Ion Intercalation Research Articles

An Enhanced Synaptic Plasticity of Electrolyte-Gated Transistors through the Tungsten Doping of an Oxide Semiconductor

Oxide electrolyte-gated transistors have shown the ability to emulate various synaptic functions, but they still require a high gate voltage to form long-term plasticity. Here, we studied electrolyte-gated transistors based on InOx with tungsten doping (W-InOx). When the tungsten-to-indium ratio increased from 0% to 7.6%, the memory window of the transfer curve increased from 0.2 V to 2 V over a small sweep range of −2 V to 2.5 V. Under 50 pulses with a duty cycle of 2%, the conductance of the transistor increased from 40-fold to 30,000-fold. Furthermore, the W-InOx transistor exhibited improved paired pulse facilitation and successfully passed the Pavlovian test after training. The formation of WO3 within InOx and its ion intercalation into the channel may account for the enhanced synaptic plasticity.

Recovery of lithium by pseudocapacitive electrodes in capacitive deionization

Lithium is a crucial component in rechargeable lithium-ion batteries for many applications, including the powering of electric vehicles and stationary energy storage systems. This investigation focused on two hybrid pseudocapacitive materials, the polystyrene sulfonate-MXene composite (PM) and the sodium titanate/graphene oxide composite (NG), for lithium ions recovery from aqueous Li+ resources. This was achieved by selectively removing unwanted divalent Ca2+ and Mg2+ ions, as well as monovalent K+ ions, through capacitive deionization (CDI) using a single-cell system, resulting in a final solution enriched with Li+ ions. Based on the ion selectivity order observed previously as Mg2+≈ Ca2+ >K+ > Li+, a series of CDI experiments were conducted with sequential steps to remove more selective ions first and to obtain a lithium-enriched solution with higher purity and maximum extracted fraction. Both PM and NG electrodes demonstrated promising performance when tested in binary, ternary, and quaternary ionic solutions with the recovered lithium solution purity in the range of 59.09 %-95.94 % and 59.75 %-77.17 %, respectively. Further, the highest enrichment factor values observed were SLi+,Mg2+; 268.1 for PM and SLi+,Ca2+; 44.25, for NG electrodes. The PSS-modified MXene composite electrode in obtaining the Li+ solution with the highest purity when separated Ca2+ from a binary solution. These findings offer valuable insights into the selective electrosorption of divalent ions over lithium ions through the utilization of ion intercalation pseudocapacitive nanocomposite electrodes. The obtained results hold significance in advancing novel non-precipitation techniques for the recovery of lithium ions from aqueous lithium resources.

Structure, Properties, and Preparation of MXene and the Application of Its Composites in Supercapacitors

Two-dimensional transition metal carbides/nitrides (MXenes) are emerging members of the two-dimensional material family, obtained by removing the A layer of the MAX phase through methods such as liquid-phase etching. This article summarizes the structure and properties of MXenes, as well as several preparation methods, including etching with hydrofluoric acid and fluoride salts, alkali-based etching, electrochemical etching, Lewis acid molten salt etching, and direct synthesis. Due to their unique two-dimensional structure and surface chemistry, MXenes exhibit good metallic conductivity, hydrophilicity, excellent flexibility, and ion intercalation properties, showing great potential in the research and application of supercapacitors and attracting widespread attention. The combination of MXene with other types of materials, including polymers, metal hydroxides, metal oxides, and carbon materials, takes advantage of composites to improve energy storage performance and shows great potential in the research and application of supercapacitors. This article provides a detailed summary of MXene composite materials and capacitor performance and introduces the research progress of MXene materials in the field of supercapacitor energy storage applications, aiming to provide references for the preparation of high-performance MXene supercapacitor electrode materials.

Cellulosic Nonwovens Incorporated with Fully Utilized MXene Precursor as Smart Pressure Sensor and Multi‐Protection Materials

