Electronic Structure Of Active Site Research Articles

Enhancing Ozone Decomposition in Humid Environments through Carbon Doping to Disrupt the Hydrogen Bond Network in Mullite YMn2O5.

The strong adsorption of water molecules at the active site of the catalyst presents significant challenges in ozone decomposition, particularly at room temperature and in humid environments. To address this issue, we doped carbon atoms into the Mn-mullite YMn2O5 catalyst to replace oxygen, resulting in efficient and stable ozone decomposition under highly humid conditions. Utilizing DFT calculations, our study demonstrated that carbon doping disrupts hydrogen bond networks on the catalyst surface, thereby reducing water adsorption. Furthermore, carbon doping regulated the electronic structure of active sites, fundamentally reversing the adsorption strength of water and ozone molecules, which avoids the decline in catalytic activity caused by competitive water adsorption. Experimentally, under room temperature and relative humidity (RH) 50%, the carbon-doped YMn2O5 catalyst maintained 100% conversion in decomposing 100 ppm of ozone for at least 24 h, surpassing the most reported catalysts against water poisoning. Furthermore, the utilization of a carbon-doped mullite-loaded air cleaner demonstrated promising application in degrading ozone. The approach of enhancing catalyst water resistance through carbon doping, which disrupts hydrogen bonds, provided valuable insights into the design of stable and efficient room-temperature ozonolysis catalysts.

Boosting Acidic Hydrogen Evolution Kinetics Induced by Weak Strain Effect in PdPt Alloy for Proton Exchange Membrane Water Electrolyzers.

Strain engineering is an effective strategy for manipulating the electronic structure of active sites and altering the binding strength toward adsorbates during the hydrogen evolution reaction (HER). However, the effects of weak and strong strain engineering on the HER catalytic activity have not been fully explored. Herein, the core-shell PdPt alloys with two-layer Pt shells (PdPt2L) and multi-layer Pt shells (PdPtML) is constructed, which exhibit distinct lattice strains. Notably, PdPt2L with weak strain effect just requires a low overpotential of 18mV to reach 10mA cm-2 for the HER and shows the superior long-term stability for 510h with negligible activity degradation in 0.5M H2SO4. The intrinsic activity of PdPt2L is 6.2 and 24.5 times higher than that of PdPtML and commercial Pt/C, respectively. Furthermore, PdPt2L||IrO2 exhibits superior activity over Pt/C||IrO2 in proton exchange membrane water electrolyzers and maintains stable operation for 100h at large current density of 500mA cm-2. In situ/operando measurements verify that PdPt2L exhibits lower apparent activation energy and accelerated ad-/desorption kinetics, benefiting from the weak strain effect. Density functional theory calculations also reveal that PdPt2L displays weaker H* adsorption energy compared to PdPtML, favoring for H* desorption and promoting H2 generation.

WN-CoS2 nanoparticles encapsulated into carbon nanotubes enable a stable and high-performance rechargeable zinc air battery

The battery performance associated with longevity are the priorities for the industrialization of rechargeable zinc air battery (ZAB). Herein, we have reported the construction of WN-CoS2 heterostructure enveloped by nitrogen and phosphorus co-doped carbon nanotubes (WN-CoS2@NPCNT). WN-CoS2@NPCNT performs a superior oxygen evolution reaction (OER) catalytic activity of 279 mV overpotential to reach 10 mA cm−2, lowered by 85 mV with relative to CoS2@NCNT attributing to the heterostructure efficiently modulating the electronic structure of active sites. Besides, the half-wave potential reaches 0.875 V vs. RHE for WN-CoS2@NPCNT under oxygen reduction reaction (ORR) condition, corresponding to a 3.2-time higher kinetic current density compared to commercial Pt/C. Due to the exceptional bifunctionality, the battery performance is 205 mW cm−2 for WN-CoS2@NPCNT, 1.54 times higher than commercial counterpart, Pt/C + IrO2. Impressively, the battery performance sustains for 1000 h for WN-CoS2@NPCNT stemming from the confinement effect caused by NPCNT. In addition, the all-solid-state ZAB shows a high-power density of 55 mW cm−2.

