Tri‐s‐triazine‐Based Crystalline Carbon Nitride Nanosheets for an Improved Hydrogen Evolution

Tri‐s‐triazine‐based crystalline carbon nitride nanosheets (CCNNSs) have been successfully extracted via a conventional and cost‐effective sonication–centrifugation process. These CCNNSs possess a highly defined and unambiguous structure with minimal thickness, large aspect ratios, homogeneous tri‐s‐triazine‐based units, and high crystallinity. These tri‐s‐triazine‐based CCNNSs show significantly enhanced photocatalytic hydrogen generation activity under visible light than g‐C₃N₄, poly (triazine imide)/Li⁺ Cl^–, and bulk tri‐s‐triazine‐based crystalline carbon nitrides. A highly apparent quantum efficiency of 8.57% at 420 nm for hydrogen production from aqueous methanol feedstock can be achieved from tri‐s‐triazine‐based CCNNSs, exceeding most of the reported carbon nitride nanosheets. Benefiting from the inherent structure of 2D crystals, the ultrathin tri‐s‐triazine‐based CCNNSs provide a broad range of application prospects in the fields of bioimaging, and energy storage and conversion.     

Metal‐Free 2D/2D Phosphorene/g‐C3N4 Van der Waals Heterojunction for Highly Enhanced Visible‐Light Photocatalytic H2 Production

The generation of green hydrogen (H₂) energy using sunlight is of great significance to solve the worldwide energy and environmental issues. Particularly, photocatalytic H₂ production is a highly promising strategy for solar‐to‐H₂ conversion. Recently, various heterostructured photocatalysts with high efficiency and good stability have been fabricated. Among them, 2D/2D van der Waals (VDW) heterojunctions have received tremendous attention, since this architecture can promote the interfacial charge separation and transfer and provide massive reactive centers. On the other hand, currently, most photocatalysts are composed of metal elements with high cost, limited reserves, and hazardous environmental impact. Hence, the development of metal‐free photocatalysts is desirable. Here, a novel 2D/2D VDW heterostructure of metal‐free phosphorene/graphitic carbon nitride (g‐C₃N₄) is fabricated. The phosphorene/g‐C₃N₄ nanocomposite shows an enhanced visible‐light photocatalytic H₂ production activity of 571 µmol h^?1 g^?1 in 18 v% lactic acid aqueous solution. This improved performance arises from the intimate electronic coupling at the 2D/2D interface, corroborated by the advanced characterizations techniques, e.g., synchrotron‐based X‐ray absorption near‐edge structure, and theoretical calculations. This work not only reports a new metal‐free phosphorene/g‐C₃N₄ photocatalyst but also sheds lights on the design and fabrication of 2D/2D VDW heterojunction for applications in catalysis, electronics, and optoelectronics.     

Improved Photocatalytic H2 Evolution over G‐Carbon Nitride with Enhanced In‐Plane Ordering

A series of rod‐like porous graphitic‐carbon nitrides (short as CNs) with enhanced in‐plane ordering have been fabricated through self‐assembled heptazine hydrate precursors for the first time. By controlling the calcination of the preformed precursors with different temperature‐rising rates, the resulted CNs (SAHEP‐CNs‐1) with the most ordered and least stacked graphitic planar are showing a tremendously improved hydrogen evolution rate of 420 μmol h^?1 under visible light and a remarkable apparent quantum efficiency of 8.9% at 420 nm, which is among the highest values for C₃N₄‐related photocatalysts in the literature. This work discloses that enhancing in‐plane ordering is one critical factor for improving the photocatalytic H₂ evolution of carbon nitride, which is an effective solution to prolong the lifetime of charge carriers by accelerating the charge transport and separation within the graphitic planar. This finding would present a facial strategy for the designing of efficient organic semiconductors for photocatalysis.     

