Effect Of Nitrogen Doping Research Articles

Monolithic Nitrogen-Doped Carbon Electrode with Hierarchical Porous Structure for Efficient Electrochemical CO2 Reduction.

N-doped carbon materials have garnered extensive development in electrochemical CO2 reduction due to their abundant sources, high structural plasticity, and excellent catalytic performance. However, the use of powder carbon materials for electrocatalytic reactions limits their current density and mechanical strength, which pose challenges for industrial applications. In this study, we synthesized a monolithic N-doped carbon electrode with high mechanical strength for efficient electrochemical reduction of CO2 to CO through a simple pyrolysis method, using phenolic resin as the precursor and ZIF-8 as the sacrificial template. At 900 °C, the decomposition of ZIF-8 and the volatilization of Zn atoms promote the formation of a hierarchical porous structure in the carbon matrix, characterized by macropores with extended mesoporous channels. Simultaneously, N active species derived from ZIF-8 are effectively generated around the pores and fully exposed. The efficient mass transfer facilitated by the hierarchical porous structure and high activity of exposed nitrogen species enables efficient conversion of CO2 to CO. When the ZIF-8 content is 30%, the catalyst achieves a Faradaic efficiency of 88.9% for CO at a low potential of -0.7 V (vs RHE), with a CO production rate of 244.05 μmol h-1 cm-2. After 50 h of potentiostatic electrolysis, the current density and FECO remain stable. This work not only provides a strategy for the synergistic effects of hierarchical porous structures and nitrogen doping but also offers an effective method to avoid using powder binders and prepare integrated, stable monolithic electrodes.

Improving the Efficiency of Luminescent Zn(II)-Modified N-Doped GOQD Nanomaterials in Parkinson's Disease Treatment: A Theoretical Mechanistic Framework Exploring Doping Effect.

Levodopa, a widely prescribed drug in Parkinson's disease treatment, stands as the foremost prodrug of dopamine. An affordable self-testing kit is utilized to monitor levodopa content in anti-parkinson drugs in human serum. A photoluminescent trinuclear Zn(II) complex [Zn3(L)2(κ1-OAc)2(κ2-OAc)2] has been synthesized, which cleaves into mononuclear ZC in aqueous solution. ZC was found to detect L-Dopa in Tris-HCl buffer, exhibiting a moderate decrease in PL-emission. The real-life utility of the ZC probe is limited, for its lower sensitivity (LOD 35.3 μM) and separation challenges. Therefore, an interface between homogeneous and heterogeneous supports has been explored, leading to the strategic development of NGOZC, where ZC was grafted onto NGOQD (Graphene oxide quantum dots). This material enables naked- eye detection under both ambient and UV light with color change from bright cyan to green, followed by dark. The nitrogen doping effect was investigated by several comparative investigations involving the synthesis of ZC-grafted GOQD, leading to enhanced quenching performance. Steady-state and time-resolved fluorescence titration study, morphological analysis, and computational calculations have been performed to get insights into the sensing mechanism. To the best of our knowledge, this as-synthesized NGOZC (LOD 1.78 nM) represents a promising strategy and platform for applications in biosensors, especially for Parkinson's and Alzheimer's diseases.

Synergistic magnetic Cu-Fe catalysts on N-doped biochar for efficient alkali lignin catalytic depolymerization into monophenols

Alkali lignin, a major by-product of papermaking, poses disposal challenges, hindering the full valorization of lignocellulose in sustainable biorefineries. One-pot lignin catalytic depolymerization (LDP) in water offers a promising route for producing valuable phenolic compounds. This study reports the successful synthesis of in-situ N-doped biochar supported CuxFey catalysts (CuxFey/N-BC) via a one-step carbothermal reduction method, enabling LDP in water without the need for external hydrogen, additives, alcohol solvent, or co-catalysts. Notably, the Cu5Fe1/N-BC could achieve remarkable catalytic performance under mild reaction conditions (280 °C, 6 h, 18 mL water), yielding 80.84±2.23 mg/g of monophenol, 56.17±1.32 % of bio-oil, and a lignin conversion rate of 80.66±0.73 %. This significantly surpassed the performance of monometallic catalysts and bare biochar. The synergistic effects of intermetallic interactions and nitrogen doping were proposed to create abundant active sites and rich pore structures, promoting efficient LDP reactions. Furthermore, the Cu5Fe1/N-BC exhibited excellent recyclability, with minimal activity loss (2.79 %) per cycle, due to its strong magnetism and favorable interactions. Mechanism investigation revealed that the Cu5Fe1/N-BC efficiently cleaved the C-O and C-C bonds in lignin, and led to the targeted production of guaiacyl phenols. This study provides valuable insights and practical strategy for valorizing lignin into valuable chemicals, advancing its utilization in various applications.

