Pyridine Nitrogen Research Articles

Adsorption effect for removing fluoride with species of nitrogen by using La-BDC-NH2/C3N4: Experiments and mechanism

Fluoride contamination has emerged as a significant global environmental concern, with prolonged consumption of fluoride-rich groundwater being a primary contributor to fluorosis. Nitrogen sites play an important role in the process of fluoride removal, but the influence of different nitrogen species on fluoride adsorption has not been clearly clarified. In this study, a lanthanide organic framework adsorbent La-MOF-NH2 was prepared by solvothermal method, and a new adsorbent La-MOF-NH2@g-C3N4 was synthesized by adding g-C3N4 rich in various nitrogen sources. The effects of adsorbent dosage, pH, temperature and co-existing anions on the adsorption of fluorine were systematically studied. Optimal conditions were identified at a dosage of 2 g/L and a pH of 3, achieving theoretical maximum adsorption capacities of 219.4406 mg/g and 63.1401 mg/g, respectively. The results of five regeneration experiments shown that La-MOF-NH2 and La-MOF-NH2@g-C3N4 have strong recovery capacity. According to the adsorption isotherm and kinetic model, the adsorption mechanism of fluoride ions is mainly hydrogen bonding and chemisorption. In addition, through the experimental characterization and mechanism study, it was proved that amino group > pyridinic nitrogen > graphitic nitrogen. It provides a good guide for designing adsorbents containing nitrogen sites.

CaCO3-activited N-doped diatom biochar for the degradation of tetracycline

In this study, a N-doped diatom biochar (DBC) was prepared by one-step pyrolysis, where CaCO3 formed by marine diatom-mediated calcification was employed as an activator. Due to the activation effect of CaCO3, the specific surface area of the obtained DBC increased by more than 10 times, and the nitrogen presented as pyrrolic nitrogen (58.9%), pyridinic nitrogen (29.7%), and graphitic nitrogen (11.4%) in the DBC. In addition, the effects of important parameters and co-existing ions on the catalytic decomposition of tetracycline (TC) by DBC were investigated by using TC as a typical pollutant and PDS as an oxidant. The DBC/PDS system exhibited high activity over a broad pH range. Through radical scavenging experiments, electron spin resonance, and electrochemical results analysis, it was found that the degradation of TC in the system included both radical and nonradical pathways, and the most dominant reactive species was 1O2. Furthermore, the surficial reactive complexes formed by PDS on the catalysts also played an important role in attacking the adsorbed TC molecules. This study proposes an eco-friendly and economical technique to construct a clean advanced oxidation process capable of treating TC wastewater by utilizing the native biomass of diatom as a metal-free and efficient biochar catalyst while simultaneously reducing the use of chemical reagents.

Synergistic Modulation of Sn2+ Oxidation and Perovskite Crystallization Induced by 4-Hydroxypyridine for Stable Lead-Free Solar Cells.

Tin perovskites present promising alternatives to lead perovskites, offering comparable optoelectronic properties alongside environmentally friendly characteristics. However, the rapid crystallization and easy oxidation of Sn2+ lead to poor film quality, further constraining the device performance. Here, 4-hydroxypyridine (4-HP) is introduced into the tin perovskite precursor for fabrication of high-quality tin perovskite films. 4-HP could modulate the colloidal size of prenucleation perovskite clusters in the precursor, thus inducing fast nucleation and retarding the crystal growth rate of tin perovskite through the formation of chemical interaction between nitrogen of pyridine and Sn2+ ions. Furthermore, the hydroxyl group on the pyridine ring contributes to suppressing the oxidation of Sn2+. As a result, the power conversion efficiency (PCE) of the devices based on 4-HP increases up to 11.3%. The stability of the unencapsulated devices shows significant improvement, retaining 100% of their initial PCEs after 2000 h of storage in N2 with 50-100 ppm of O2. This research presents a novel approach to the synchronized regulation of tin perovskite crystallization and the suppression of Sn2+ oxidation.

