and formic acid accompanied with the C-C bond cleavage. Crucially, we examine how vacancies and vacancy-induced catalytic mechanisms work during AORs on NiOx Hy species.

Selective Electroreduction of 5-Hydroxymethylfurfural to Dimethylfuran in Neutral Electrolytes via Hydrogen Spillover and Adsorption Configuration Adjustment.

5-Hydroxymethylfurfural (HMF), one of the essential C6 biomass derivatives, has been deeply investigated in electrocatalytic reduction upgrading. Nevertheless, the high product selectivity and rational design strategy of electrocatalysts for electrocatalytic HMF reduction is still a challenge. Here, a high selective electro-reduction of HMF to dimethylfuran (DMF) on palladium (Pd) single atom loaded on titanium dioxide (Pd SA/TiO2 ) via hydrogen spillover and adsorption configuration adjustment in neutral electrolytes is achieved. Combining density functional theory calculations and in situ characterization, it is revealed that Pd single atom could weaken the interaction between Pd atoms and adsorbed hydrogen (*H) to promote the *H spillover for increasing *H coverage on the surface and maintain the tilted adsorption configuration to activate C═O bond; thus the selectivity of DMF on Pd SA/TiO2 increases to 90.33%. Besides, it is elaborated that low *H coverage on TiO2 favors the formation of bis(hydroxymethyl)hydro-furoin (BHH), and the flat adsorption configuration of HMF on Pd nanoparticles benefits to form 2,5-dihydroxymethylfuran (DHMF). This work provides a promising approach for modifying electrocatalysts to realize the selective electroreduction of HMF to value-added products.

Reducing the Ir-O Coordination Number in Anodic Catalysts based on IrOx Nanoparticles towards Enhanced Proton-exchange-membrane Water Electrolysis.

Due to the robust oxidation conditions in strong acid oxygen evolution reaction (OER), developing an OER electrocatalyst with high efficiency remains challenging in polymer electrolyte membrane (PEM) water electrolyzer. Recent theoretical research suggested that reducing the coordination number of Ir-O is feasible to reduce the energy barrier of the rate-determination step, potentially accelerating the OER. Inspired by this, we experimentally verified the Ir-O coordination number's role at model catalysts, then synthesized low-coordinated IrOx nanoparticles toward a durable PEM water electrolyzer. We first conducted model studies on commercial rutile-IrO2 using plasma-based defect engineering. The combined in situ X-ray absorption spectroscopy (XAS) analysis and computational studies clarify why the decreased coordination numbers increase catalytic activity. Next, under the model studies' guidelines, we explored a low-coordinated Ir-based catalyst with a lower overpotential of 231 mV@10 mA cm-2 accompanied by long durability (100 h) in an acidic OER. Finally, the assembled PEM water electrolyzer delivers a low voltage (1.72 V@1 A cm-2 ) as well as excellent stability exceeding 1200 h (@1 A cm-2 ) without obvious decay. This work provides a unique insight into the role of coordination numbers, paving the way for designing Ir-based catalysts for PEM water electrolyzers.

Trimetallic Oxide Electrocatalyst for Enhanced Redox Activity in Zinc-Air Batteries Evaluated by In Situ Analysis.

Researchers are investigating innovative composite materials for renewable energy and energy storage systems. The major goals of this studies are i) to develop a low-cost and stable trimetallic oxide catalyst and ii) to change the electrical environment of the active sites through site-selective Mo substitution. The effect of Mo on NiCoMoO4 is elucidated using both in situ X-ray absorption spectroscopy and X-ray diffraction analysis. Also, density functional theory strategies show that NiCoMoO4 has extraordinary catalytic redox activity because of the high adsorption energy of the Mo atom on the active crystal plane. Further, it is demonstrated that hierarchical nanoflower structures of NiCoMoO4 on reduced graphene oxide can be employed as a powerful bifunctional electrocatalyst for oxygen reduction/evolution reactions in alkaline solutions, providing a small overpotential difference of 0.75 V. Also, Zn-air batteries based on the developed bifunctional electrocatalyst exhibit outstanding cycling stability and a high-power density of 125.1 mW cm-2 . This work encourages the use of Zn-air batteries in practical applications and provides an interesting concept for designing a bifunctional electrocatalyst.

Novel GdTaO4 phase for efficient photocatalytic degradation of organic dye under visible light irradiation: An X-ray spectroscopic investigation.