Enhanced removal of lead ions from wastewaters by electrochemical adsorption using nitrogen-doped Ti3C2Tx MXene

As a two-dimensional material containing transition metal carbides and nitrides, MXene is often used in capacitive deionization for its excellent hydrophilic and pseudocapacitive properties. Nitrogen doping is widely used to improve the adsorption properties of certain materials. However, the effect of nitrogen doping on the electrochemical adsorption properties of MXene remains unclear. In this work, nitrogen-doped Ti3C2Tx MXene was synthesized using a simple hydrothermal method to achieve highly selective and efficient removal of Pb(II) at a constant cell voltage. The concentration of Pb(II) decreased from 4.95 to 0.02 mg L−1 in a 100 mg L−1 NaCl supporting electrolyte after electrosorption. The removal efficiency of Pb(II) reached 99.5%, whereas it was only 15.2% for Na+. The introduction of nitrogen functional groups increased the electrical conductivity and layer spacing of MXene, thereby improving the pseudocapacitive adsorption performance in the presence of Pb(II). The complexation function of the Ti-OH group on nitrogen-doped Ti3C2Tx surface increased and contributed to the selective adsorption of Pb(II). The removal efficiency of Pb(II) increased with increasing solution pH and cell voltage, reaching the maximum value at pH 5.0 and 1.5 V, respectively. The effect of supporting electrolyte type on the removal of Pb(II) was negligible. In addition, the removal efficiency for mixed heavy metal ion solutions, including Cu(II), Ni(II), and Pb(II), exceeded 79.0%. It exhibited the highest removal efficiency for Pb(II) at 97.9%. After five cycles of electrochemical adsorption–desorption, the nitrogen-doped Ti3C2Tx maintained a stable Pb(II) removal efficiency of 97.0%. This work provides a promising material for the electrochemical removal of low-concentration heavy metal ions from wastewaters.

Combined experimental and density functional theory approaches to address different mechanisms of nitrogen and sulfur doping on the enhancement of capacitive performance of hierarchical porous biochars

Activated carbon derived from biomass as hierarchical porous biochars (HPB) has been developed as electrode materials for supercapacitors. Nitrogen is known as the doping element that enhances quantum capacitance, but the mechanisms of sulfur doping on the quantum capacitance enhancement remain ambiguous. In this study, conventional approaches to assess the characteristics and capacitive performance of biochars were combined with density functional theory (DFT) calculations to assess different mechanisms of nitrogen and sulfur doping. The Bbiochar samples were prepared from the pyrolyzed fish bone powder at 800 °C without additional doping possessed a specific capacitance of 240 F g−1 at 1 A/g within 1 M H2SO4. Interestingly, additional nitrogen doping through urea mixing and additional sulfur doping through thiosulfate mixing prior to the pyrolysis enhanced the specific capacitance of biochar samples to exceed 400 F g−1 under the same condition. The urea mixed sample possessed low porosity but high charge transfer resistance, while the thiosulfate mixed sample possessed high porosity but low charge transfer resistance. The different underlying mechanisms were discussed through DFT calculations on graphene models designed based on the x-ray photoelectron spectroscopy (XPS) results. Nitrogen-doped configurations with topological defects mainly stored charge at the dangling atoms and possessed a relatively high quantum capacitance. Meanwhile, doped configurations of oxidized sulfur groups required relatively low formation energy and possessed large bond dipoles, corresponding to larger pore size and surface area of the thiosulfate mixed biochars. Understanding the contrary between effects of nitrogen and sulfur doping could resolve the bottleneck on enhancing the performance of electronic double layer supercapacitors.