Modulating Hydrogen Adsorption by Unconventional p–d Orbital Hybridization over Porous High‐Entropy Alloy Metallene for Efficient Electrosynthesis of Nylon‐6 Precursor

AbstractRenewable electricity driven electrosynthesis of cyclohexanone oxime (C6H11NO) from cyclohexanone (C6H10O) and nitrogen oxide (NOx) is a promising alternative to traditional environment‐unfriendly industrial technologies for green synthesis of C6H11NO. Precisely controlling the reaction pathway of the C6H10O/NOx‐involved electrochemical reductive coupling reaction is crucial for selectively producing C6H11NO, which is yet still challenging. Herein, we report a porous high‐entropy alloy PdCuAgBiIn metallene (HEA‐PdCuAgBiInene) to boost the electrosynthesis of C6H11NO from C6H10O and nitrite, achieving a high Faradaic efficiency (47.6 %) and almost 100 % yield under ambient conditions. In situ Fourier transform infrared spectroscopy and theoretical calculations demonstrate that unconventional orbital hybridization between d‐block metals and p‐block metals could regulate the local electronic structure of active sites and induce electron localization of electron‐rich Pd sites, which tunes the active hydrogen supply, facilitates the generation and enrichment of key intermediates NH2OH* and C6H10O*, and efficiently promotes their C−N coupling to selectively produce C6H11NO.

Crystal-dependent doping effects over MnO2 for Fenton-like catalysis optimization

Heteroatom doping is one of the most important strategies to improve the Fenton-like activity of heterogenous catalysts by optimizing the coordination environment and electronic structure of active sites. However, the doping effect on the crystal structure that governs the atom orientation and chemical stability of catalysts remains largely elusive. Here, we report the rational design and synthesis of a series of fluorine-doped MnO2 catalysts with different crystal phases (denoted as F-α-, F-β-, F-γ-, and F-δ-MnO2), aiming to reveal the crystal-dependent disparity of doping effects in PMS activation. Results demonstrate that fluorine doping exhibits selectivity towards specific crystal structures of MnO2 catalyst. The γ-MnO2 with a lowest Mn average oxidation state (AOS) significantly enhances the adsorption and activation of PMS upon fluorine doping, outperforming other MnO2 counterparts (i.e., α, β, and δ-type). Interestingly, we identify a strong linear correlation (R2 = 0.99) between the degradation rate constant variation (Δk) and ΔAOS divergence of MnO2 catalysts before and after fluorine doping, revealing a novel structure–activity relationship for Fenton-like catalysis optimization. In addition, a nonradical pathway with synergism of 1O2 and active surface-complex contributes greatly to pollutant removal in the developed F-γ-MnO2/PMS system, thereby demonstrating outstanding degradation performance towards electron-rich organics. This work provides fundamental insights into the crystal structure–activity relationship in the disparity of doping effect, which may inspire the rational design of efficient Fenton-like catalysts for wastewater treatment.

Modulating the electronic structure of PdCoP nanonetworks alloy for efficient electro-catalysis of methanol oxidation

Modulating the d-orbital electronic structure of active metals by doping heteroatoms is efficient for the electro-catalysis of methanol oxidation reaction (MOR). However, precise doping hybrid atoms into the lattices of alloy catalysts remains challenging. Herein, the selected doping of electron-rich P atoms at the active site of Pd was achieved by hydrothermal reduction. We found that P atoms prefer to bond Pd atoms, thus tuning the electronic structure of active sites in PdCoP alloy. Consequently, the tailored PdCoP catalyst exhibited remarkable mass activity of 2.13 A mgPd−1 towards MOR, which surpasses most reported Pd-based alloy nanocatalysts. Theoretical calculations revealed that the tailored d-band center of Pd in PdCoP catalyst exhibited moderate adsorption of CO and OH intermediates, thus maximizing the MOR performance. The current work highlights the fabrication of P-doped Pd-based catalysts for realizing high MOR, which can be further extended to other energy-related applications.

Morphological and Surface Electronic Structure Design of Alloys Electrocatalyst for Alkaline HER

Among the various hydrogen production methods, water electrolysis provides numerous advantages, including high purity of the produced hydrogen and low carbon emission. In this context, one of the concerns is associated with the replacement, or partial replacement, of noble-metal electrocatalyst for hydrogen evolution reaction (HER) by low-cost, commercially viable ones. To achieve this objective, alloying provides a direct way to tailor the electronic structure of active site and hence is expected to effectively reduce the usage of noble metal. Furthermore, increasing the surface area through morphology design is considered a promising method for enhancing catalyst activity. Among the diverse strategies to increase the surface area, dealloying plays a unique role by generating porous structure, thereby offering advantages in terms of cost-effectiveness and controllable structure. In this study, we have synthesized various Zn-Ni based alloy electrocatalysts using a facile solvothermal method, followed by a dealloying process. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and inductively coupled plasma mass spectrometry are used to examine the morphology, composition, and electronic structure. The electrochemical performance is investigated using linear sweep voltammetry, electrochemical impedance spectroscopy, cyclic voltammetry, and electrochemical specific surface area analyses. We demonstrate that resulting HER alloy electrocatalyst exhibits a low overpotential and Tafel slope, and good stability over 200 hours.