The novel GdTaO4 phase exhibits good photocatalytic activity under visible light irradiation and holds great promise for the removal of organic dyes from industrial wastes. The GdTaO4 samples were synthesized using the hydrothermal and calcination process with different weight ratios of gadolinium nitrate hydrate (G) and tantalum pentachloride (T), and their structural studies confirmed the formation of the GdTaO4 (GT) phase. Among the samples, GT-4 (with a weight ratio of 4:1) exhibited the highest photocatalytic activity for the degradation of Methyl Orange (MO) dye under visible light irradiation. To enhance the photocatalytic performance, H2O2 was used as a green additive, and the photocatalytic abilities were examined by varying dye types and concentrations. X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) revealed the local atomic and electronic structures around Ta and Gd and highlighted the contribution of Gd3+ to the GT system, which is a crucial factor in supporting the enhanced photocatalytic performance. Moreover, in-situ XAS at Gd M5-edge and O K-edge were examined under illumination/dark conditions to explore the electronic structures of photo-excited electron transition in the photocatalytic process. The analytical results provided strong evidence correlating the electronic structure and photocatalytic property of the GT. This study demonstrates that GdTaO4 exhibits good photocatalytic activity under visible light irradiation, making it a promising new Ta-based photocatalyst for the effective removal of organic dyes from industrial wastes.

Defect-Rich SnO2 Nanofiber as an Oxygen-Defect-Driven Photoenergy Shield against UV Light Cell Damage.

Usually, most studies focus on toxic gas and photosensors by using electrospinning and metal oxide polycrystalline SnO2 nanofibers (PNFs), while fewer studies discuss cell-material interactions and photoelectric effect. In this work, the controllable surface morphology and oxygen defect (VO) structure properties were provided to show the opportunity of metal oxide PNFs to convert photoenergy into bio-energy for bio-material applications. Using the photobiomodulation effect of defect-rich polycrystalline SnO2 nanofibers (PNFs) is the main idea to modulate the cell-material interactions, such as adhesion, growth direction, and reactive oxygen species (ROS) density. The VO structures, including out-of-plane oxygen defects (op-VO), bridge oxygen defects (b-VO), and in-plane oxygen defects (ip-VO), were studied using synchrotron analysis to investigate the electron transfer between the VO structures and conduction bands. These intragrain VO structures can be treated as generation-recombination centers, which can convert various photoenergies (365-520 nm) into different current levels that form distinct surface potential levels; this is referred to as the photoelectric effect. PNF conductivity was enhanced 53.6-fold by enlarging the grain size (410 nm2) by increasing the annealing temperature, which can improve the photoelectric effect. In vitro removal of reactive oxygen species (ROS) can be achieved by using the photoelectric effect of PNFs. Also, the viability and shape of human bone marrow mesenchymal stem cells (hMSCs-BM) were also influenced significantly by the photobiomodulation effect. The cell damage and survival rate can be prevented and enhanced by using PNFs; metal oxide nanofibers are no longer only environmental sensors but can also be a bio-material to convert the photoenergy into bio-energy for biomedical science applications.

Direct Dioxygen Radical Coupling Driven by Octahedral Ruthenium-Oxygen-Cobalt Collaborative Coordination for Acidic Oxygen Evolution Reaction.

The acidic oxygen evolution reaction (OER) has long been the bottleneck of proton exchange membrane water electrolyzers given its harsh oxidative and corrosive environments. Herein, we suggest an effective strategy to greatly enhance both the acidic OER activity and stability of Co3O4 spinel by atomic Ru selective substitution on the octahedral Co sites. The resulting highly symmetrical octahedral Ru-O-Co collaborative coordination with strong electron coupling effect enables the direct dioxygen radical coupling OER pathway. Indeed, both experiments and theoretical calculations reveal a thermodynamically breakthrough heterogeneous diatomic oxygen mechanism. Additionally, the active Ru-O-Co units are well-maintained upon the acidic OER thanks to the electron transfer from surrounding electron-enriched tetrahedral Co atoms via bridging oxygen bonds that suppresses the overoxidation and thus dissolution of active Ru and Co species. Consequently, the prepared catalyst, even with a low Ru mass loading of ca. 42.8 µg cm-2, exhibits an attractive acidic OER performance with a low overpotential of 200 mV and a low potential decay rate of 0.45 mV h-1 at 10 mA cm-2. Our work suggests an effective strategy to significantly enhance both the acidic OER activity and stability of low-cost electrocatalysts.

Synthesis and characterization of visible-light-driven novel CuTa2O6 as a promising practical photocatalyst.