Synergic Effects of Chemical Reduction and Nitrogen Doping on the Structural and Electrical Properties of N‐ZnO/N‐rGO Nanostructures

Synergic Effects of Chemical Reduction and Nitrogen Doping on the Structural and Electrical Properties of N‐ZnO/N‐rGO Nanostructures

Hierarchically porous carbon foams coated with carbon nitride: Insights into adsorbents for pre-combustion and post-combustion CO2 separation

Adsorption is fundamental to many industrial processes, including separation of carbon dioxide from other gases in pre- or post-combustion gas mixtures. Adsorbents should have high capacity and selectivity, which are both intimately linked with surface area, pore size distribution, and surface energy. Porous carbons are cheap and scalable adsorbents, but greater understanding of how their textural properties and surface chemistry affects their performance is needed. Here, we investigate the effect of nitrogen doping on CO2 adsorption. Microporous carbon foams with large surface area (>2500 m2 g−1) and pore volume (1.6 cm3 g−1) are synthesized, then coated with varying amounts of carbon nitride (up to 17 at% nitrogen) to achieve high CO2 uptake (25.5 mmol g−1) and selectivity (CO2:N2 = 21), whilst also giving insights into the relationship between structure and function. At low pressure (relevant to post-combustion capture), moderate carbon nitride loading leads to enhanced uptake and selectivity by combining large ultramicropore volume with the introduction of Lewis base sites, leading to high isosteric heat of adsorption. Higher carbon nitride loading further increases selectivity but lowers uptake by blocking micropores. Conversely, at high pressure (relevant to pre-combustion capture) the uncoated carbon foam displays superior uptake, because mesoporosity is the dominant factor in this regime, rather than the presence of ultramicropores. Finally, the samples displayed excellent regeneration under repeated adsorption–desorption cycles, and breakthrough curves were measured. These results underscore the delicate balance required for optimal material design when applying porous carbon adsorbents to CO2 separation processes. Moving forward, improved adsorbents will contribute to the proliferation of carbon capture and storage (CCS) and carbon capture and utilisation (CCU) technologies, ultimately contributing reduced anthropogenic CO2 emissions.

Crystal and band structures of N-doped Ti3O5 coatings: Experiments and first-principles calculations

N-doped α-phase Ti3O5 has received limited attention in both theoretical and experimental studies compared to N-doped TiO2. This work focuses on the production and analysis of N-doped Ti3O5 coatings, which can be facilely produced using air-based sputtering. First-principles calculations were employed to investigate the crystal and band structures of N-doped Ti3O5. The results revealed that substitutional nitrogen doping within the investigated range preserved the orthorhombic structure of Ti3O5. As the N-doping concentrations increased, Ti3O5 exhibited a transition from metallic to semiconducting characteristics, confirmed by the density of states and refined band calculations. The calculated bandgaps in the semiconductor regime aligned well with the limited experimental results, demonstrating the pronounced narrowing effect of nitrogen doping. Integrating these calculations with experimental findings enhances the understanding of the crystalline and physical properties of N-doped Ti3O5 coatings.

New insights into the role of nitrogen doping in microporous carbon on the capacitive charge storage mechanism: From ab initio to machine learning accelerated molecular dynamics

Fundamental understandings of the relationship between ion-electrode interaction and structural feature in porous carbon electrodes at a molecular level provides guidelines for the design of high-performance electric double layer supercapacitors. It is certified by experiments that porous carbon structures doped with nitrogen show enhanced capacitive performance. However, in the theoretical simulations, the fundamental charge storage mechanism is still elusive. In particular, the recent experimental result shows that the generally ignored nitrolic nitrogen (N5) in porous carbon exhibits a positive effect on capacitance, while graphitic nitrogen (N3) does the opposite, which is against with the simulation results based the 2D-modeled porous graphene structure. Here, we perform ab initio molecular dynamics simulations on the N3 and N5-doped carbon/electrolyte interfaces, including both 2D planar and 3D microporous carbon electrodes. Our calculation indicates that N3 in the 3D pore hinders the electrolyte transport, while N5-doped micropore still serves as an electrolyte transport channel through the formation of H-bond. The charge storage mechanism is further elucidated by the analysis of the well equilibrated interfaces obtained from the machine learning force field accelerated molecular dynamics. Our work provides a new insight into the effect of nitrogen doping in 3D porous carbon, which is exactly opposite to the 2D planar graphene. Therefore, we emphasize that differences in the electrochemical conditions of 2D planar and 3D microporous carbon electrodes should be fully considered when analyzing the effects of surface chemistry on charge storage mechanisms.