Introducing oxygen vacancies to tune cobalt oxide by Mn doped for high-effective overall water-splitting

The design of efficient bifunctional electrocatalysts for overall water splitting is an essential task for the production of hydrogen. Co3O4 has been developed as highly efficient OER electrocatalysts but with almost no activity for HER. The formation of oxygen vacancies in Co3O4 could significantly enhance the OER and HER activity, Mn-doping are relatively infrequent in this field. In this work, Co3O4 is modified by doping Mn to introduced oxygen vacancies for high-efficiency water splitting performance. The Mn doped Co3O4 shows excellent performance towards hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) with a low overpotential at 10 mA·cm−2 of 157 mV and 265 mV, and an applied potential of 1.54 V at 10 mA·cm−2. The excellent electrocatalytic performance is mainly attributed to oxygen vacancies in Co3O4, rational adjustment of the electronic structure of active sites to increase the intrinsic activity of Co3O4. The Mn doped Co3O4 can be a promising bifunctional electrocatalyst for overall water splitting.

Modulating Hydrogen Adsorption by Unconventional p-d Orbital Hybridization over Porous High-Entropy Alloy Metallene for Efficient Electrosynthesis of Nylon-6 Precursor.

Renewable electricity driven electrosynthesis of cyclohexanone oxime (C6H11NO) from cyclohexanone (C6H10O) and nitrogen oxide (NOx) is a promising alternative to traditional environment-unfriendly industrial technologies for green synthesis of C6H11NO. Precisely controlling the reaction pathway of the C6H10O/NOx-involved electrochemical reductive coupling reaction is crucial for selectively producing C6H11NO, which is yet still challenging. Herein, we report a porous high-entropy alloy PdCuAgBiIn metallene (HEA-PdCuAgBiInene) to boost the electrosynthesis of C6H11NO from C6H10O and nitrite, achieving a high Faradaic efficiency (47.6 %) and almost 100 % yield under ambient conditions. In situ Fourier transform infrared spectroscopy and theoretical calculations demonstrate that unconventional orbital hybridization between d-block metals and p-block metals could regulate the local electronic structure of active sites and induce electron localization of electron-rich Pd sites, which tunes the active hydrogen supply, facilitates the generation and enrichment of key intermediates NH2OH* and C6H10O*, and efficiently promotes their C-N coupling to selectively produce C6H11NO.

Tailoring the peroxidase-like properties of Mo atom nanoclusters/N-MXene nanozymes for sensitive colorimetric detection of glutathione

Although nanozyme engineering has made tremendous progress, there is a huge gap between them and natural enzymes due to the enormous challenge of precisely adjusting the geometric and electronic structure of active sites. Considering that intentionally adjusting the metal-carrier interactions may bring the promising catalytic activity, in this work, a novel Mo atom nanocluster is successfully synthesized using nitrogen-doped Mxene (MoACs/N-MXene) nanozymes as carriers. The constructed MoACs/N-MXene displays excellent peroxidase-like catalytic activity and kinetics, outweighing its N-MXene and Mo nanoparticles (NPs)-MXene references and natural horse radish peroxidase. This work not only reports a successful example of MoACs/N-MXene nanozyme as a guide for achieving peroxidase-mimic performance of nanozymes for colorimetric glutathione sensing at 0.29 μM, but also expands the application prospects of two-dimensional MXene nanosheets by reasonably introducing metal atomic clusters and nonmetal atom doping and exploring related nanozyme properties.