Smart utilization of bimetallic NiCo alloy supported carbon dots and sulfur quantum dots derived 3D nanocomposite for oxygen evolution reaction

The increasing demand for highly active and stable electrocatalysts for the oxygen evolution reaction (OER) in future energy-conversion systems has driven researchers to explore novel alternatives to Pt-based catalysts. Among these alternatives, zero-dimensional quantum dots have emerged as promising candidates due to their high surface area and intrinsic electrocatalytic activity, which lead to significant breakthroughs in electrocatalytic performance. Herein, we conducted a preliminary investigation into the application of bimetallic NiCo alloy deposited on metal-free quantum dots (carbon dots and sulfur quantum dots) derived nano sponge for the oxygen evolution reaction. The synthesized NiCo-CDs-800 exhibited remarkable electrocatalytic OER activity, achieving a current density of 10 mA cm−2 with only 221 mV overpotential, far surpassing commercial RuO2 electrocatalysts. The excellent electrocatalytic activity can be attributed primarily to high electrochemically active area (168.97 mF cm−2), the presence of large proportion of oxygen vacancies (68.61 %), rich pyridinic nitrogen structure (29.30 %) with strong water adsorption, and synergistic effect of bimetals as supported by density functional theory calculations. Meanwhile, the newly prepared NiCo-SQDs-700 under the similar procedure demonstrate a satisfied OER performance and competing stability when compared to NiCo-CDs. These findings open a new avenue for the application of metal free CDs and SQDs to the growing family of metal@QDs.

Exploring the factors influencing the ketoenamine-enolimine tautomeric equilibrium of pyridoxal 5′-phosphate in branched-chain aminotransferases

Pyridoxal 5′-phosphate (PLP), the active form of vitamin B6, is a critical coenzyme for various enzymes. It generates a Schiff base with the substrate and exhibits ketoenamine and enolimine tautomeric forms due to intramolecular proton transfer. This study aims to ascertain the predominant tautomeric form of the PLP Schiff base in MtIlvE and analyze its influencing factors. Molecular dynamics simulations indicate that the ketoenamine tautomer has higher binding free energy than the enolimine tautomer. Density functional theory calculations suggest that, despite their ability to interconvert at a relatively low energy barrier, the ketoenamine tautomer is thermodynamically more stable. Factors affecting the keto-enol tautomeric equilibrium were investigated by constructing various QM-cluster models. Our results demonstrate that both the protonation of the pyridine nitrogen and the presence of Tyr209, which stabilizes the O3 anion, shift the tautomeric equilibrium toward the ketoenamine configuration. These findings provide a theoretical basis for investigating enzyme catalytic mechanisms.

Computational Justification Towards Detection of Dual Anions on a Single Molecular Platform: The Role of Solvent in Decoration of Dual Channels

ABSTRACTRatiometric optical detection of analytes is a convenient strategy as the technique is devoid of relative error and background correction. Herein, solvent‐guided ratiometric optical recognition of fluoride and bisulfate anions by a low‐cost, “off‐the‐shelf” bioactive molecule, harmane (HRH) is thoroughly explored. Interestingly, solvent plays a dynamic role in the selective recognition of the dual anions via the dual channels of HRH in an intelligent manner. The probe displays high‐fidelity recognition behavior towards fluoride ion in an aprotic solvent (acetonitrile) and towards bisulfate ion in a protic environment (acetonitrile/water; 5:1; v/v). Both the channels of HRH are very selective for a particular anion (F−/HSO4−) in a specific solvent. Organized and comprehensive theoretical calculation denotes that hydrogen bonding between the acidic pyrrolic proton of HRH and fluoride for the first channel and the acidic proton of bisulfate and the pyridinic nitrogen for the second channel of HRH led to the formation of a hydrogen‐bonded ion pair (HBIP). Consequently, significant optical changes are observed in the visible region, which is convenient for real‐life detection of F− and HSO4− independently. The essential role of solvent in tuning the dual channels of HRH is an important artifact in the literature of fundamental photochemistry.

High pyridine nitrogen regulates the d-band center in single atom iron electrocatalyst for promoted oxygen reduction

The design and development of a high pyridine nitrogen anchored Fe single atom (Fe SA) catalyst for efficient oxygen reduction reaction (ORR) are extremely urgent but still ambiguous. In this effort, we proposed a high-temperature pyrolysis strategy coupled with the pre-coordination of active sites to construct the N-doped carbon (NC) nanobox embedded with Fe SA moiety. Expectantly, the well-regulated FeSA@NC electrocatalyst delivered superior electrochemical ORR activity, evidenced by a promoted half-wave potential of 0.928 V and a decent limiting current density of 6.01 mA/cm2 in 0.1 M KOH solution. Beyond that, the resulting FeSA@NC product afforded a large peak power density of 267 mW/cm2 and satisfactory long-term stability. The theoretical calculation revealed that the increased pyridine nitrogen helps to promote the capture of more electrons at the Fe active site, thus optimizing the d-band center of the catalyst, and reasonably regulating the adsorption energy barrier of *OH species on the catalyst surface, both contributing to the boosted ORR performance. More importantly, this designed preparation strategy can be easily extended to the constructions of other transition metals (e.g., Co, Ni, Cu)-based SA catalysts, thus presenting a universal synthesis method for other similar SA catalyst systems in the future.