N-doped carbon achieved by pyrolyzing urea and active carbon for the capacitive deionization coupled PMS oxidation system

Tetracyclines are among the most widely used antibiotics, and the saline organic wastewater generated during their production has caused serious environmental problems. Thus, it is imperative to develop effective methods for treating this antibiotic wastewater. In this study, we examined the structural characteristics and electrochemical performance of nitrogen-doped carbon materials and assessed the effects of nitrogen doping on the performance of a peroxymonosulfate (PMS)-coupled membrane capacitive deionization (MCDI) system for removing tetracycline (TC) and salt. Having optimized the carbonization temperature and system operating parameters, we observed that in response to an increase in carbonization temperature, there was an increase in the abundance of surface functional groups in the material, which promoted the ion migration capacity of the electrode and PMS activation sites. In addition, we observed that nitrogen doping can alter the electrical properties of carbon materials, provide a larger number of adsorption sites, and enhance the interactions between carbon structures and salt ions, thereby improving material properties. Under optimal operating conditions, the salt adsorption and tetracycline removal rates reached 30.2 % and 61.8 %, respectively. Our findings in this study provide a feasible method for the treatment of saline tetracycline wastewater.

Effect of Nitrogen Doping on the Photocatalytic Properties and Antibiofilm Efficacy of Reduced TiO2 Nanoparticles.

Nanomaterial-mediated antibacterial photodynamic therapy (aPDT) emerges as a promising treatment against antibiotic-resistant bacterial biofilms. Specifically, titanium dioxide nanoparticles (TiO2 NPs) are being investigated as photosensitizers in aPDT to address biofilm related diseases. To enhance their photocatalytic performance in the visible spectral range for biomedical applications, various strategies have been adopted, including reduction of TiO2 NPs. However, despite improvements in visible-light photoactivity, reduced TiO2 NPs have yet to reach their expected performance primarily due to the instability of oxygen vacancies and their tendency to reoxidize easily. To address this, we present a two-step approach to fabricate highly visible-light active and stable TiO2 NP photocatalysts, involving nitrogen doping followed by a magnesium-assisted reductive annealing process. X-ray photoelectron spectroscopy analysis of the synthesized reduced nitrogen-doped TiO2 NPs (H:Mg-N-TiO2 NPs) reveals that the presence of nitrogen stabilizes oxygen vacancies and reduced Ti species, leading to increased production of reactive oxygen species under visible-light excitation. The improved aPDT efficiency translates to a 3-fold enhancement in the antibiofilm activity of nitrogen-doped compared to undoped reduced TiO2 NPs against both Gram-positive (Streptococcus mutans) and Gram-negative (Porphyromonas gingivalis, Fusobacterium nucleatum) oral pathogens. These results underscore the potential of H:Mg-N-TiO2 NPs in aPDT for combating bacterial biofilms effectively.

Examining the dual effect of copper nanoparticles and nitrogen doping on Cu@N-TiO2

Abstract The study of six compositions of Cu@N-TiO2 with different amounts of copper and nitrogen synthesized using a sol–gel method is reported. X-ray diffraction patterns and Raman spectra indicated the formation of a single anatase TiO2 phase in all materials without evidence of secondary phases including copper or nitrogen. Electron microscopy images showed a homogeneous distribution of the copper particles around a TiO2 matrix, just as that the insertion of nitrogen did not have a significant effect on the morphology of the particles. X-ray photoelectron spectroscopy analysis confirmed that nitrogen was inserted in the atomic arrangement of titanium dioxide, while copper was presented mainly as metallic element on the TiO2 surface. Characterization of the optical properties and photoactivity test confirm that band gap strongly depends on the copper and nitrogen content phenomenon attributed to the combined presence of modifiers over the TiO2 surface and the promotion of a plasmonic effect, which displaced the absorption UV bands to higher wavelengths with respect to un-doped TiO2. The catalytic test performed using rhodamine-B as probe molecule, confirm that TiCuN2 and TiCuN3 samples exhibit the best decomposition percentages of 38 and 36 % respectively. Such results confirm the surface plasmon resonance effect associated to Cu particles on the TiO2 as main cause in the increase in current along synthesized samples and the use of cyclic voltammetry technique to identify these effects between 0.0 and 1.5 V.