Mesoporous Polymeric Cyanamide‐Triazole‐Heptazine Photocatalysts for Highly‐Efficient Water Splitting

Conjugated polymers are promising light harvesters for water reduction/oxidation due to their simple synthesis and adjustable bandgap. Herein, both cyanamide and triazole functional groups are first incorporated into a heptazine‐based carbon nitride (CN) polymer, resulting in a mesoporous conjugated cyanamide‐triazole‐heptazine polymer (CTHP) with different compositions by increasing the quantity of cyanamide/triazole units in the CN backbone. Varying the compositions of CTHP modulates its electronic structures, mesoporous morphologies, and redox energies, resulting in a significantly improved photocatalytic performance for both H₂ and O₂ evolution under visible light irradiation. A remarkable H₂ evolution rate of 12723 µmol h^?1 g^?1 is observed, resulting in a high apparent quantum yield of 11.97% at 400 nm. In parallel, the optimized photocatalyst also exhibits an O₂ evolution rate of 221 µmol h^?1 g^?1, 9.6 times higher than the CN counterpart, with the value being the highest among the reported CN‐based bifunctional photocatalysts. This work provides an efficient molecular engineering approach for the rational design of functional polymeric photocatalysts.     

Light‐Driven ZnO Brush‐Shaped Self‐Propelled Micromachines for Nitroaromatic Explosives Decomposition

Self‐propelled micromachines have recently attracted lots of attention for environmental remediation. Developing a large‐scale but template‐free fabrication of self‐propelled rod/tubular micro/nanomotors is very crucial but still challenging. Here, a new strategy based on vertically aligned ZnO arrays is employed for the large‐scale and template‐free fabrication of self‐propelled ZnO‐based micromotors with H₂O₂‐free light‐driven propulsion ability. Brush‐shaped ZnO‐based micromotors with different diameters and lengths are fully studied, which present a fast response to multicycles UV light on/off switches with different interval times (2/5 s) in pure water and slow directional motion in aqueous hydrogen peroxide solution in the absence of UV light. Light‐induced electrophoretic and self‐diffusiophoretic effects are responsible for these two different self‐motion behaviors under different conditions, respectively. In addition, the pH of the media and the presence of H₂O₂ show important effects on the motion behavior and microstructure of the ZnO‐based micromotors. Finally, these novel ZnO‐based brush‐shaped micromotors are demonstrated in a proof‐of‐concept study on nitroaromatic explosive degradation, i.e., picric acid. This work opens a completely new avenue for the template‐free fabrication of brush‐shaped light‐responsive micromotors on a large scale based on vertically aligned ZnO arrays.     

Black Phosphorus Revisited: A Missing Metal‐Free Elemental Photocatalyst for Visible Light Hydrogen Evolution

Metal‐free elemental photocatalysts for hydrogen (H₂) evolution are more advantageous than the traditional metal‐based inorganic photocatalysts since the nonmetal elements are generally cheaper, more earth‐abundant, and environmentally friendly. Black phosphorus (BP) has been attracting increasing attention in recent years based on its anisotropic 2D layered structure with tunable bandgap in the range of 0.3–2.0 eV; however, the application of BP for photocatalytic H₂ evolution has been scarcely reported experimentally although being theoretically predicted. Herein, for the first time, the visible light photocatalytic H₂ evolution of BP nanosheets prepared via a facile solid‐state mechanochemical method by ball‐milling bulk BP is reported. Without using any noble metal cocatalyst, the visible light photocatalytic hydrogen evolution rate of BP nanosheets reaches 512 µmol h^?1 g^?1, which is ≈18 times higher than that of the bulk BP, and is comparable or even higher than that of graphitic carbon nitrides (g‐C₃N₄).     

Effective Fixation of Carbon in g‐C3N4 Enabled by Mg‐Induced Selective Reconstruction

The methodology of metal‐involved preparation for carbon materials is favored by researchers and has attracted tremendous attention. Decoupling this process and the underlying mechanism in detail are highly required. Herein, the intrinsic mechanism of carbon fixation in graphitic carbon nitride (g‐C₃N₄) via the magnesium‐involved carbonization process is reported and clarified. Magnesium can induce the displacement reaction with the small carbon nitride molecule generated by the pyrolysis of g‐C₃N₄, thus efficiently fixing the carbon onto the in situ template of Mg₃N₂ product to avoid the direct volatilization. As a result, the N‐doped carbon nanosheet frameworks with interconnected porous structure and suitable N content are constructed by reconstruction of carbon and nitrogen species, which exhibit a comparable photoelectric conversion efficiency (8.59%) and electrocatalytic performances to that of Pt (8.40%) for dye‐sensitized solar cells.     