Engineering the Active Sites of MOF‐derived Catalysts: From Oxygen Activation to Activate Metal‐Air Batteries†

Comprehensive SummaryThe electrochemical processes of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play a crucial role in various energy storage and conversion systems. However, the inherently slow kinetics of reversible oxygen reactions present an urgent demand for the development of efficient oxygen electrocatalysts. Recently, metal‐organic framework (MOF) derivatives have attracted extensive attention in electrocatalysis research due to their unique porous structure, abundant active sites, and tunable structural properties. Especially, the optimization of the electronic structure of active sites in MOF derivatives has been proven as an effective strategy to enhance the catalytic activity. In this review, we provide an overview of the electronic structure optimization strategies for active sites in MOF derivatives as advanced catalysts in various O—O bond activation reactions, including the construction of synergistic effects between multiple sites, the development of heterogeneous interfaces, the utilization of metal support interactions, and the precise modulation of organic ligands surrounding catalytic active sites at the atomic level. Furthermore, this review offers theoretical insights into the oxygen activation and catalytic mechanisms of MOF derivatives, as well as the identification of active sites. Finally, the potential challenges and prospects of MOF derivatives in electrocatalysis are discussed. This review contributes to the understanding and advancement of efficient oxygen electrocatalysis in energy systems. Key Scientists

Porous TiN-based ceramic electrode with N-modified Co-based Nanorods/TiN heterointerfaces for efficient overall water splitting

The development of high-performance electrocatalytic electrodes for overall water splitting is a crucial issue to realize renewable hydrogen production. This paper presents the in situ growth of N-modified Co-based nanorods on porous TiN ceramic membranes using the hydrothermal method and thermal NH3 treatment, resulting in a novel self-supported electrocatalytic electrode with abundant heterointerfaces, denoted as NCTN-x-y (x: nitridation temperature; y: nitridation time). In the alkaline medium (1 M KOH), the NCTN-350-2 electrode displays the best hydrogen evolution reaction (HER) activity (ƞ10 = 66 mV), and the NCTN-250-3 electrode manifests the best oxygen evolution reaction (OER) performance (ƞ10 = 270 mV). Accordingly, these two electrodes comprise an electrolyzer, which features a current density of 10 mA cm−2 at a low cell voltage of 1.63 V. The good electrocatalytic performance can be attributed to the abundant heterointerfaces formed between the porous TiN ceramic membrane and the N-modified Co-based nanorods, in conjunction with the hierarchical pore structure of the TiN ceramic membrane. Theoretical calculations identify that the construction of heterointerfaces modulates the electronic structure of active sites, thereby promoting the dissociation of H2O, optimizing the H* adsorption energy (ΔGH*), and accelerating the reaction kinetics, which ultimately improve the electrocatalytic activity of electrode.

Modulating electronic structure of active sites on iron-based nanoparticles enhances peroxymonosulfate activation

Herein, iron-based nanoparticle catalysts with heteroatoms anchored on nitrogen-doped carbon layers were constructed and applied to peroxymonosulfate (PMS) activation for antibiotic degradation. Results showed that S doping was beneficial to PMS activation, while P doping reduced the activation efficiency. The S-doped catalysts achieved 100% removal of sulfamethoxazole (SMX) within 15 min with a normalized rate constant of 130.4 min−1 M−1. Electron paramagnetic resonance and scavenging tests proved that high-valent iron-oxo species (HV-FeO) and singlet oxygen (1O2) mediated non-radical oxidation dominated the SMX degradation. Theoretical calculations and experiments elucidated that the electron-rich S atom donated electrons during PMS activation, which changed the valence state of Fe and enhanced the adsorption energy to PMS (Eads = −11.219 eV), resulting in excellent catalytic activity. This work elucidated the effects of heteroatoms on the electronic structure of active site in nanoparticles and provided guidance for the development of advanced catalysts for PMS activation.

Ni─Co─O─S Derived Catalysts on Hierarchical N-doped Carbon Supports with Strong Interfacial Interactions for Improved Hybrid Water Splitting Performance.

Simultaneously improving electrochemical activity and stability is a long-term goal for water splitting. Herein, hierarchical N-doped carbon nanotubes on carbon nanowires derived from PPy are grown on carbon cloth, serving as a support for NiCo oxides/sulfides. The hierarchical electrodes annealed in N2 or H2/N2 display improved intrinsic activity and stability for hydrogen evolution reaction (HER) and glucose oxidation reaction. Compared with Pt/C||Ir/C in alkaline media, the glucose electrolysis assembled with electrodes exhibits a cell voltage of 1.38V at 10mAcm-2, durability for >12h at 50mAcm-2, and resistance to glucose/gluconic acid poisoning. In addition, electrocatalysts can also be applied in ethanol oxidation reactions. Systematic characterizations reveal the strong interactions between NiCo and N-doped carbon support-induced partial charge transfer at the interface and regulate the local electronic structure of active sites. Density functional theory calculations demonstrate that the synergistic effect between N-doped carbon supports, metallic NiCo, and NiCo oxides/sulfides optimize the adsorption energy of H2O and the H* free energy for HER. The energy barrier of the dehydrogenation of glucose effectively decreased. This work will attract attention to the role of metal-support interactions in enhancing the intrinsic activity and stability of electrocatalysts.