Correction to “Effect of Nitrogen Doping and Oxygen Vacancy on the Oxygen Reduction Reaction on the Tetragonal Zirconia(101) Surface”

Correction to “Effect of Nitrogen Doping and Oxygen Vacancy on the Oxygen Reduction Reaction on the Tetragonal Zirconia(101) Surface”

Mild modification of sponge-like carbon: Ammonia post-treatment for enhanced CO2 adsorption and suitability for supercapacitors

During the synthesis of carbon-based CO2 adsorbents and supercapacitors, the introduction of nitrogen atoms into the carbon matrix has been identified as a means to enhance their performance. Nevertheless, the intricate effects of nitrogen doping on material properties pose a significant challenge in developing efficient methodologies. In this investigation, porous carbons resembling sponges were fabricated utilizing macadamia nut shells as a precursor and a dual salt comprising K2C2O4-KCl as an activating agent. Subsequent modification of the materials through ammonia post-treatment facilitated the production of nitrogen-doped porous carbon. The alterations in surface characteristics and pore morphology after ammonia treatment were meticulously examined to unravel the underlying mechanism of this modification process. The samples under scrutiny showcased remarkable CO2 adsorption capacities, peaking at 6.97 mmol/g at 0 °C and 4.65 mmol/g at 25 °C. Employing mathematical models to probe the influence of pore structure and surface properties on CO2 adsorption efficacy proved to be fruitful. A linear correlation was established to depict CO2 adsorption behavior, underscoring the joint impact of ultramicropore volume and nitrogen content on the adsorption process. Notably, the material exhibited a specific capacitance of 290.4F/g at a current density of 0.5 A/g within a three-electrode configuration, demonstrating commendable rate capability and cyclic stability. The pivotal findings from this inquiry emphasize that ammonia post-treatment represents a gentle modification strategy exerting minimal influence on the pore architecture, thereby efficaciously enhancing both CO2 adsorption and electrochemical performance.

Synergistic effect of pore generation and nitrogen doping on the enhanced CO2 capture and selectivity of carbon nanofibers

The porosity and heteroatom doping of carbon materials are crucial for their adsorption capacity and selectivity toward CO2. Herein, nitrogen-doped microporous carbon nanofibers (CNFs) were prepared by carbonizing electrospun polyacrylonitrile (PAN) nanofibers, using nitrogen-rich polyvinylpyrrolidone (PVP) as porogen and nitrogen source simultaneously. The synergistic effect of pore generation and nitrogen doping improved the porosity and preserved a substantial nitrogen content in the CNFs. Compared to the nitrogen-free polyethylene glycol (PEG) porogen, the incorporation of PVP can facilitate nitrogen doping during the carbonization process. With an increasing amount of PVP addition, the specific surface area of the CNFs significantly expanded to 410 m2/g, maintaining a high nitrogen content of 10.32 wt%. The porosity and nitrogen functionalities (Pyridinic N and pyrrolic N) collaborated synergistically in determining CO2 adsorption capacity, with elevated nitrogen content resulted in improved selectivity. The CNFs exhibited remarkable IAST CO2/N2 (10:90) selectivity of 38 and cycling stability, demonstrating their potential for long-term practical applications. This work provides unique inspiration for the design of porous nanofibers with exceptional CO2 adsorption capacity and selectivity.

Nitrogen‐containing microporous carbon with specific morphology for non‐metallic catalytic NO oxidation at room temperature: The effect of morphology and nitrogen doping

AbstractThe optimization of the gas diffusion path and surface coordination environment through morphology control can improve the intrinsic activity of the catalyst in NO oxidation reactions. Microporous nanosheets, nanowires, and spheres of carbon were constructed using resorcinol and formaldehyde as carbon sources, melamine as nitrogen source, and graphene oxide or carbon nanowires as structure‐directing agents to reveal the effects of morphology and nitrogen‐doping on NO oxidation activity at room temperature. With the increase of coating thickness, the ultramicroporous structure becomes pronounced and the nitrogen content increases, which contribute to the improvement of steady‐state NO conversion. The 2D microporous nanosheets (TDC‐200) with sheet structure shows prominent diffusion and adsorption capability than 1D nanowires and sphere, which shortens the gas diffusion path and enhances the efficient utilization of ultramicropores, thereby presenting the highest NO oxidation activity of 78.4% at room temperature. The results of DFT calculations further demonstrate that doping of nitrogen atoms could significantly reduce the (2NO + O2)ads energy barrier and accelerate the reaction. This study provides a deeper understanding of the NO oxidation on non‐metallic catalyst.

Nanoindentation and relaxation behavior of nitrogen doped zirconium based bulk metallic glass

In this paper, the effect of nitrogen doping on the mechanical properties of Zr-based bulk metallic glasses (BMGs) was studied by nano indentation experiment, and the correlation mechanism between microstructure evolution and mechanical properties was analyzed. The results show that the serrations events exhibited by metallic glasses during nanoindentation are related to the loading rates. With the decreasing loading rate, more obvious serrations events occur in the loading segment, which is attributed to the sufficient time for shear bands to multiply and propagate at low rates. The addition of nitrogen will induce the generation of more flow defects. Compared with BMGs without nitrogen, the nitrogen-doped Zr-based BMGs exhibit more serration events due to introducing more flow defects to form the shear transformation zones (STZs) and subsequently facilitating the shear bands to multiply. The possible relationships between the structural evolution, shear band initiation and propagation, and relaxation behavior of nitrogen doped and non doped metallic glasses were discussed.