Light‐Switchable Oxygen Vacancies in Ultrafine Bi5O7Br Nanotubes for Boosting Solar‐Driven Nitrogen Fixation in Pure Water

Solar‐driven reduction of dinitrogen (N₂) to ammonia (NH₃) is severely hampered by the kinetically complex and energetically challenging multielectron reaction. Oxygen vacancies (OVs) with abundant localized electrons on the surface of bismuth oxybromide‐based semiconductors are demonstrated to have the ability to capture and activate N₂, providing an alternative pathway to overcome such limitations. However, bismuth oxybromide materials are susceptible to photocorrosion, and the surface OVs are easily oxidized and therefore lose their activities. For realistic photocatalytic N₂ fixation, fabricating and enhancing the stability of sustainable OVs on semiconductors is indispensable. This study shows the first synthesis of self‐assembled 5 nm diameter Bi₅O₇Br nanotubes with strong nanotube structure, suitable absorption edge, and many exposed surface sites, which are favorable for furnishing sufficient visible light‐induced OVs to realize excellent and stable photoreduction of atmospheric N₂ into NH₃ in pure water. The NH₃ generation rate is as high as 1.38 mmol h^?1 g^?1, accompanied by an apparent quantum efficiency over 2.3% at 420 nm. The results presented herein provide new insights into rational design and engineering for the creation of highly active catalysts with light‐switchable OVs toward efficient, stable, and sustainable visible light N₂ fixation in mild conditions.     

Photoconversion‐Tunable Fluorophore Vesicles for Wavelength‐Dependent Photoinduced Cancer Therapy

Photoconversion tunability of fluorophore dye is of great interest in cancer nanomedicine such as fluorescence imaging, photodynamic therapy (PDT), and photothermal therapy (PTT). Herein, this paper reports wavelength‐dependent photoconversional polymeric vesicles of boron dipyrromethene (Bodipy) fluorophore for either PDT under 660 nm irradiation or PTT under 785 nm irradiation. After being assembled within polymeric vesicles at a high drug loading, Bodipy molecules aggregate in the conformations of both J‐type and H‐type, thereby causing red‐shifted absorption into near‐infrared region, ultralow radiative transition, and ideal resistance to photobleaching. Such vesicles further possess enhanced blood circulation, preferable tumor accumulation, as well as superior cell uptake as compared to free Bodipy. In particular, the vesicles mainly generate abundant intracellular singlet oxygen for PDT treatment under 660 nm irradiation, while they primarily produce a potent hyperthermia for PTT with tumor ablation through singlet oxygen‐synergized photothermal necrosis under 785 nm irradiation. This approach provides a facile and general strategy to tune photoconversion characteristics of fluorophore dyes for wavelength‐dependent photoinduced cancer therapy.     

Oxidized g‐C3N4 Nanospheres as Catalytically Photoactive Linkers in MOF/g‐C3N4 Composite of Hierarchical Pore Structure

A unique composite of the copper‐based metal–organic framework (Cu‐benzene tricarboxylic acid (BTC)) with oxidized graphitic carbon nitride nanospheres is synthesized. For comparison, a hybrid material consisting of g‐C₃N₄ and Cu‐BTC is also obtained. Their surface features are analyzed using Fourier transform infrared spectroscopy, X‐ray diffraction, sorption of nitrogen, thermal analysis, scanning electron microscopy, photoluminescence, and diffuse reflectance UV–Vis spectroscopy. The results suggest that the formed nanospheres of oxidized g‐C₃N₄ act as linkers between the copper sites, playing a crucial role in the composite building process. Their incorporation to the Cu‐BTC framework causes the development of new mesoporosity. Remarkable alterations in the optical properties, as a result of the coordination of oxygen containing functional groups of the oxidized graphitic carbon nitride to the copper atoms of the framework, suggest an increase in photoreactivity. On the other hand, for the hybrid material consisting of Cu‐BTC and g‐C₃N₄, the unaltered pore volume and optical properties support the formation of a physical mixture rather than of a composite. The tests on reactive adsorption and detoxification of G‐series organophosphate nerve agent surrogate show the enhanced performance of the composite as catalysts and photocatalyst in visible light.     

