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Metal single‐atom catalysts represent one of the most promising non‐noble metal catalysts for the oxygen reduction reaction (ORR). However, they still suffer from insufficient activity and, particularly, durability for practical applications. Leveraging density functional theory (DFT) and machine learning (ML), we unravel an unexpected collective effect between FeN4OH sites, CeN4OH motifs, Fe nanoparticles (NPs), and Fe−CeO2 NPs. The collective effect comprises differently‐weighted electronic and geometric interactions, whitch results in significantly enhanced ORR activity for FeN4OH active sites with a half‐wave potential (E1/2) of 0.948 V versus the reversible hydrogen electrode (VRHE) in alkaline, relative to a commercial Pt/C (E1/2, 0.851 VRHE). Meanwhile, this collective effect endows the shortened Fe−N bonds and the remarkable durability with negligible activity loss after 50,000 potential cycles. The ML was used to understand the intricate geometric and electronic interactions in collective effect and reveal the intrinsic descriptors to account for the enhanced ORR performance. The universality of collective effect was demonstrated effective for the Co, Ni, Cu, Cr, and Mn‐based multicomponent ensembles. These results confirm the importance of collective effect to simultaneously improve catalytic activity and durability. [ABSTRACT FROM AUTHOR]

Designing high-performance electrocatalysts toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is essential to reduce the activation barrier and optimize free adsorption energy of reactive intermediates. Herein, we report that incorporating high-valence Cr into NiSe2 (CrxNi1−xSe2) kinetically and thermodynamically expedites elementary steps of both HER and OER. The as-prepared Cr0.05Ni0.95Se2 catalyst displays excellent HER and OER activities, with low overpotentials of 89 and 272 mV at the current density of 10 mA·cm−2 (j10), respectively, and remains stable during operation for 30 h. A low cell voltage of only 1.59 V is required to drive j10 in alkaline media. In situ Raman spectroscopy reveals that Cr incorporation facilitates the formation of NiOOH active species during the OER process. Meanwhile, theoretical explorations demonstrate that high-valence Cr incorporation efficiently accelerates water dissociation kinetics and improves H* adsorption during HER process, lowering the activation barrier of OER and optimizing the adsorption energy of oxygen-based intermediate, thus kinetically and thermodynamically enhancing the intrinsic performance of NiSe2 for over water splitting. This strategy provides a new horizon to design transition metal based electrocatalysts in the clean energy field. [ABSTRACT FROM AUTHOR]

Photocatalytic water splitting holds great promise as a sustainable and cost‐effectiveness alternative for the production of hydrogen. Nevertheless, the practical implementation of this strategy is hindered by suboptimal visible light utilization and sluggish charge carrier dynamics, leading to low yield. MXene is a promising cocatalyst due to its high conductivity, abundance of active sites, tunable terminal functional groups, and great specific surface area. Homo‐interface has perfect lattice matching and uniform composition, which are more conducive to photogenerated carriers' separation and migration. In this study, a novel ternary heterogeneous photocatalyst, a‐TiO2/H‐TiO2/Ti3C2 MXene (MXTi), is presented using an electrostatic self‐assembly method. Compared to commercial P25, pristine anatase, and rutile TiO2, as‐prepared MXTi exhibit exceptional photocatalytic hydrogen evolution performance, achieving a rate of 0.387 mmol h−1. The significant improvement is attributable to the synergistic effect of homo‐interface engineering and Ti3C2 MXene, which leads to widened light absorption and efficient carrier transportation. The findings highlight the potential of interface engineering and MXene cocatalyst loading as a proactive approach to enhance the performance of photocatalytic water splitting, paving the way for more sustainable and efficient hydrogen production. [ABSTRACT FROM AUTHOR]

MXene quantum dots (MQDs) offer wide applications owing to the abundant surface chemistry, tunable energy‐level structure, and unique properties. However, the application of MQDs in electrochemical energy conversion, including hydrogen evolution reaction (HER), remains to be realized, as it remains a challenge to precisely control the types of surface groups and tune the structure of energy levels in MQDs, owing to the high surface energy–induced strong agglomeration in post‐processing. Consequently, the determination of the exact catalytically active sites and processes involved in such an electrocatalysis is challenging because of the complexity of the synthetic process and reaction conditions. Herein, we demonstrated the spontaneous evolution of the surface groups of the Ti2CTx MQDs (x: the content of O atom), i.e., replacement of the ‐Cl functional groups by O‐terminated ones during the cathode reaction. This process resulted in a low Gibbs free energy (0.26 eV) in HER. Our steady Ti2COx/Cu2O/Cu foam systems exhibited a low overpotential of 175 mV at 10 mA cm−2 in 1 M aq. KOH, and excellent operational stability over 165 h at a constant current density of −10 mA cm−2. [ABSTRACT FROM AUTHOR]