Coordination Environment Engineering to Regulate the Adsorption Strength of Intermediates in Single Atom Catalysts for High-performance CO2 Reaction Reduction.

The modulation of the coordination environment of single atom catalysts (SACs) plays a vital role in promoting CO2 reduction reaction (CO2RR). Herein, N or B doped Fe-embedded graphyne (Fe-GY), Fe-nXGYm (n = 1, 2, 3; X = N, B; m = 1, 2, 3), are employed as probes to reveal the effect of the coordination environment engineering on CO2RR performance via heteroatom doping in SACs. The results show that the doping position and number of N or B in Fe-GY significantly affects catalyst activity and CO2RR product selectivity. In comparison, Fe-1NGY exhibits high-performance CO2RR to CH4 with a low limiting potential of -0.17V, and Fe-2NGY3 is demonstrated as an excellent CO2RR electrocatalyst for producing HCOOH with a low limiting potential of -0.16V. With applied potential, Fe-GY, Fe-1NGY, and Fe-2NGY3 exhibit significant advantages in CO2RR to CH4 while hydrogen evolution reaction is inhibited. The intrinsic essence analysis illustrates that heteroatom doping modulates the electronic structure of active sites and regulates the adsorption strength of the intermediates, thereby rendering a favorable coordination environment for CO2RR. This work highlights Fe-nXGYm as outstanding SACs for CO2RR, and provides an in-depth insight into the intrinsic essence of the promotion effect from heteroatom doping.

Theory-guided design of S-doped Fe/Co dual-atom nanozymes for highly efficient oxidase mimics.

The advent of dual-atom nanozymes (DAzymes) featuring distinctive bimetallic active sites garnered significant attention, representing enhanced iterations of conventional single-atom nanozymes. The quest for an effective and universal strategy to modulate the catalytic activity of DAzymes posed a formidable challenge, yet few published reports addressed this. Herein, we designed and synthesized S-doped Fe/Co DAzymes (S-FeCo-NC) under theoretical guidance and revealed their excellent oxidase-like activity. Experimental and theoretical calculations indicated that the superior oxidase-like activity exhibited by S-FeCo-NC was attributed to the S-doping, which modulated the local electronic structure of the dual-atom active site. This modulation of the local electronic structure significantly optimizes oxygen adsorption energy, thereby accelerating the rate of enzyme-catalyzed reactions. As a proof-of-concept, this study integrated S-FeCo-NC with the cascade inhibition reaction of acetylcholinesterase (AChE) to devise a sensitive analytical platform for detecting organophosphorus pesticides. This study paved the way for elucidating the correlation between the local electronic structure of the active site and enzyme activity, offering novel methodologies and insights for the rational design of DAzymes.

Spin states of metal centers in electrocatalysis.

Understanding the electronic structure of active sites is crucial in efficient catalyst design. The spin state, spin configurations of d-electrons, has been frequently discussed recently. However, its systematic depiction in electrocatalysis is lacking. In this tutorial review, a comprehensive interpretation of the spin state of metal centers in electrocatalysts and its role in electrocatalysis is provided. This review starts with the basics of spin states, including molecular field theory, crystal field theory, and ligand field theory. It further introduces the differences in low spin, intermediate spin, and high spin, and intrinsic factors affecting the spin state. Popular characterization techniques and modeling approaches that can reveal the spin state, such as X-ray absorption microscopy, electron spin resonance spectroscopy, Mössbauer spectroscopy, and density functional theory (DFT) calculations, are introduced as well with examples from the literature. The examples include the most recent progress in tuning the spin state of metal centers for various reactions, e.g., the oxygen evolution reaction, oxygen reduction reaction, hydrogen evolution reaction, carbon dioxide reduction reaction, nitrogen reduction reaction, nitrate reduction reaction, and urea oxidation reaction. Challenges and potential implications for future research related to the spin state are discussed at the end.