AbstractCurrently, multifunctional MXene‐integrated wearable textiles (MWTs) are particularly appealing due to their various applications such as health monitoring, smart protection, and medical treatment. However, scalable manufacture of durable, stable, and high‐performance multifunctional MWTs still face challenges due to the poor oxidation stability of MXene and low utilization of precursor titanium aluminum carbide (MAX). Herein, an improved preparation strategy for zinc ion (Zn2+) intercalation is proposed to create high antioxidative MXene (ZM) and exceptionally conductive and printable gel ink based on MXene sediments (ZMS‐ink), while multifunctional wearable textiles are fabricated using spray‐coating and screen‐printing techniques on cellulosic nonwoven textiles (CNWs), achieving the complete utilization of MXene precursor. Benefiting from the inherent disordered stacking and porous structure of CNWs, along with the highly conductive ZM and ZMS‐ink, as‐prepared smart, wearable and green‐based pressure sensor offered proper breathability, high sensitivity (2602.26 kPa−1), wide sensing range (0–141 kPa), and excellent cycling stability (>5000 cycles). Additionally, the sensor exhibited efficient photothermal/photodynamic therapy antibacterial activity and exceptional electromagnetic interference shielding performance (57.5 dB). Therefore, this work paves the way for the future development of integrated and scalable multifunctional wearable devices building on the environmental‐friendly CNWs incorporated with fully utilized MAX, offering a green and cost‐effective approach.

Two-dimensional/three-dimensional hierarchical self-supporting potassium ammonium vanadate@MXene hybrid film for superior performance aqueous zinc ion batteries

Currently, aqueous zinc ion batteries (AZIBs) have grown to be a good choice for large-scale energy storage systems due to their high theoretical specific capacity, low redox potential, low cost, and non-toxicity of the aqueous electrolyte. However, it is still challenging to obtain high specific capacity and stability suitable cathodes. Herein, hierarchical self-supporting potassium ammonium vanadate@MXene (KNVO@MXene) hybrid films were prepared by vacuum filtration method. Due to the three-dimensional nanoflower structure of KNVO with dual ions intercalation, high conductivity of two-dimensional Ti3C2Tx MXene, and the hierarchical self-supporting structure, the AZIB based on the KNVO@MXene hybrid film cathode possessed superior specific capacity (481 mAh/g at 0.3 A/g) and cycling stability (retaining 125 mAh/g after 1000 cycles at a high current density of 10 A/g). In addition, the storage mechanism was revealed by various ex-situ characterizations. Hence, a new viewpoint for the preparation of AZIB self-supporting cathode materials is presented.

Revealing the role of calcium ion intercalation of hydrated vanadium oxides for aqueous zinc-ion batteries

Exploring suitable high-capacity V2O5-based cathode materials is essential for the rapid advancement of aqueous zinc ion batteries (ZIBs). However, the typical problem of slow Zn2+ diffusion kinetics has severely limited the feasibility of such materials. In this work, unique hydrated vanadates (CaVO, BaVO) were obtained by intercalation of Ca2+ or Ba2+ into hydrated vanadium pentoxide. In the CaVO//Zn and BaVO//Zn batteries systems, the former delivered up to a 489.8 mAh g−1 discharge specific capacity at 0.1 A g−1. Moreover, the remarkable energy density of 370.07 Wh kg−1 and favorable cycling stability yard outperform BaVO, pure V2O5, and many reported cathodes of similar ionic intercalation compounds. In addition, pseudocapacitance analysis, galvanostatic intermittent titration (GITT) tests, and Trasatti analysis revealed the high capacitance contribution and Zn2+ diffusion coefficient of CaVO, while an in-depth investigation based on EIS elucidated the reasons for the better electrochemical performance of CaVO. Notably, ex-situ XRD, XPS, and TEM tests further demonstrated the Zn2+ insertion/extraction and Zn-storage mechanism that occurred during the cycle in the CaVO//Zn battery system. This work provides new insights into the intercalation of similar divalent cations in vanadium oxides and offers new solutions for designing cathodes for high-capacity aqueous ZIBs.

Highly active and durable NiCoP electrocatalyst through Ga ion intercalation strategy for long-lasting water electrolysis

Developing non-precious catalysts with optimal catalytic performance is very crucial for sustainable energy-related systems. However, the sluggish kinetics and low efficiency limits their practical applications. Herein, we report several Ga intercalated NiCoP nanoneedle (Ga-NiCoP) catalysts. It indicates that the introduction of Ga ions increases the exposed active sites and accelerates the species reconstruction. The prepared catalyst drives HER with an overpotential of 348 mV at 500 mA cm−2 and 270 mV at 100 mA cm−2 for OER. Meanwhile, it achieves a cell voltage of 1.47 V at current density 10 mA cm−2 in a two-electrode system and maintains stability for 150 h. This work provides a general approach to fabricate some other non-precious metal electrocatalysts to produce hydrogen.

Tuning MXene Properties through Cu Intercalation: Coupled Guest/Host Redox and Pseudocapacitance.