Structure – Catalytic Behavior Relationships in TiO2-Carbon Composite Supported Pt Electrocatalysts: A Case Study

Composite types of supports made of TiO2 and carbonaceous materials provide higher stability for the Pt electrocatalysts under the working conditions of polymer electrolyte membrane fuel cells than the traditional carbon supports. We have demonstrated in our previous work that composites with general formula of 75 wt.% Ti(1-x)MoxO2-25 wt.% C (x = 0–0.2; C = traditional Black Pearls (BP) carbon) were promising supports which provided increased stability for the Pt electrocatalysts. In this study, the effect of nitrogen doping of the carbonaceous component of the composite was explored. 75 wt.% TiO2-25 wt.% carbon composite supports were prepared using graphite oxide (GO), N-doped GO and N-doped multilayer graphene. Electrocatalysts were made by loading the supports with 20 wt.% Pt. The systems were compared based on their physicochemical properties determined by low-temperature nitrogen adsorption, X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and conductivity measurements. The activity of the catalysts was investigated by conventional methods in a 3-electrode electrochemical cell. The results of various characterization methods contributed to the understanding of the difference in the electrochemical properties of N-free and N-containing catalyst samples. While GO was favorable for this composite supported catalyst, its N-doping strongly influenced the growth of TiO2, forming an almost continuous coating of small TiO2 crystals. This quasi-insulating TiO2 layer between the Pt catalytic sites and the conductive part of the composite resulted in poor electrochemical activity. Mixing the sample with carbon improved its conductivity, which resulted in a significant increase in the oxygen reduction activity.

Effect of nitrogen doping on characteristics of SiTe Ovonic threshold switch for selectors

In this study, the effect of nitrogen doping on silicon telluride (SiTe) chalcogenide materials has been investigated to enhance the performance of the Ovonic threshold switch (OTS) selector devices especially on the off-current density to reduce sneak current. The nitrogen doped SiTe (N–SiTe) device demonstrates significant improvement in selector performance including low off-current (18 nA) and low off-current density (3.4 × 10−4 kA/cm2) resulting in high selectivity (5.5 × 104), low power operation at threshold voltage of 0.96 V, enhanced voltage window (0.24 V), fast switching with slope of < 2.97 mV/dec and potentially fast pulse response/switching speed. Besides, analyses by Raman and X–ray photoelectron spectroscopies indicate that the nitrogen doping changes predominant orbital and bonding configuration and decreases Te lone pairs that act as traps, thus suppressing subthreshold conduction. Increased optical bandgap by nitrogen doping also results in reduced leakage current as well as higher threshold voltage. First-principles calculations reveal that localized electrons with high density near nitrogen are responsible for reduced subthreshold conduction of the chalcogenide. Our results provide new guidance in material selection by demonstrating the effect of nitrogen doping to improve OTS selector performance on an arsenic-free binary chalcogenide.

Surface-modified graphite felt incorporating synergistic effects of TiO2 decoration, nitrogen doping, and porous structure for high-performance vanadium redox flow batteries

Construction of porous surface, decoration of metal oxide, and introduction of defects are three major strategies to improve the electrocatalytic capability of graphite felt (GF) for vanadium redox flow battery (VRFB). In this study, we have successfully achieved the urea-assisted deposition of TiO2 onto GF, resulting in a synergistic effect that realizes the three modifications mentioned above, through a facile one-pot approach. During the post-annealing process, the decorated TiO2 can further undergo carbon-thermal reduction to etch the GF surface, leading to a porous surface. Additionally, the defective structures such as oxygen defects and nitrogen doping also be can simultaneously incorporated in the modified GF. As a result, the modified GF shows a dramatically improved electrocatalytic capability towards the VO2+/VO2+ redox reactions due to better hydrophilicity, larger surface area, and numerous oxygen defects. The VRFB with the modified GF electrode can deliver the coulombic efficiency (CE), voltage efficiency (VE), and energy efficiency (EE) of 95.0, 81.8, and 77.8 %, respectively, at 160 mA/cm2, which are much better than those of VRFB based on untreated GF.