The electrochemical decomposition of water plays a critical role in green and sustainable energy. However, the development of efficient and low-cost non-noble metal catalysts to overcome the high potential of the anodic oxygen evolution reaction (OER) is still challenging. In this work, electrocatalysts with high OER activity were obtained by doping Co/Fe bimetals into Ni3S2 (CF-NS) via a simple single-step hydrothermal method by adjusting the doping ratio of bimetals. A series of characterization studies revealed that the introduction of a Co/Fe co-dopant increased the number of active sites and improved the electroconductibility, while optimizing the electronic structure of Ni3S2. Meanwhile, Fe-induced high valence Ni contributed to the production of an OER active phase NiOOH. The unique dendritic crystal morphology facilitated the disclosure of the active sites and the expansion of mass transfer channels. The optimized sample required a low overpotential of 146 mV to obtain a current density of 10 mA cm−2 in 1.0 M KOH solution. The optimized sample also operated stably for at least 86 h. In sum, the proposed method looks very promising for designing efficient, stable, and low-cost non-precious metal catalysts with high conductivity and multiple active sites, useful for future synthesis of transition metal sulfide catalysts. [ABSTRACT FROM AUTHOR]

Lithium metal has been recognized as the most promising anode material due to its high capacity and low electrode potential. However, the high reactivity, infinite volume variation, and uncontrolled dendrites growth of Li during long‐term cycling severely limit its practical applications. To address these issues, herein, a novel 3D Al/Mg/Li alloy (denoted as AM‐Li) anode is designed and constructed by a facile smelting‐rolling strategy, which improves the surface stability, electrochemical cycling stability, and rate capability in lithium metal batteries. Specifically, the optimized AM‐Li|AM‐Li symmetric cell exhibits low polarization voltage (< 20 mV) and perfect cycling stability at 1 mA cm−2‐1 mAh cm−2 for more than 1600 h. Moreover, the AM‐Li|NCM811 full cell exhibits superior rate capability up to 5 C and excellent cyclability for 100 cycles at 0.5 C with a high capacity retention of 90.8%. The realization of lithium‐poor or lithium‐free anode materials will be a major development trend of anode materials in the future. Therefore, the research shows that the construction of 3D alloy framework is beneficial to improve the cycling stability of Li anodes by suppressing the volume expansion effect and Li dendrite growth, which will promote the further development of lithium‐poor metal anodes. [ABSTRACT FROM AUTHOR]

Efficient electrocatalytic reactions require a coordinated active center that may provide a properly reaction intermediates adsorption in water splitting. Herein, a Ni active center coordination reconstruction method achieved by multidimensional modulation of phase transition, iodine coordination, and vacancy defects is designed and implemented. This coordination reconstruction results in the successful synthesis of Ni5P4−xIx/Ni2P nanocorals that show outstanding bifunctional catalytic activity due to deep optimization of the adsorption energy. The overpotentials of hydrogen evolution reaction and oxygen evolution reaction at 10 mA cm−2 are 46 and 163 mV, respectively. Only 1.46 V is required to drive alkaline overall water splitting. Novel coordination environment is investigated by electron paramagnetic resonance spectroscopy and extended X‐ray absorption fine structure spectroscopy. A 4D integrated material design strategy of "thermodynamic stability‐electronic properties‐charge transfer‐adsorption energy" for water‐splitting catalysts is proposed. This coordination reconstruction concept and material design method provide new perspectives for the research of novel catalysts. [ABSTRACT FROM AUTHOR]

Accelerating slow water dissociation kinetics is key to boosting the hydrogen evolution reaction (HER) in alkaline media. We report the synthesis of atomically dispersed MoOx species anchored on Rh metallene using a one‐pot solvothermal method. The resulting structures expose the oxide‐metal interfaces to the maximum extent. This leads to a MoOx‐Rh catalyst with ultrahigh alkaline HER activity. We obtained a mass activity of 2.32 A mgRh−1 at an overpotential of 50 mV, which is 11.8 times higher than that of commercial Pt/C and surpasses the previously reported Rh‐based electrocatalysts. First‐principles calculations demonstrate that the interface between MoOx and Rh is the active center for alkaline HER. The MoOx sites preferentially adsorb and dissociate water molecules, and adjacent Rh sites adsorb the generated atomic hydrogen for efficient H2 evolution. Our findings illustrate the potential of atomic interface engineering strategies in electrocatalysis. [ABSTRACT FROM AUTHOR]