From UV to Near‐Infrared Light‐Responsive Metal–Organic Framework Composites: Plasmon and Upconversion Enhanced Photocatalysis

The exploitation of photocatalysts that harvest solar spectrum as broad as possible remains a high‐priority target yet grand challenge. In this work, for the first time, metal–organic framework (MOF) composites are rationally fabricated to achieve broadband spectral response from UV to near‐infrared (NIR) region. In the core–shell structured upconversion nanoparticles (UCNPs)‐Pt@MOF/Au composites, the MOF is responsive to UV and a bit visible light, the plasmonic Au nanoparticles (NPs) accept visible light, whereas the UCNPs absorb NIR light to emit UV and visible light that are harvested by the MOF and Au once again. Moreover, the MOF not only facilitates the generation of “bare and clean” Au NPs on its surface and realizes the spatial separation for the Au and Pt NPs, but also provides necessary access for catalytic substrates/products to Pt active sites. As a result, the optimized composite exhibits excellent photocatalytic hydrogen production activity (280 µmol g^?1 h^?1) under simulated solar light, and the involved mechanism of photocatalytic H₂ production under UV, visible, and NIR irradiation is elucidated. Reportedly, this is an extremely rare study on photocatalytic H₂ production by light harvesting in all UV, visible, and NIR regions.     

Ultrahigh‐Performance Self‐Powered Flexible Double‐Twisted Fibrous Broadband Perovskite Photodetector

Self‐powered flexible photodetectors without an external power source can meet the demands of next‐generation portable and wearable nanodevices; however, the performance is far from satisfactory becuase of the limited match of flexible substrates and light‐sensitive materials with proper energy levels. Herein, a novel self‐powered flexible fiber‐shaped photodetector based on double‐twisted perovskite–TiO₂–carbon fiber and CuO–Cu₂O–Cu wire is designed and fabricated. The device shows an ultrahigh detectivity of 2.15 × 10¹³ Jones under the illumination of 800 nm light at zero bias. CuO–Cu₂O electron block bilayer extends response range of perovskite from 850 to 1050 nm and suppresses dark current down to 10^?11 A. The fast response speed of less than 200 ms is nearly invariable after dozens of cycles of bending at the extremely 90 bending angle, demonstrating excellent flexibility and bending stability. These parameters are comparable and even better than reported flexible and even rigid photodetectors. The present results suggest a promising strategy to design photodetectors with integrated function of self‐power, flexibility, and broadband response.     

Enhanced Solar‐to‐Hydrogen Generation with Broadband Epsilon‐Near‐Zero Nanostructured Photocatalysts

The direct conversion of solar energy into fuels or feedstock is an attractive approach to address increasing demand of renewable energy sources. Photocatalytic systems relying on the direct photoexcitation of metals have been explored to this end, a strategy that exploits the decay of plasmonic resonances into hot carriers. An efficient hot carrier generation and collection requires, ideally, their generation to be enclosed within few tens of nanometers at the metal interface, but it is challenging to achieve this across the broadband solar spectrum. Here the authors demonstrate a new photocatalyst for hydrogen evolution based on metal epsilon‐near‐zero metamaterials. The authors have designed these to achieve broadband strong light confinement at the metal interface across the entire solar spectrum. Using electron energy loss spectroscopy, the authors prove that hot carriers are generated in a broadband fashion within 10 nm in this system. The resulting photocatalyst achieves a hydrogen production rate of 9.5 µmol h^?1 cm^?2 that exceeds, by a factor of 3.2, that of the best previously reported plasmonic‐based photocatalysts for the dissociation of H₂ with 50 h stable operation.     

Cu2+‐Modified Metal–Organic Framework Nanoparticles: A Peroxidase‐Mimicking Nanoenzyme

The synthesis and characterization of UiO‐type metal–organic framework nanoparticles (NMOFs) composed of Zr⁴⁺ ions bridged by 2,2′‐bipyridine‐5,5′‐dicarboxylic acid ligands and the postmodification of the NMOFs with Cu²⁺ ions are described. The resulting Cu²⁺‐modified NMOFs, Cu²⁺‐NMOFs, exhibit peroxidase‐like catalytic activities reflected by the catalyzed oxidation of Amplex‐Red to the fluorescent Resorufin by H₂O₂, the catalyzed oxidation of dopamine to aminochrome by H₂O₂, and the catalyzed generation of chemiluminescence in the presence of luminol/H₂O₂. Also, the Cu²⁺‐NMOFs mimic NADH peroxidase functions and catalyze the oxidation of dihydronicotinamide adenine dinucleotide, NADH, to nicotinamide adenine dinucleotide, NAD⁺, in the presence of H₂O₂. The Cu²⁺‐NMOFs‐catalyzed generation of chemiluminescence in the presence of luminol/H₂O₂ is used to develop a glucose sensor by monitoring the H₂O₂ formed by the aerobic oxidation of glucose to gluconic acid in the presence of glucose oxidase. Furthermore, loading the Cu²⁺‐NMOFs with fluorescein and activating the catalyzed generation of chemiluminescence in the presence of luminol/H₂O₂ yield an efficient chemiluminescence resonance energy transfer (CRET) process to the fluorescein reflected by the activation of the fluorescence of the dye (λ = 520 nm, CRET efficiency 35%).     