MXenes are 2D transition metal carbides, nitrides, and/or carbonitrides that can be intercalated with cations through chemical or electrochemical pathways. While the insertion of alkali and alkaline earth cations into Ti3C2Tx MXenes is well studied, understanding of the intercalation of redox-active transition metal ions into MXenes and its impact on their electronic and electrochemical properties is lacking. In this work, we investigate the intercalation of Cu ions into Ti3C2Tx MXene and its effect on its electronic and electrochemical properties. Using X-ray absorption spectroscopy (XAS) and ab initio molecular dynamics (AIMD), we observe an unusual phenomenon whereby Cu2+ ions undergo partial reduction upon intercalation from the solution into the MXene. Furthermore, using in situ XAS, we reveal changes in the oxidation states of intercalated Cu ions and Ti atoms during charging. We show that the pseudocapacitive response of Cu-MXene originates from the redox of both the Cu intercalant and Ti3C2Tx host. Despite highly reducing potentials, Cu ions inside the MXene show an excellent stability against full reduction upon charging. Our findings demonstrate how electronic coupling between Cu ions and Ti3C2Tx modifies electrochemical and electronic properties of the latter, providing the framework for the rational design and utilization of transition metal intercalants for tuning the properties of MXenes for various electrochemical systems.

Cobalt doped K-birnessite as ultrastable cathode for aqueous calcium-ion batteries

Aqueous Ca ion batteries (ACIBs) are one of the emerging energy-storage technologies due to their low costs and low polarization strength. Birnessite-MnO2 is one kind of promising cathode because of its large interlayer distance for facile Ca2+ ion intercalation and high theoretical specific capacity (241 mAh g−1), but the inferior cycling performance significantly limits its application in ACIBs. Herein, 2% Co-doped K-birnessite K0.11Co0.02Mn0.98O2·1.4H2O (CB-2) with superior structural stability is reported for the first time. The Co-doped K-birnessite exhibits enhanced conductivity and capacitance ability. Moreover, after Co doping, the Mn–O ionic bond is shortened and the banding energy is reduced, which effectively inhibits the Jahn-Taller effect and improves the thermodynamic stability. More interestingly, we find that Ca2+ can restrain the irreversible transition of birnessite from layered to spinel. CB-2 cathode delivers an excellent rate performance of 181.2 mAh g−1 at 200 mA g−1 and structural stability of 1000 cycles at 2 A g−1 with 90.4% capacity retention. Finally, a stable ACIB is constructed by using the CB-2 cathode and polyimide anode, which shows a decent specific capacity of 51.9 mAh g−1 at 200 mA g−1 and superior cycling stability. This demonstrates effective foreign metal ion doping for K-birnessite to achieve superior Ca2+ storage in aqueous batteries.

Confluence of ZnO and PTFE Binder for Enhancing Performance of Thin‐Film Lithium‐Ion Batteries

Developing anode materials with high specific capacity and cycling stability is vital for improving thin‐film lithium‐ion batteries. Thin‐film zinc oxide (ZnO) holds promise due to its high specific capacity, but it suffers from volume changes and structural stress during cycling, leading to poor battery performance. In this research, we ingeniously combined polytetrafluoroethylene (PTFE) with ZnO using a radio frequency (RF) magnetron co‐sputtering method, ensuring a strong bond in the thin‐film composite electrode. PTFE effectively reduced stress on the active material and mitigated volume change effects during Li+ ion intercalation and deintercalation. The composite thin films are thoroughly characterized using advanced techniques such as X‐ray diffraction, scanning electron microscopy, and X‐ray photoelectron spectroscopy for investigating correlations between material properties and electrochemical behaviors. Notably, the ZnO/PTFE thin‐film electrode demonstrated an impressive specific capacity of 1305 mAh g−1 (=7116 mAh cm−3) at a 0.5C rate and a remarkable capacity retention of 82% from the 1st to the 100th cycle, surpassing the bare ZnO thin film (50%). This study provides valuable insights into using binders to stabilize active materials in thin‐film batteries, enhancing battery performance.