Electrochemical detection of human papillomavirus DNA based on an ultrasensitive electrochemical sensing platform using N-graphene paper

Human papillomavirus (HPV) is the primary cause of cervical cancer, a major global health concern affecting women worldwide. Early detection of high-risk HPV genotypes is crucial for timely intervention and reducing disease burden. However, current detection methods often lack sensitivity, speed, or cost-effectiveness, especially in resource-limited settings. This work addresses this critical need by developing an ultrasensitive electrochemical biosensing platform based on nitrogen-doped graphene paper electrodes for quantifying high-risk HPV16 DNA sequences. The N-graphene nanohybrid, fabricated via simple solvothermal treatment of biomass-derived graphene oxide, demonstrated significantly enhanced electrical and electrocatalytic properties compared to undoped graphene. DNA detection was achieved through characteristic oxidation signals of guanine bases, which displayed a wide linear dynamic range (0.5–100 μg/mL), low detection limit (75 pg/mL), and excellent reproducibility (relative standard deviation <3.5 %). Detailed spectroscopic and electrochemical analyses revealed the key roles of pyridinic nitrogen defects in improving interfacial charge transfer kinetics and mitigating biofouling issues. This synergistic combination of high electrical conductivity and versatile surface functionality paves the way for equipment-free, point-of-care genosensor devices tailored for quantitative biomarker screening in resource-constrained environments.

Pharmaceutical salt of isoniazid−orotic acid with optimized solubility, dissolution rate, and tabletability

Isoniazid (INH) is a first-line antitubercular drug characterized by its high solubility and rapid absorption following oral administration, which poses challenges in maintaining sustained therapeutic concentrations. To address this issue, we have developed a novel pharmaceutical salt of INH with orotic acid (OA). Single-crystal X-ray diffraction (XRD) analysis revealed that intermolecular proton transfer occurs between the carboxyl group of OA and the pyridine nitrogen site of INH, resulting in a salt comprising INHH+ cations and OA− anions. Solubility and dissolution studies indicated that INH−OA exhibits significantly reduced solubility and decelerated intrinsic dissolution rate (IDR). Specifically, solubility reductions were observed to be 74.24% in pH 1.2 HCl solution and 90.29% in pH 6.8 phosphate buffer solution. The IDR of the salt was found to be 2.62% and 0.96% of that of pure INH in pH 1.2 and pH 6.8 aqueous media, respectively. Additionally, INH−OA demonstrated improved tabletability. These findings suggest that the formation of this salt significantly enhances the pharmaceutical properties of INH.

Modality-Tunable Exfoliated N-Doped Graphene as Effective Electrolyte Additive for High-Performance Lithium-Sulfur Batteries.

While chemically doped graphene has shown great promise, the lack of cost-effective manufacturing has hindered its use. This study utilizes a facile fabrication approach for modality-tunable N-doped graphene via thermal annealing of aqueous-phase-exfoliated few-layered graphene from a Taylor-Couette reactor. This method demonstrates a high level of N-doping (27 atom % N) and offers modality tunability of the C-N bond without foregoing scalability and green chemistry principles. The resulting N-doped graphene, with varying N content and doping modality, is utilized in the lithium-sulfur battery electrolyte to address low ionic conductivity, lithium polysulfide (LiPS) shuttling, and Li anode instability. The study reveals that higher N content and pyridinic N modality graphene in the electrolyte positively influence battery performance. The results are 2-fold: higher overall N content improves capacity retention (73%) after 225 cycles at 0.2 C, and pyridinic-type nitrogen demonstrates the best performance at high C rates, exhibiting a 4-fold capacity increase relative to the reference cell at 2 C. Further, the computational study validates the adsorption affinity of LiPS to pyridinic nitrogen and improved Li+ mobility on the graphene backbone observed experimentally. This first experimental study on the impact of N-dopant concentration and modality on electrochemical performance provokes insights into tailoring N functionalization to achieve superior electrochemical performance.