Self‐Assembled Ordered Three‐Phase Au–BaTiO3–ZnO Vertically Aligned Nanocomposites Achieved by a Templating Method

Complex multiphase nanocomposite designs present enormous opportunities for developing next‐generation integrated photonic and electronic devices. Here, a unique three‐phase nanostructure combining a ferroelectric BaTiO₃, a wide‐bandgap semiconductor of ZnO, and a plasmonic metal of Au toward multifunctionalities is demonstrated. By a novel two‐step templated growth, a highly ordered Au–BaTiO₃–ZnO nanocomposite in a unique “nanoman”‐like form, i.e., self‐assembled ZnO nanopillars and Au nanopillars in a BaTiO₃ matrix, is realized, and is very different from the random three‐phase ones with randomly arranged Au nanoparticles and ZnO nanopillars in the BaTiO₃ matrix. The ordered three‐phase “nanoman”‐like structure provides unique functionalities such as obvious hyperbolic dispersion in the visible and near‐infrared regime enabled by the highly anisotropic nanostructures compared to other random structures. Such a self‐assembled and ordered three‐phase nanocomposite is obtained through a combination of vapor–liquid–solid (VLS) and two‐phase epitaxy growth mechanisms. The study opens up new possibilities in the design, growth, and application of multiphase structures and provides a new approach to engineer the ordering of complex nanocomposite systems with unprecedented control over electron–light–matter interactions at the nanoscale.     

Dendrite‐Free Sodium‐Metal Anodes for High‐Energy Sodium‐Metal Batteries

Sodium (Na) metal is one of the most promising electrode materials for next‐generation low‐cost rechargeable batteries. However, the challenges caused by dendrite growth on Na metal anodes restrict practical applications of rechargeable Na metal batteries. Herein, a nitrogen and sulfur co‐doped carbon nanotube (NSCNT) paper is used as the interlayer to control Na nucleation behavior and suppress the Na dendrite growth. The N‐ and S‐containing functional groups on the carbon nanotubes induce the NSCNTs to be highly “sodiophilic,” which can guide the initial Na nucleation and direct Na to distribute uniformly on the NSCNT paper. As a result, the Na‐metal‐based anode (Na/NSCNT anode) exhibits a dendrite‐free morphology during repeated Na plating and striping and excellent cycling stability. As a proof of concept, it is also demonstrated that the electrochemical performance of sodium–oxygen (Na–O₂) batteries using the Na/NSCNT anodes show significantly improved cycling performances compared with Na–O₂ batteries with bare Na metal anodes. This work opens a new avenue for the development of next‐generation high‐energy‐density sodium‐metal batteries.     

Twinned Growth of Metal‐Free,Triazine‐Based Photocatalyst Films as Mixed‐Dimensional (2D/3D) van der Waals Heterostructures

Design and synthesis of ordered, metal‐free layered materials is intrinsically difficult due to the limitations of vapor deposition processes that are used in their making. Mixed‐dimensional (2D/3D) metal‐free van der Waals (vdW) heterostructures based on triazine (C₃N₃) linkers grow as large area, transparent yellow‐orange membranes on copper surfaces from solution. The membranes have an indirect band gap (E _g,opt = 1.91 eV, E _g,elec = 1.84 eV) and are moderately porous (124 m² g^?1). The material consists of a crystalline 2D phase that is fully sp² hybridized and provides structural stability, and an amorphous, porous phase with mixed sp²–sp hybridization. Interestingly, this 2D/3D vdW heterostructure grows in a twinned mechanism from a one‐pot reaction mixture: unprecedented for metal‐free frameworks and a direct consequence of on‐catalyst synthesis. Thanks to the efficient type I heterojunction, electron transfer processes are fundamentally improved and hence, the material is capable of metal‐free, light‐induced hydrogen evolution from water without the need for a noble metal cocatalyst (34 µmol h^?1 g^?1 without Pt). The results highlight that twinned growth mechanisms are observed in the realm of “wet” chemistry, and that they can be used to fabricate otherwise challenging 2D/3D vdW heterostructures with composite properties.     