Hollow mushroom nanomaterials for potentiometric sensing of Pb2+ ions in water via the intercalation of iodide ions into the polypyrrole matrix

Abstract Herein, the synthesis of a sensor for the determination of lead (Pb2+) ions via the intercalation of iodide ions into the polypyrrole matrix is performed. It demonstrated a Nernstian slope of 31.7 mV/decade, indicating a linear response within the concentration range of 10−5–10−1 M. The detection limit achieved is 9.10−6 M, indicating the sensor’s sensitivity to low concentrations of Pb2+. The effectiveness of the Ppy/I− sensor in Pb2+ sensing is confirmed through cyclic voltammetry, where a peak potential of −0.2 V is observed. The sensitivity of the sensor for Pb2+ detection is measured to be 2 µA/M. Moreover, the Ppy/I− sensor exhibits a negative response to interfering ions, which enhances its selectivity for Pb2+ detection. Furthermore, when tested with natural water samples such as tap or underground water, which are typically free of lead ions, the sensor demonstrates a negative response to normal interfering ions commonly found in such samples. The Ppy/I− sensor offers several advantages, including the ability to detect Pb2+ ions at very low concentrations, a flexible and adaptable design, and a cost-effective preparation technique. These features make it a promising tool for accurate and efficient detection of Pb2+ ions.

Building stabilized Cu0.17Mn0.03V2O5−□·2.16H2O cathode enables an outstanding room‐/low‐temperature aqueous Zn‐ion batteries

AbstractVanadium oxide cathode materials with stable crystal structure and fast Zn2+ storage capabilities are extremely important to achieving outstanding electrochemical performance in aqueous zinc‐ion batteries. In this work, a one‐step hydrothermal method was used to manipulate the bimetallic ion intercalation into the interlayer of vanadium oxide. The pre‐intercalated Cu ions act as pillars to pin the vanadium oxide (V‐O) layers, establishing stabilized two‐dimensional channels for fast Zn2+ diffusion. The occupation of Mn ions between V‐O interlayer further expands the layer spacing and increases the concentration of oxygen defects (Od), which boosts the Zn2+ diffusion kinetics. As a result, as‐prepared Cu0.17Mn0.03V2O5−□·2.16H2O cathode shows outstanding Zn‐storage capabilities under room‐ and low‐temperature environments (e.g., 440.3 mAh g−1 at room temperature and 294.3 mAh g−1 at −60°C). Importantly, it shows a long cycling life and high capacity retention of 93.4% over 2500 cycles at 2 A g−1 at −60°C. Furthermore, the reversible intercalation chemistry mechanisms during discharging/charging processes were revealed via operando X‐ray powder diffraction and ex situ Raman characterizations. The strategy of a couple of 3d transition metal doping provides a solution for the development of superior room‐/low‐temperature vanadium‐based cathode materials.

Defect engineering unveiled: Enhancing potassium storage in expanded graphite anode

Expanded graphite (EG) stands out as a promising material for the negative electrode in potassium-ion batteries. However, its full potential is hindered by the limited diffusion pathway and storage sites for potassium ions, restricting the improvement of its electrochemical performance. To overcome this challenge, defect engineering emerges as a highly effective strategy to enhance the adsorption and reaction kinetics of potassium ions on electrode materials. This study delves into the specific effectiveness of defects in facilitating potassium storage, exploring the impact of defect-rich structures on dynamic processes. Employing ball milling, we introduce surface defects in EG, uncovering unique effects on its electrochemical behavior. These defects exhibit a remarkable ability to adsorb a significant quantity of potassium ions, facilitating the subsequent intercalation of potassium ions into the graphite structure. Consequently, this process leads to a higher potassium voltage. Furthermore, the generation of a diluted stage compound is more pronounced under high voltage conditions, promoting the progression of multiple stage reactions. Consequently, the EG sample post-ball milling demonstrates a notable capacity of 286.2 mAh g-1 at a current density of 25 mA g−1, showcasing an outstanding rate capability that surpasses that of pristine EG. This research not only highlights the efficacy of defect engineering in carbon materials but also provides unique insights into the specific manifestations of defects on dynamic processes, contributing to the advancement of potassium-ion battery technology.

A Review on the Upgradation of Biomass-derived Hard Carbon Materials

Abstract: Sodium-ion battery is a promising alternative to lithium-ion battery because of its abundant raw material resources, low price, and high specific capacity. Amorphous carbon materials (hard carbon) have micropores and impurities, facilitating the intercalation of sodium ions to form "quasi-metallic sodium," resulting in a high sodium storage capacity and a low sodium storage potential. Consequently, hard carbon is one of the most widely studied negative electrode materials. It can be prepared from biomass by thermochemical conversion and has the advantages of large specific capacity, low cost, good cycling stability, and renewability. This review focuses on the recent advances in biomass-based hard carbon materials. Firstly, the preparation methods of hard carbon, including precursor selection, pretreatment, drying methods, and carbonization processes, are summarized. Secondly, the effects of precursor composition and heteroatom doping structure and properties of hard carbon are examined, and the changes in carbon material pores during the activation process, as well as the selection of optimal drying method, pyrolysis temperature, carbonization temperature, activator dosage, and additive, are discussed. Thirdly, the impact of preparation methods on hard carbon's cost, efficiency, and stability is briefly summarized, and the relevant improvement measures and prospects are proposed. Finally, some insights are provided into preparing highperformance biomass-based anode materials for sodium-ion batteries.