Constructing NiSe2/MoSe2 Mott–Schottky Heterojunctions Onto N‐doped Brain Coral‐Carbon Spheres by Phase Separation Strategies for Advanced Energy Conversion Applications

AbstractConstructing Mott–Schottky heterojunctions in nanohybrids is an effective strategy for facilitating electron transfer and optimizing the electronic structure of active sites; however, challenges remain. Herein, a selenium‐induced phase separation strategy is proposed and successfully construct NiSe2/MoSe2 Mott–Schottky heterojunctions on N‐doped brain coral carbon nanospheres (N‐BCCSs). Owing to built‐in electric fields, optimized electronic density, and unique nanoflake/sphere structures, the designed NiSe2/MoSe2@N‐BCCSs carbon‐based Mott–Schottky catalysts achieved satisfactory electrocatalytic performance. When serving as a counter electrode for the triiodide reduction reaction (IRR), a power conversion efficiency of 8.49% is obtained, which outperformed that of conventional Pt electrodes (7.80%). When the NiSe2/MoSe2@N‐BCCSs are used as electrocatalysts for the hydrogen evolution reaction (HER), their overpotential (η10) is as low as 119 mV, which is significantly better than that of other transition‐metal selenides. This research demonstrates a new concept for constructing Mott–Schottky heterojunctions and provides a new direction for investigating multifunctional carbon‐based composites.

Immobilizing Bimetallic RuCo Nanoalloys on Few-Layered MXene as a Robust Bifunctional Electrocatalyst for Overall Water Splitting.

Doping Co atoms into Ru lattices can tune the electronic structure of active sites, and the conductive MXene can adjust the electrical conductivity of catalysts, which are both favorable for improving the electrocatalytic activity of the catalyst for water splitting. Here, ruthenium-cobalt bimetallic nanoalloys coupled with exfoliated Ti3 C2 Tx MXene (RuCo-Ti3 C2 Tx ) have been constructed by ice-templated and thermal activation. Due to the strong interaction between the RuCo nanoalloys and conductive MXene, RuCo-Ti3 C2 Tx not only exhibits an excellent hydrogen evolution reaction (HER) performance with a low overpotential and Tafel slope (60 mV, 34.8 mV dec-1 in 0.5 M H2 SO4 and 52 mV, 38.7 mV dec-1 in 1 M KOH), but also good oxygen evolution reaction (OER) performance in an alkaline electrolyte (266 mV, 111.1 mV dec-1 in 1 M KOH). The assembled RuCo-Ti3 C2 Tx ||RuCo-Ti3 C2 Tx electrolyzer requires a lower potential (1.56 V) than does the Pt/C||RuO2 electrolyzer at 10 mA cm-2 . A boosted catalytic HER activity from immobilizing the RuCo nanoalloys on MXene was unveiled by density functional theory calculations. This study provides a feasible and efficient strategy for developing MXene-based catalysts for overall water splitting.

Overlooked role of void-nanoconfined effect in emerging pollutant degradation: Modulating the electronic structure of active sites to accelerate catalytic oxidation

The efficient removal of emerging pollutant from water is the ultimate frontiers of advanced oxidation processes (AOPs), yet it is challenging to obtain higher catalytic activity and oxidation rate. Herein, a sustainable solution was proposed by optimizing the curvature of confined structure to modulate the electronic state of the active sites in nanochannels for improving the catalytic activity. In addition, the confined effect can enhance the oxidation rate by shorting the mass transfer of active species and pollutants. A void-nanoconfined nanoreactor was prepared by loading Fe2O3 into the nanochannels (<5 nm) of the hollow carbon sphere. An enhancement of 3 orders of magnitude was obtained in the degradation rate constant of void-nanoconfined catalytic system toward sulfamethoxazole (SMX) (6.25 min−1) compared with the non-confined system. The kinetics enhancement was attributed to the larger electron potential difference between the outer and inner nanochannel caused by the curvature increase of carbon sphere, accelerating the electron transfer, so that the energy barrier of SMX degradation reaction was reduced by 31 kcal/mol with the assistance of confinement energy. Importantly, the NC-IN/PDS system exhibited outstanding removal efficiency for the actual river water using a continuous flow reactor. This work provides a new insight into designing an efficient and stable catalytic nanoreactor, enriching the domain of advanced wastewater treatment strategies.