Pinning Down Small Populations of Photoinduced Intermediates Using Transient Absorption Spectroscopy and Time-Dependent Density Functional Theory Difference Spectra to Provide Mechanistic Insight into Controlling Pyridine Azo Dynamics with Protons.

In this work, the impact of protonation on the photoisomerization (trans → cis) and reversion (cis → trans) of three pyridine-based azo dyes (PyrN) is investigated by using a combination of transient absorption spectroscopy and time-dependent density functional theory computed difference spectra. The photophysical behaviors of the PyrN dyes are altered by the addition of one or two protons. Protonation of basic pyridine nitrogens results in an ultrafast accelerated reversion mechanism after photoisomerization, while protonation of azo bond nitrogens restricts cis isomer formation entirely. Computed difference spectra provide spectral signatures that are critical for the assignment of low-population long-lived states, providing direct evidence of the accelerated reversion mechanism. Thus, the addition of organic acids can selectively control the photophysics of azo dyes for a wide range of applications, including materials design and pharmaceuticals.

Multilayer Porous Fe/Co-N-MWCNT Electrocatalyst For Rechargeable Zinc-Air Batteries.

The design of efficient, stable, low-cost non-precious metal-based electrocatalysts with enhanced oxygen reduction reaction (ORR) activity has garnered significant attention in the scientific community. This study introduces a novel electrocatalyst, Fe/Co-N-MWCNT, synthesized through the in-situ growth of ZIF-8 and Fe/Co-Phen on multi-walled carbon nanotubes (MWCNTs), followed by pyrolysis at varying temperatures to optimize its properties. The inclusion of Fe and Co during the pyrolysis process facilitated the creation of metal active sites and Fe-Co, enhancing electron transfer and ORR activity. Compared to Pt/C (E1/2=0.854 V, JL=4.90 mA cm-2), Fe/Co-N-MWCNT exhibited a similar half-wave potential (E1/2=0.812 V) and an improved limiting current density (JL=5.37 mA cm-2). Moreover, Fe/Co-N-MWCNT displayed remarkable stability, showing only a 7 mV negative shift in E1/2 after 2000 cycles. Ampere response testing indicated a current decay of only 7.8 % for Fe/Co-N-MWCNT after 10000 s, while Pt/C experienced a decay of about 18.4 %. The exceptional catalytic stability of Fe/Co-N-MWCNT positions it as a promising candidate for rechargeable zinc-air batteries, attributed to its high pyridinic nitrogen content, unique structure, and abundant metal active sites.

Bifunctional electrode materials: Enhancing microbial fuel cell efficiency with 3D hierarchical porous Fe3O4/Fe-N-C structures

The rational development of high-performance anode and cathode electrodes for microbial fuel cells (MFCs) is crucial for enhancing MFC performance. However, complex synthesis methods and single-performance electrode materials hinder their large-scale implementation. Here, three-dimensional hierarchical porous (3DHP) Fe3O4/Fe-N-C composites were prepared via the hard template method. Notably, Fe3O4/Fe-N-C-0.04-600 demonstrated uniformly dispersed Fe3O4 nanoparticles and abundant Fe-Nx and pyridinic nitrogen, showing excellent catalytic performance for oxygen reduction reaction (ORR) with a half-wave potential (E1/2) of 0.74 V (vs. RHE), surpassing Pt/C (0.66 V vs. RHE). Moreover, Fe3O4/Fe-N-C-0.04-600 demonstrated favorable biocompatibility as an anode material, enhancing anode biomass and extracellular electron transfer efficiency. Sequencing results confirmed its promotion of electrophilic microorganisms in the anode biofilm. MFCs employing Fe3O4/Fe-N-C-0.04-600 as both anode and cathode materials achieved a maximum power density of 831.8 ± 27.7 mW m−2, enduring operation for 38 days. This study presents a novel approach for rational MFC design, emphasizing bifunctional materials capable of serving as anode materials for microorganism growth and as cathode catalysts for ORR catalysis.