Constructing earth‐abundant water splitting electrocatalysts performing platinum‐like activity is promising for the hydrogen economy but still a challenging task. Herein, the ultrafine CoMnP nanocrystals confined in amorphous carbon nanosheets are designed and implemented by a topological transformation strategy from layer double hydroxide/carbon interconnected structures in one single nanosheet. The unique interconnected structure favors the exposure of active sites and enables stronger electronic coupling effect between the two phases. Experimental results and density functional theory simulations reveal that the surrounding amorphous carbon and Mn dopants synergistically enable better electron delocalization capacity of Co sites, potentially providing enhanced conductivity and optimal reaction energetics during hydrogen evolution. The as‐prepared catalyst exhibits hydrogen evolution reaction performances superior to that of Pt/C under alkaline media with an overpotential of 114 mV at 100 mA cm–2. This work highlights the rational fabrication of transition metal‐based electrocatalysts via spatially confined growth for efficient water electrolysis. [ABSTRACT FROM AUTHOR]

The devise and fabrication of highly efficient electrocatalysts have momentous practical significance for the development of future hydrogen energy systems. However, their potential uses in support construction are not well studied. In this work, a highly efficient electrocatalyst is developed for the hydrogen evolution reaction by anchoring single Pt atoms and clusters into functional amorphous pentlandite Fe5Ni4S8 (or FNS) to yield Pt–FNS composites. Amorphous FNS still provides great conductivity to the composites, thereby promoting rapid charge transfer. The presence of abundant defects in Pt–FNS composite catalysts induces pleasant atomic dispersion and anchoring of Pt species. In addition, the formation of single Pt atoms combined with clusters and low‐Pt‐loading improves the utilization of Pt and reduces the cost. The turnover frequency analysis suggests Pt–FNS systems possess significant unit catalytic activity. The synergetic catalytic effect issued from high conductivity, abundant active sites and elevated intrinsic activity forms Pt–FNS systems with efficient pH‐universal catalytic activity. The systems exhibit low overpotentials of only 30, 65, and 98 mV at 10 mA cm−2 under acidic, alkaline, and neutral conditions, respectively. In sum, the proposed route looks promising for the fabrication of new electrocatalysts with improved properties. [ABSTRACT FROM AUTHOR]

The grand challenge in the development of atomically dispersed metallic catalysts is their low metal-atom loading density, uncontrollable localization and ambiguous interactions with supports, posing difficulty in maximizing their catalytic performance. Here, we achieve an interface catalyst consisting of atomic cobalt array covalently bound to distorted 1T MoS2 nanosheets (SA Co-D 1T MoS2). The phase of MoS2 transforming from 2H to D-1T, induced by strain from lattice mismatch and formation of Co-S covalent bond between Co and MoS2 during the assembly, is found to be essential to form the highly active single-atom array catalyst. SA Co-D 1T MoS2 achieves Pt-like activity toward HER and high long-term stability. Active-site blocking experiment together with density functional theory (DFT) calculations reveal that the superior catalytic behaviour is associated with an ensemble effect via the synergy of Co adatom and S of the D-1T MoS2 support by tuning hydrogen binding mode at the interface. While single-atom catalysis offers an efficient materials usage, the ambiguous interactions with supports poses a difficulty in understanding catalytic performances. Here, authors show an ensemble effect via synergy of Co adatoms and the S of MoS2 supports to boost hydrogen evolution activities. [ABSTRACT FROM AUTHOR]