Research on Sodium Storage Performance of Cu and Mg Doped P2 Type Layered Oxide Cathode Materials

The P2-type Ni–Mn-based oxide cathode materials have drawbacks such as the Jahn-Teller effect and crystal phase transition under high pressure. In this study, Cu and Mg modifications were introduced to inhibit the P2–O2 phase transition and increase the lattice spacing, thereby reducing the resistance of sodium ion de-embedding and intercalation to improve the overall electrochemical performance of the battery. A series of P2-type Na0.67Ni0.33−xMn0.67CuxO2 and Na0.67Ni0.33−xMn0.67MgxO2 cathode materials were synthesized through solid-state reaction. Cu substitution significantly alters the structural stability and electrochemical properties. In the voltage range from 1.5 V to 4.2 V and at 0.1 C, the initial discharge specific capacity of Na0.67Ni0.18Mn0.67Cu0.15O2 was 167 mAh·g−1, with 86 mAh·g−1 remaining after 100 cycles at 1 C. Additionally, a high discharge specific capacity of 207 mAh·g−1 was achieved with 0.075 Mg doping, suggesting that part of O2− participated in the internal electrochemical reaction. Furthermore, the rate performance of Na0.67Ni0.28Mn0.67Mg0.05O2 was found to be the best. This phenomenon was attributed to the inactive Mg2+ retaining more Na+ in the interlayer, inhibiting crystal structure transformation and Jahn-Teller distortion. The larger radius of Mg2+ increased the layer spacing, widened the Na+ de-embedding channels, and increased the diffusion coefficient.

Evolution of α-V2O5 into electrochemically transformed NaV3O8 structure: Structural changes and supercapacitor application

Nowadays, cost-effective and environmentally friendly supercapacitors (SCs) with high energy and power densities are gaining significant research attention since they could broaden the application of capacitors. The present study demonstrates a low-cost green synthesis technique to prepare the α-V2O5 phase using Aloe Vera leaf extract. X-ray diffraction technique confirmed the formation of the orthorhombic α-V2O5 phase. The prepared α-V2O5 was employed as an electrode material for SC application. During an electrochemical cyclic voltammetry test in Na2SO4 electrolyte, Na+ ions intercalation and de-intercalation processes resulted in a phase transformation of α-V2O5 to NaV3O8. Structural transformation (i.e., orthorhombic to monoclinic crystal structure) and morphological changes were also observed during the electrochemical phase conversion process. This electrochemical phase transformation process improved the overall supercapacitive performance of the α-V2O5 material. Such electrochemically converted NaV3O8 displayed a maximum specific capacitance of 640.1 F g−1 at 0.5 A g−1 with a long cyclic stability. Furthermore, the AC // NaV3O8 asymmetric SC coin cell device delivered a maximum energy density of 62.6 Wh kg−1 and a power density of 7.3 kW kg−1 along with an excellent cycling stability of ∼81 % over 5000 GCD cycles.

The Prospective Applications of Arising Nanostructured Dielectric Materials in Storage of Energy: A Comprehensive Review

Background: The manufacture and study of innovative materials that enable the availability of relevant technologies are vital in light of the energy demands of various human activities and the need for a substantial shift in the energy matrix. Objective: A strategy based on the creation of enhanced applications for batteries has been devised to reduce the conversion, storage, and feeding of renewable energy like fuel cells and electrochemical capacitors. Methods: Conductive polymers (CP) can be utilised instead of traditional inorganic chemicals. Electrochemical energy storage devices with similar capabilities can be built using approaches based on the production of composite materials and nanostructures. Results: CP's nanostructuring is notable for its concentration on synergistic coupling with other materials, which sets it apart from other nanostructures that have been developed in the preceding two decades. This is due to the fact that, when paired with other materials, their distinctive morphology and adaptability significantly enhance performance in areas like the suppression of ionic diffusion trajectories, electronic transport and the improvement of ion penetrability and intercalation spaces. Conclusion: The present study forecasts the wide-ranging modern applications of diverse nanostructured dielectric materials along with its future prospectives. The potential contributions of nanostructured carbon nanotubes to the development of innovative materials for energy storage devices are also critically discussed in this context, which delivers a summary of the present state of information on this emerging topic.