Preparation of Carbon‐Rich g‐C3N4 Nanosheets with Enhanced Visible Light Utilization for Efficient Photocatalytic Hydrogen Production

Exfoliation of layered bulk g‐C₃N₄ (CNB) to thin g‐C₃N₄ sheets in nanodomains has attracted much attention in photocatalysis because of the intriguing properties of nanoscaled g‐C₃N₄. This study shows that carbon‐rich g‐C₃N₄ nanosheets (CNSC) can be easily prepared by self‐modification of polymeric melon units through successively thermally treating bulk g‐C₃N₄ in an air and N₂ atmosphere. The prepared CNSC not only retain the outstanding properties of nanosheets, such as large surface area, high aspect ratios, and short charges diffusion distance, but also overcome the drawback of enlarged bandgap caused by the quantum size effect, resulting in an enhanced utilization of visible light and photoinduced electron delocalization ability. Therefore, the as‐prepared CNSC show a high hydrogen evolution rate of 39.6 µmol h^?1 with a turnover number of 24.98 in 1 h at λ > 400 nm. Under irradiation by longer wavelength of light (λ > 420 nm), CNSC still exhibit a superior hydrogen evolution rate, which is 72.9 and 5.4 times higher than that of bulk g‐C₃N₄ and g‐C₃N₄ nanosheets, respectively.     

Metal‐Cluster‐Decorated TiO2 Nanotube Arrays: A Composite Heterostructure toward Versatile Photocatalytic and Photoelectrochemical Applications

Recent years have witnessed increasing interest in the solution‐phase synthesis of atomically precise thiolate‐protected gold clusters (Au_x); nonetheless, research on the photocatalytic properties of Au_x–semiconductor nanocomposites is still in its infancy. In this work, recently developed glutathione‐capped gold clusters and highly ordered nanoporous layer‐covered TiO₂ nanotube arrays (NP‐TNTAs) are employed as nanobuilding blocks for the construction of a well‐defined Au_x/NP‐TNTA heterostructure via a facile electrostatic self‐assembly strategy. Versatile photocatalytic performances of the Au_x/NP‐TNTA heterostructure which acts as a model catalyst, including photocatalytic oxidation of organic pollutant, photocatalytic reduction of aromatic nitro compounds and photoelectrochemical (PEC) water splitting under simulated solar light irradiation, are systematically exploited. It is found that synergistic interaction stemming from monodisperse coverage of Au_x clusters on NP‐TNTAs in combination with hierarchical nanostructure of NP‐TNTAs reinforce light absorption of Au_x/NP‐TNTA heterostructure especially within visible region, hence contributing to the significantly enhanced photocatalytic and PEC water splitting performances. Moreover, photocatalytic and PEC mechanisms over Au_x/NP‐TNTA heterostructure are elucidated and corresponding reaction models were presented. It is anticipated that this work could boost new insight for photocatalytic properties of metal‐cluster‐sensitized semiconductor nanocomposites.     

Proton‐Functionalized Two‐Dimensional Graphitic Carbon Nitride Nanosheet: An Excellent Metal‐/Label‐Free Biosensing Platform

Ultrathin graphitic carbon nitride (g‐C₃N₄) nanosheets, due to their interesting two‐dimensional graphene‐like structure and unique physicochemical properties, have attracted great research attention recently. Here, a new approachis developed to prepare, for the first time, proton‐functionalized ultrathin g‐C₃N₄ nanosheets by sonication‐exfoliation of bulk g‐C₃N₄ under an acid condition. This method not only reduces the exfoliation time from more than 10 h to 2 h, but also endows the nanosheets with positive charges. Besides retaining the properties of g‐C₃N₄, the obtained nanosheets with the thickness of 2–4 nm (i.e., 6–12 atomic monolayers) also exhibit large specific surface area of 305 m² g^?1, enhanced fluorescence intensity, and excellent water dispersion stability due to their surface protonation and ultrathin morphology. The well‐dispersed protonated g‐C₃N₄ nanosheets are able to interact with negatively charged heparin, which results in the quenching of g‐C₃N₄ fluorescence. A highly sensitive and highly selective heparin sensing platform based on protonated g‐C₃N₄ nanosheets is established. This metal‐free and fluorophore label‐free system can reach the lowest heparin detection limit of 18 ng mL^?1.