Boosting the activity of nitrogen-doped carbon catalyst by the guided formation of active sites and enhanced scavenging on reactive oxygen species under the regulation of cerium

The design of nitrogen-doped carbon materials with high density of active sites is of paramount importance for catalysis of the oxygen reduction reaction (ORR). Herein, an efficient oxygen reduction electrocatalyst (CL-Fe/(Fe,Ce)xOy-NC) is developed by planting carbon nanotubes with encapsulated Fe/(Fe,Ce)xOy particles on porous carbon polyhedron particles derived from calcinated ZIF-8 framework. The introduction of Ce evidently promotes the formation of pyridinic nitrogen, graphitic nitrogen and metal nitrogen species in carbon matrix, enhancing the catalytic activity towards the ORR. The Ce oxide in the catalyst effectively scavenges the active oxygen species in ORR process. Under the synergistic effect of high specific surface area with Ce species, the CL-Fe/(Fe,Ce)xOy-NC has a better half-wave potential (0.861 V vs. RHE), faster kinetics (44.13 mV dec−1) and is more stable than the commercial Pt/C catalyst. The zinc-air battery assembled with CL-Fe/(Fe,Ce)xOy-NC has the highest power density of 195 mW cm−2, energy density of 858 Wh kg−1, and better durability. This work presents a novel approach to enhance the efficacy of nitrogen-doped carbon-based catalysts, paving a possible way to substitute the precious platinum catalysts for a variety of electrochemical energy devices.

Unveiling the Role of Pyridinic Nitrogen and Diacetylene in the Hydrogen Evolution Reaction through Model Catalysts Prepared by On-Surface Reactions.

Metal-free carbon materials (MFCMs) have extensive applications in electrocatalysis because of their comparable catalytic activity to that of Pt/C in some cases. Understanding the structure-property relationship is crucial for the reasonable design of more efficient catalysts. To reveal the structure-property relationship of the hydrogen evolution reaction (HER), we prepared nanowire model catalysts on single-crystalline Au(111) electrodes through state-of-the-art on-surface synthesis. Temperature-dependent experiments were conducted to evaluate the HER activity of the nanoribbons functionalized with pyridinic nitrogen and diacetylene. According to our electrochemical results (overpotential, current density j0, and apparent activation energy), we demonstrate that the participation of diacetylene can promote the catalytic reaction for the HER through a synergistic effect. Based on the analysis of the activation entropy for the model catalysts, we attribute the synergistic effect of diacetylene groups to the large area of π···H-O bonding in the electric double layer, thus providing direct insight into the structural-property relationship of polymerized nanoribbons for the HER through the rational design of precursor structures. The nanoribbons prepared by on-surface synthesis can serve as prototype systems for model catalytic research on MFCMs.

Nitrogen and Oxygen Dual‐Doped Carbon as High‐Rate Long‐Cycle‐Life Anode Materials for Lithium‐Ion Batteries

Defect‐type carbon, doped with nitrogen and oxygen, is synthesized using the high‐temperature solid‐phase method. X‐ray photoelectron spectroscopy analysis reveals the presence of nitrogen, including pyridine nitrogen, pyrrole nitrogen, and graphitized nitrogen, incorporated into the carbon structure. Additionally, oxygen is introduced into carbon, with both CO and CO functionalities are observed. Transmission electron microscopy and scanning electron microscopy indicate that all samples exhibit a morphology of carbon microblocks with localized turbocharged lattice regions. Electrochemical tests demonstrate that the nitrogen‐ and oxygen‐doped carbon microblocks exhibit excellent cycling performance and high rate capacity. Specifically, at current densities of 1 and 2 A g−1, the rate capacity remains at 385.6 and 214.4 mA h g−1, respectively. Furthermore, the discharge capacity at 5 A g−1 remains at 58.3 mA h g−1 on the 3500th cycle. The defects introduced by nitrogen and oxygen doping not only enhance reactivity and electronic conductivity but also improve lithium‐ion diffusion dynamics.

Controlling the optoelectronic properties of nitrogen-doped carbon quantum dots using biomass-derived precursors in a continuous flow system