Coexistence of Ferromagnetism and Ferroelectricity in Cu-Intercalated Bilayer CrI3.

Design of two-dimensional (2D) multiferroic materials with two or more ferroic orders in one structure is highly desired in view of the development of next-generation electronic devices. Unfortunately, experimental or theoretical discovery of 2D intrinsic multiferroic materials is rare. Using first-principles calculation methods, we report the realization of multiferroics that couple ferromagnetism and ferroelectricity by intercalating Cu atoms in bilayer CrI3, Cux@bi-CrI3 (x = 0.03, 0.06, and 0.25). Our results show that the intercalation of Cu atoms leads to the inversion symmetry breaking of bilayer CrI3 and produces intercalation density-dependent out-of-plane electric polarization, around 18.84-90.31 pC·cm-2. Moreover, the switch barriers of Cux@bi-CrI3 in both polarization states are small, ranging from 0.31 to 0.69 eV. Furthermore, the magnetoelectric coupling properties of Cux@bi-CrI3 can be modulated via varying the metal ion intercalation density, and half-metal to semiconductor transition can be occurred by decreasing the intercalation density of metal ions. Our work paves a practical path for 2D magnetoelectron coupling devices.

Engineering Antibonding Orbital Occupancy for Enhanced Sodium‐Ion Intercalation Kinetics in Transition Metal Oxides

AbstractIn the quest to elevate the sodium‐ion intercalation kinetics of transition metal oxide electrodes, the intrinsic low conductivity of these materials often acts as a bottleneck, restricting Na+ storage. Herein, the mechanism behind sodium‐ion diffusion kinetics in MnO2 is explored, specifically focusing on the manipulation of π* antibonding orbital occupancy. This is accomplished through strategic doping with strongly electron‐withdrawing Rh3+ (t2g6eg0), enhancing the hybridization of Mn 3d‐O 2p orbitals and significantly increasing the electrical conductivity of MnO2. Density functional theory (DFT) calculations and X‐ray absorption spectroscopy (XAS) results demonstrate that the smaller orbital energy difference between Rh3+ eg and Mn4+ t2g, compared to that between Rh3+ eg and Mn4+ eg, fosters direct electron transfer from the Mn4+ t2g to the vacant Rh3+ eg. This electron movement induces an upshift in the Mn‐t2g orbital energy levels while concurrently diminishing the occupancy of π* antibonding orbitals formed via Mn t2g‐O 2p hybridization. The resultant Rh‐MnO2 electrode exhibits an impressive specific capacity of 335 F g−1 at 1 A g−1 and a substantial rate capacity of 224.8 F g−1 at 20 A g−1. This investigation elucidates the intricate mechanism underlying the sluggish kinetics of sodium ion intercalation within transition metal oxide frameworks.

Interface Chemical Bond Enhanced Ions Intercalated Carbon Nitride/CdSe‐Diethylenetriamine S‐Scheme Heterojunction for Photocatalytic H2O2 Synthesis in Pure Water

AbstractPhotosynthesis of hydrogen peroxide (H2O2) is regarded as an economically efficient and environmentally friendly synthesis method. However, the scalability of photocatalytic H2O2 production (PHP) is hindered by the sluggish reaction kinetics and rapid recombination of photogenerated charge carriers. In this study, an organic amine‐constrained ions intercalated carbon nitride/CdSe‐diethylenetriamine (K+/I−‐CN/CdSe‐D) S‐scheme heterojunction is synthesized using an organic–inorganic hybrid approach and employed for PHP for the first time. The optimization of the heterojunction interface by I− and K+ ions contributed to enhanced light absorption capabilities and reduced interlayer charge transfer distance. Concurrently, the synergy of C─Se bonds at interface effectively modulated the electron transfer pathways. The coordination environment and charge transfer mechanism are thoroughly investigated by extended X‐ray absorption fine structure and in situ irradiated X‐ray photoelectron spectroscopy. The H2O2 production rate of 40%K+/I−‐CN/CdSe‐D reached 2240.23 µmol h−1 g−1 in pure water. This study highlights the significance of dual tuning of interface chemical bonds and ionic intercalation as an effective strategy for enhancing the photocatalytic H2O2 , paving the way for further advancements in PHP technology.