Successful atom-by-atom controlling over surface and subsurface termination in a series of Fe−Pt intermetallic catalysts, via regulating the order degree of Fe/Pt, enables finely tuning their hydrogen evolution performance and thereof harvesting the superior hydrogen production with merits of a unique Fe/Pt coordination and oxidation-resistant Pt-rich surface. [Display omitted] Controlling the atomic arrangement of elemental atoms in intermetallic catalysts to govern their surface and subsurface properties is a crucial but challenging endeavor in electrocatalytic reactions. In hydrogen evolution reaction (HER), adjusting the d-band center of the conventional noble-metallic Pt by introducing Fe enables the optimization of catalytic performance. However, a notable gap exists in research on the effective transition from disordered Fe/Pt alloys to highly ordered intermetallic compounds (IMCs) such as FePt 3 in the alkaline HER, hampering their broader application. In this study, a series of catalysts FePt 3 - x H (x = 5, 6, 7, 8 and 9) supported on carbon nanotubes (CNTs) were synthesized via a simple impregnation method, along with a range of heat treatment processes, including annealing in a reductive atmosphere, to regulate the order degree of the arrangement of Fe/Pt atoms within the FePt 3 catalyst. By using advanced microscopy and spectroscopy techniques, we systematically explored the impact of the order degree of FePt 3 in the HER. The as-prepared FePt 3 -8H exhibited notable HER catalytic activity with low overpotentials (η = 37 mV in 1.0 mol L−1 KOH) at j = 10 mA cm−2. The surface of the L1 2 FePt 3 -8H catalyst was demonstrated to be Pt-rich. The Pt on the surface was not easily oxidized due to the unique Fe/Pt coordination, resulting in significant enhancement of HER performance. [ABSTRACT FROM AUTHOR]

The development of low-price and highly efficient catalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) has always been challenging with regard to water splitting. Pyrrhotite Fe 7 S 8 has become a research hotspot due to its abundant reserves, high electrical conductivity and excellent catalytic activity. In general, introducing metal heteroatoms into transition metal sulfides (TMSs) can effectively enhance the activity and stability of TMSs. Herein, Co-doped pyrrhotite Fe 7 S 8 nanosheets were obtained by a straightforward two-step method consisting of hydrothermal treatment followed by subsequent heat treatment. Results from XPS analysis and contact angle measurements showed that doping optimized the chemical environment around iron atoms and enhanced the adsorption of water molecules on the surface of Fe 7 S 8 , thereby greatly improving the electrocatalytic efficiency of water electrolysis. Compared with other counterparts, Co 0 · 95 Fe 6 · 05 S 8 exhibited superior OER activity with an overpotential of 311 mV at a current density of 10 mA cm−2, and higher performance towards HER with an overpotential of 284 mV at 10 mA cm−2 in alkaline solution. In sum, Co 0 · 95 Fe 6 · 05 S 8 is promising as a bifunctional catalyst for water splitting under alkaline conditions. [ABSTRACT FROM AUTHOR]

Preventing agglomeration and corrosion of metal electrocatalysts at nanoscale is crucial for electrochemical energy conversion, such as fuel cell and overall water splitting, where all the oxygen evolution reaction (OER), hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) are the core. Herein, an effective strategy is developed for preparing multifunctional self-supporting electrocatalysts with uniformly distributed cobalt nanoparticles and clusters. Benefiting from good electrical conductivity and multiple active sites, the trifunctional self-supporting catalyst free from stacking and aggregating exhibits excellent OER and HER activities with an overpotential of 270 and 110 mV to obtain a current density of 10 mA cm−2 in alkaline media. The ORR performance was tested in 0.1 M KOH solution with a half-wave potential of ∼0.80 V and a limiting current density of ∼ −4.8 mA cm−2. Our finding provides an opportunity for the rational design of multifunctional and highly-efficient self-supporting electrocatalysts towards the integration of electrochemical energy conversion. Image 1 [ABSTRACT FROM AUTHOR]

Single-atom catalysts have attracted extensive attention due to their unique performances and high atom utilization. However, is single atom always the best? Here we found a reverse case that nickel metaphosphate (NPO) supported nanoparticles (Ru n) is much better than single atoms (Ru s) for all pH hydrogen evolution. The mass activity of Ru n -NPO is 3.8 times higher than that of Ru s -NPO, and 21.4 times higher than that of Pt/C in alkaline media. The results show that Ru nanoparticle possess lower valence state than single atom, providing optimized Ru-H bond strength and suitable hydrogen adsorption free energy. As a novel support, NPO is also essential for firmly anchoring Ru and transporting electrons for optimizing the d -band center, and eventually accelerating the H 2 O dissociation in rate-limiting Volmer step. This work gives Ru-NPO promising potential for practical hydrogen production, and sheds light on the exploration of supported metal catalysts in energy conversion-related fields. [Display omitted] • Nickel metaphosphate (NPO) supported Ru catalyst is developed for all pH HER. • Ru nanoparticles exhibit better HER activity than Ru single atoms. • NPO optimizes the thermodynamic parameter of Ru through metal-support interactions. • The sluggish kinetics of Ru in Volmer step have been speed up. [ABSTRACT FROM AUTHOR]