In this work, the novel CuTa2O6 phase was successfully synthesized by the hydrothermal and followed by the calcination process. The X-ray diffraction pattern confirms the formation of different phases. At a low temperature, CuTa2O6 exhibits the orthorhombic phase, whereas, at a higher temperature, it underwent a phase transition to a cubic crystal structure. X-ray photoelectron spectroscopic results suggest the presence of all the elements (Cu, Ta, and O). The optical studies were carried out using a UV-Vis DRS spectrophotometer. FESEM images confirm the spherical-shaped particles for the sample annealed at a high temperature. The local atomic and electronic structures around Cu and the contribution of the Cu oxidation state in the CuTa2O6 system were determined by X-ray absorption spectroscopy. To investigate the effective usage of CuTa2O6 in treating wastewater, its photocatalytic activity was investigated by evaluating its use in the photodegradation of MO dye under visible light irradiation. Moreover, the prepared CuTa2O6 photocatalyst exhibits significant photocatalytic activity in the degradation of MO dye and shows excellent stability; it is therefore a promising material for potential use in a practical photocatalyst. The CuTa2O6 photocatalyst suggests an alternative avenue of research into effective photo-catalysts for solar hydrogen water splitting.

Surface Adsorbed Hydroxyl: A Double-Edged Sword in Electrochemical CO2 Reduction over Oxide-Derived Copper.

Oxide-derived Cu (OD-Cu) featured with surface located sub-20 nm nanoparticles (NPs) created via surface structure reconstruction was developed for electrochemical CO2 reduction (ECO2 RR). With surface adsorbed hydroxyls (OHad ) identified during ECO2 RR, it is realized that OHad , sterically confined and adsorbed at OD-Cu by surface located sub-20 nm NPs, should be determinative to the multi-carbon (C2 ) product selectivity. In situ spectral investigations and theoretical calculations reveal that OHad favors the adsorption of low-frequency *CO with weak C≡O bonds and strengthens the *CO binding at OD-Cu surface, promoting *CO dimerization and then selective C2 production. However, excessive OHad would inhibit selective C2 production by occupying active sites and facilitating competitive H2 evolution. In a flow cell, stable C2 production with high selectivity of ∼60 % at -200 mA cm-2 could be achieved over OD-Cu, with adsorption of OHad well steered in the fast flowing electrolyte.

Unraveling the electrophilic oxygen-mediated mechanism for alcohol electrooxidation on NiO.

Aqueous organic electrosynthesis such as nucleophile oxidation reaction (NOR) is an economical and green approach. However, its development has been hindered by the inadequate understanding of the synergy between the electrochemical and non-electrochemical steps. In this study, we unravel the NOR mechanism for the primary alcohol/vicinal diol electrooxidation on NiO. Thereinto, the electrochemical step is the generation of Ni3+-(OH)ads, and the spontaneous reaction between Ni3+-(OH)ads and nucleophiles is an electrocatalyst-induced non-electrochemical step. We identify that two electrophilic oxygen-mediated mechanisms (EOMs), EOM involving hydrogen atom transfer (HAT) and EOM involving C-C bond cleavage, play pivotal roles in the electrooxidation of primary alcohol to carboxylic acid and the electrooxidation of vicinal diol to carboxylic acid and formic acid, respectively. Based on these findings, we establish a unified NOR mechanism for alcohol electrooxidation and deepen the understanding of the synergy between the electrochemical and non-electrochemical steps during NOR, which can guide the sustainable electrochemical synthesis of organic chemicals.

Tuning Electronic State and Charge Transport in B←N-Containing 2D Polymer Heterostructures with Efficient Photocatalytic Performance.

Linear-conjugated polymers (LCPs) are excellent semiconductor photocatalysts. However, its inherent amorphous structures and simple electron transport channels restrict efficient photoexcited charge separation and transfer. Herein, "2D conjugated engineering" is employed to design high-crystalline polymer photocatalysts with multichannel charge transport by introducing alkoxyphenyl sidechains. The electronic state structure and electron transport pathways of the LCPs are investigated using experimental and theoretical calculations. Consequently, the 2D B←N-containing polymers (2DPBN) exhibit excellent photoelectric characteristics, which enable the efficient separation of electron-hole and rapidly transfer photogenerated carriers to the catalyst surface for efficient catalytic reactions. Significantly, the further hydrogen evolution of 2DPBN-4F heterostructures can be achieved by increasing the fluorine content of the backbones. This study highlights that the rational design of LCP photocatalysts is an effective strategy to spur further interest in photofunctional polymer material applications.