The synthesis of carbon quantum dots (CQDs) from high molecular weight biomass-derived precursors poses a significant challenge due to the complex molecular structures and low conversion efficiency. This work demonstrates a green, rapid, and sustainable continuous hydrothermal flow synthesis (CHFS) approach for nitrogen-doped carbon quantum dots (NCQDs) from various biomass-derived precursors, including high molecular weight polymeric sources like chitosan, lignin, and humic acid. We find that the precursor structure significantly impacts the size of the fabricated NCQDs and their optical properties. Citric acid, a low molecular weight precursor, yields NCQDs with excitation-independent emission, higher quantum yields, and low non-radiative losses, while NCQDs derived from polymeric precursors exhibit excitation-dependent, red-shifted, and lower efficiency emission. Theoretical calculations, performed to understand the configuration and distribution of nitrogen dopants within the NCQD structure, show that pyridinic and graphitic nitrogen atoms exhibit a strong preference to aggregate near the centre of the edge of the NCQD and not in the vertices nor in the graphitic core, thus affecting the HOMO and LUMO, bandgap, and light absorption and emission wavelengths. The life cycle assessment (LCA) analysis highlights the green and scalable advantages of the CHFS process for producing NCQDs compared to batch methods, making it a sustainable and economically viable approach for large-scale NCQD synthesis from high molecular weight biomass-derived precursors. Hence, the combination of experimental data and theoretical calculations provides a comprehensive understanding of the structure-property relationships in these NCQDs.

Aminotriazine derived N-doped mesoporous carbon with a tunable nitrogen content and their improved oxygen reduction reaction performance.

The electrocatalytic activity of carbon materials is highly dependent on the controlled modulation of their composition and porosity. Herein, mesoporous N-doped carbon with different amounts of nitrogen was synthesized through a unique strategy of using a high nitrogen containing CN precursor, 3-amino 1,2,4 triazine (3-ATZ) which is generally used for the preparation of carbon nitrides, integrated with the combination of a templating method and high temperature treatment. The nitrogen content and the graphitisation of the prepared materials were finely tuned with the simple adjustment of the carbonisation temperature (800-1100 °C). The optimised sample as an electrocatalyst for oxygen reduction reaction (ORR) exhibited an onset potential of 0.87 V vs. RHE with a current density of 5.1 mA cm-2 and a high kinetic current density (Jk) of 33.1 mA cm-2 at 0.55 V vs. RHE. The characterisation results of the prepared materials indicated that pyridinic and graphitic nitrogen in the carbon framework promoted ORR activity with improved four-electron selectivity and excellent methanol tolerance and stability. DFT calculations demonstrated that the structural and planar defects in the N-doped carbon regulated the surface electronic properties of the electrocatalyst, leading to a reduction in the energy barrier for the ORR activity. This strategy has the potential to unlock a platform for designing a series of catalysts for electrochemical applications.

Nitrogen-rich carbon nanosheets supported copper catalysts for oxidative carbonylation of ethanol

Two-dimensional (2D) nitrogen-rich carbon nanosheets NC-x with a nitrogen content of 5.2 %-6.8 wt% were characterized by a one-step co-pyrolysis method and employed as Cu catalyst supports for oxidative carbonylation of ethanol. Carbon nanosheets with abundant nitrogen defects were achieved by tuning the dosage of ammonium oxalate, in which the Cu/NC-12 catalyst performed excellent activity. Furthermore, Cu/NC-x catalysts presented significantly superior catalytic activity than that of copper/carbon nanosheets (Cu/C) catalyst, it can be ascribed to the most suitable nitrogen doping to promote the exposure and dispersion of Cu species and pyridine nitrogen served as the main anchor sites to increase the ratio of Cu+/(Cu++Cu0). Density functional theory calculations further proved that introducing nitrogen atoms into carbon nanosheets effectively reinforced binding to Cu4 and adsorption of intermediates with NC, and a remarkable activity on Cu/NC-12 was achieved by a more favorable insertion of CO in the rate-determining step.

Graphene with suitable-size nitrogen-doped cavity being an excellent photocatalyst for proton-coupled electron transfer in water splitting

Aiming to attain porous carbon nitride photocatalysts with high specific surface area, abundant active sites, broad absorption range and effective electron-hole separation, we remove carbon rings from graphene and replace all the edge carbon atoms of the cavity with nitrogen atoms. The accurate electronic structures and exciton properties of the proposed materials are revealed by the ab initio many-body Green's function theory. Computational results show that the absorption of the designed materials can cover both the visible and the near-infrared light region. The exciton binding energies of the materials are one order of magnitude lower than those of the typical two-dimensional photocatalyst graphitic carbon nitride. Due to the formation of hydrogen bonds between pyridinic nitrogen atoms and water molecules during water splitting, the key excited-state proton-coupled electron transfer reactions are barrierless. These findings could serve as guidelines for the realization of high-performance metal-free two-dimensional photocatalysts.