Fe 5 Ni 4 S 8 /Ni 3 S 2 is a highly efficient and robust bifunctional electrocatalyst for overall water splitting due to its charge transport double-channel structure and strong electronic interaction. [Display omitted] • The stepped rod-shaped Ni 3 S 2 3D nanoarray structure supplied the system with sufficient active sites. • The double-channel structure, which consisted of high-conductivity Fe 5 Ni 4 S 8 and NF, provided an increase in the rate of internal charge transfer. • The overall water splitting device with appropriate samples achieved 1.64 V@10 mA cm−2 cell voltage. And it remained active for at least 120 h at an industrial-grade high current density (500 mA cm−2). Overall water splitting technology is critical for the future of a clean and sustainable hydrogen energy infrastructure. Ni 3 S 2 (NS) is considered a good performing oxygen evolution reaction (OER) catalyst, but exhibits unsatisfactory hydrogen evolution reaction (HER) activity. In this study, Fe 5 Ni 4 S 8 (FNS) material was incorporated into an NS nanoarray, generating a low-cost, efficient, and stable bifunctional FNS/NS heterostructure for electrolyzed water catalysts. The hydrophilicity of pretreated FNS was quite high, whereas the stepped rod-shaped NS structure had a large number of radial active sites. Additionally, the high-conductivity of FNS and nickel foam (NF) provided a double-channel structure for rapid internal charge transfer. The interconnecting a network of FNS, rod-shaped NS nanoarray, and NF substrate enabled one to accomplish a synergistic effect of enhanced kinetics and activity of OER, HER, and overall water splitting. To achieve a current density of 10 mA cm−2 in 1.0 M KOH solution, only overpotentials of 248 and 94 mV were required. Moreover, the voltage of the constructed FNS/NS||FNS/NS double-electrode battery system was only 1.64 V@10 mA cm−2, but the battery could have run for at least 120 h at an industrial current density of 500 mA cm−2. Therefore, this study offers a rational design of heterostructures as bifunctional electrocatalysts for overall water splitting. [ABSTRACT FROM AUTHOR]

Fe 5 Ni 4 S 8−x electrocatalysts toward HER were developed through surface reconstruction and vacancy engineering. The optimal electrocatalyst exhibited the overpotential of 107 mV@10 mA cm−2 and a small Tafel slope of 40 mV dec−1 in acidic media. [Display omitted] • The surface reconstruction in (3 1 1) facets of pentlandite exposes more active sites. • Sulfur vacancies generated at the site bridging two metal cubes can provide bimetallic catalytic sites. • Pentlandite with appropriate sulfur vacancy content exhibited high HER activity. Transition metal sulfide pentlandite, (Fe, Ni) 9 S 8 , emerges as a prominent catalyst for electrolytic hydrogen evolution reaction (HER) owing to high conductivity and stability. In order to investigate the effect of sulfur (S) vacancy content on the HER activity of (Fe, Ni) 9 S 8 for optimal HER activity, controlled levels of S vacancies need to be generated. Herein, Fe 5 Ni 4 S 8− x electrocatalysts toward HER were developed through surface reconstruction and S vacancy engineering through a simple heat treatment method. The surface reconstruction could regulate the surface structure to be more stable and lead to a higher number of exposed active sites. S vacancies provided an Fe–Ni synergistic effect to facilitate the hydrogen adsorption, further improving catalytic activity. The optimal Fe 5 Ni 4 S 8− x electrocatalyst exhibited the overpotential of 107 mV at 10 mA cm−2 in acidic media. Tafel slope and electrochemical impedance spectroscopy further demonstrate that the proposed thermal treatment to modulate the S vacancy content is a feasible approach to further accelerate the HER kinetics. This study provides valuable insights for the rational formulation of high-efficiency pentlandite electrocatalysts. [ABSTRACT FROM AUTHOR]

Development of efficient electrocatalysts requires construction of catalytic surfaces with moderate H adsorption energy. Here, we address this challenge by Br-induced formation of P-poor defective nickel phosphide and show that the H adsorption energy can be optimized by regulating the vacancy concentration. We show that when such defective Ni 12 P 5−x Br x nanoparticles are distributed on the surface of Ni 2 P nanosheets (Ni 12 P 5−x Br x /Ni 2 P NS), excellent catalytic activity for water splitting is obtained in alkaline media. Density functional theory computations revealed that Br doping induce the formation of a P-poor nickel phosphide with vacancies, leading to an optimal H adsorption strength with a volcano-type relationship. This is the best reported for a non-precious metal phosphide at present: the overpotential for HER is 18 mV at 10 mA cm−2 and 155 mV for OER. This leads to an exceptionally low cell voltage requirement of only 1.44 V to drive overall water splitting in an alkaline electrolyzer. [Display omitted] • Br-induced nickel phosphide formation energy change achieves P-poor defective phase configuration. • Multi-level regulation of vacancy content, morphology and catalytic performance by temperature is achieved. • DFT calculations show that Ni 12 P 5−x Br x shows a volcano-type relationship related to vacancy content. [ABSTRACT FROM AUTHOR]

[Display omitted] • Pyridine conjugated graphitic carbon nitride is successfully synthesized. • As-prepared catalyst exhibits superior photocatalytic hydrogen evolution. • Modulated localization of electron cloud density in as-prepared catalyst. • Narrowed bandgap and enhanced carriers' separation efficiency in as-prepared catalyst. High photogenerated carrier recombination and poor visible light response in symmetry graphitic carbon nitride are two classical problems for photocatalytic hydrogen evolution. In this work, we rationally design a novel carbon nitride (DPCN) with asymmetric embeddedness of pyridine ring. The embedded pyridine ring modulates the localization of electron cloud density, resulting in a narrowed bandgap and an enhanced carriers' separation efficiency. They are further confirmed by UV–vis spectra and femtosecond transient absorption (fs-TA) spectroscopy, whose results are consistent with DFT theoretical calculations. This DPCN catalyst shows enhanced photocatalytic hydrogen evolution rate of 180.5 μmol h−1 and the apparent quantum efficiency of 14.6 % at 420 nm, surpassing most reported g-C 3 N 4 -based photocatalysts. This work provides a new sight on designing two-dimensional photocatalysts by modulating the localization of electron cloud density through breaking topological symmetry. [ABSTRACT FROM AUTHOR]

[Display omitted] • Intramolecular heterostructured carbon nitride is successfully synthesized. • The as-prepared sample exhibits superior photocatalytic hydrogen production. • Rapid separation and transfer of photogenerated carriers in as-prepared sample. • The addition of salt mixture regulates the localized electronic structure. Efficient separation and transfer of photogenerated carriers is vital for efficient photocatalytic hydrogen evolution. We report development of a new type of intramolecular heterostructure graphitic carbon nitride with heptazine-triazine (CN-HT) by use of a one-step thermal polymerization method. This intramolecular heterostructure changes the electronic structure to promote charge transfer and enhances the adsorption of H*. The as-prepared CN-HT exhibits superior photocatalytic hydrogen evolution of 88.29 μmol/h, which is 14.2 times that of pristine CN. The apparent quantum yield is 10.1% at 400 nm and 9.6% at 450 nm. The efficient separation and transfer of photogenerated carriers as well as the expanded visible light absorption in this intramolecular CN heterostructure contribute to the efficient utilization of photogenerated carriers, thus enhancing the photocatalytic hydrogen evolution. [ABSTRACT FROM AUTHOR]

Asymmetric Embedding Benzene Ring in graphite carbon nitride changes local charge distribution and electron transfer kinetics, and promote the photocatalytic water splitting to produce hydrogen at a higher rate. • The A-GCN is successfully prepared using dicyandiamide and terephthalonitrile. • Embedding benzene regulate the localized electronic structure. • Theoretical results predicts the localized asymmetry promotes the charge transfer. • For hydrogen production, the A-GCN-1.0 displays 10.8 times as good as pristine GCN. Preventing the high carrier recombination rate of graphitized C 3 N 4 (GCN) is an urgent problem to be solved for its application as a photocatalyst for hydrogen production. Here, we first rationally embed the benzene ring in GCN to modify the local symmetry without changing its long-order structure. Theoretical calculation predicts that this design can change the electronic structure and promote the effective charge transfer in GCN. The benzene ring embedded GCN is successfully prepared by copolymerization using dicyandiamide and terephthalonitrile as precursors. Photoluminescence (PL) and time-resolved transient PL (TRPL) spectra confirm that the electron transfer efficiency of the benzene ring embed GCN is greatly improved. This nanomaterial displays 10.8 times higher photocatalytic hydrogen production rate than that of pristine GCN with the apparent quantum yield of 11.3% at 400 nm and 9% at 420 nm. This work provides a novel strategy for designing high-efficiency two-dimensional (2D) photocatalytic materials for water splitting. [ABSTRACT FROM AUTHOR]