Search Results (102)

Defect engineering can effectively regulate the catalytic activity of single-atom catalysts anchored on the graphene substrate. Based on graphene with topological defects consisting of 5,7-membered carbon rings, we designed and investigated twenty transition metal single-atom catalysts TM-N₄-C57 (TM = Sc~Cu, Zr~Mo, Ru, Rh, Hf~Ir) for electrocatalytic nitrogen reduction reaction (NRR) using density functional theory (DFT) calculations. Employing a screening strategy that considers binding energy, N₂ adsorption, catalytic activity, selectivity, and thermal stability, we ultimately screened out two electrocatalysts (Mo-N₄-C57 and W-N₄-C57) with excellent catalytic activity and selectivity. The NRR pathways on these two catalysts proceed through distal and consecutive pathways, with limiting potentials of −0.19 and −0.53 V for Mo-N₄-C57 and W-N₄-C57, respectively. The activity origin was elucidated through the analysis of partial density of states (PDOS) and crystal orbital Hamilton populations (COHP), suggesting that the interaction between Mo and NH₂ in the *NH₂ intermediate is relatively weak. An excellent linear relationship between U_L and ICOHP has been identified, suggesting it as a descriptor. This work provides a theoretical basis for designing efficient NRR catalysts with modified second coordination spheres. Full article

Nitrogen (N₂), constituting the majority of Earth’s atmosphere, remains indispensable for biological systems and underpins modern agriculture and industry. Traditionally, the Haber–Bosch process has been essential for synthesizing ammonia (NH₃) from N₂ under high temperature and pressure, but it contributes significantly to global CO₂ emissions. Recently, carbon-free electrocatalytic nitrogen reduction (e-NRR) has emerged as a promising, eco-friendly, and cost-effective approach for green NH₃ production under mild conditions using renewable energy, offering a sustainable alternative to the fossil fuel dependent Haber–Bosch process. This work explores NRR by contrasting the limitations of Haber–Bosch with the advantages of electrocatalysis. Despite progress, electrochemical N₂ reduction to NH₃ production remains challenging due to low activity, poor selectivity, stability, efficiency, and detection issues. Developing efficient e-NRR electrocatalysts is crucial to enhance activity, suppress hydrogen evolution reaction (HER), boost NH₃ yield, and improve Faradaic efficiency. This review highlights the role of layered double hydroxide (LDH) catalysts in e-NRR, summarizing the fundamental process, reaction pathways, and synthesis strategies. Ammonia detection methods, key metrics, and potential contamination issues are compared to inform standard NRR measurement protocols. Lastly, we summarize key findings to synthesize and improve LDH electrocatalysts for NH₃ production and a sustainable, carbon-free N₂ economy. Full article

Ammonia is an ideal candidate for clean energy in the future, and its large-scale production has long relied on the Haber–Bosch process, which operates at a high temperature and pressure. However, this process faces significant challenges due to the growing demand for ammonia and the increasing need for environmental protection. The high energy consumption and substantial CO₂ emissions associated with the Haber–Bosch method have greatly limited its application. Consequently, increasing research efforts have been devoted to developing green ammonia synthesis technologies. Among these, the electrocatalytic nitrogen reduction reaction (NRR), which uses water and nitrogen as raw materials to synthesize NH₃ under mild conditions, has emerged as a promising alternative. This method offers the potential for carbon neutrality and decentralized production when coupled with renewable electricity. However, it is important to note that the current energy efficiency and ammonia production rates of NRR under ambient aqueous conditions generally lag behind those of modern Haber–Bosch processes integrated with green hydrogen (H₂). As the core of the NRR process, the performance of electrocatalysts directly impacts the efficiency, energy consumption, and product selectivity of the entire reaction. To date, significant efforts have been made to identify the most suitable electrocatalysts. In this paper, we focus on the current research status of metal catalysts—including both precious and non-precious metals—as well as non-metal catalysts. We systematically review important advances in performance optimization, innovative design strategies, and mechanistic analyses of various catalysts. We clarify innovative optimization strategies for different catalysts and summarize and compare the catalytic effects of various catalyst types. Finally, we discuss the challenges facing electrocatalysis research and propose possible future development directions. Through this paper, we aim to provide guidance for the preparation of high-efficiency NRR catalysts and the future industrial application of electrochemical ammonia synthesis. Full article

The escalating problem of nitrate pollution, coupled with the environmental burden of the Haber-Bosch process, has spurred intense interest in the electrocatalytic nitrate reduction reaction (eNO₃RR) as a sustainable route for simultaneous wastewater treatment and ammonia production. However, the efficiency and selectivity of eNO₃RR are hampered by the multi-step proton-coupled electron transfer process and the competing hydrogen evolution reaction. This review provides a comprehensive and critical overview of recent advances in understanding and designing catalysts for eNO₃RR. We begin by elucidating the fundamental mechanisms and key reaction pathways, followed by a discussion on how critical parameters (e.g., electrolyte microenvironment, applied potential, reactor design) dictate performance. Further discussion of recent advances in catalysts, including single-metal catalysts, alloy catalysts, transition metal compounds, single-atom catalysts, carbon-based non-metal catalysts, and composite catalysts, highlights their significant roles in enhancing both the efficiency and selectivity. A distinctive feature of this review is its consistent critical assessment of catalysts through the dual lenses of practicality and sustainable development. Finally, we outline prevailing challenges and propose future research directions aimed at developing scalable and commercially viable electrocatalytic systems for green nitrogen management. Full article

The hierarchical porosity and active sites of porous carbon materials have significant impacts on the oxygen reduction reaction (ORR) process. The heteroatom-doped porous carbon materials (Z67-900, Z8-900, Z11-900, Z12-900) were synthesized by pyrolysis of ZIFs to reveal the synergistic effect of hierarchical porosity and Co-N_x sites. The structures of prepared materials were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectra, and nitrogen adsorption. The results of electrocatalytic performance show that Z67-900 has the best performance among the four materials prepared. The onset potential (E₀) of Z67-900 is close to commercial Pt/C (20%), and the half-wave potential (E_1/2) of Z67-900 is 80 mV positive than that of Pt/C in an O₂-saturated 0.1 M KOH solution (1600 rpm) with sweep rate of 5 mV·s⁻¹. Moreover, Z67-900 has better methanol resistance. The hierarchical pore structure of Z67-900 facilitates mass transfer, while the Co-N_x sites provide active catalytic centers. This study provides a solid foundation for the rational design of highly efficient ZIF-derived heteroatom-doped catalysts. Full article

The advancement of efficient energy conversion and storage technologies is fundamentally linked to the development of electrochemical systems, including fuel cells, batteries, and electrolyzers, whose performance depends on key electrocatalytic reactions: hydrogen evolution (HER), oxygen evolution (OER), oxygen reduction (ORR), carbon dioxide reduction (CO₂RR), and nitrogen reduction (NRR). Beyond catalyst design, the electrolyte microenvironment significantly influences these reactions by modulating charge transfer, intermediate stabilization, and mass transport, making electrolyte engineering a powerful tool for enhancing performance. This review provides a comprehensive analysis of how fundamental electrolyte properties, including pH, ionic strength, ion identity, and solvent structure, affect the mechanisms and kinetics of these five reactions. We examine in detail how the electrolyte composition and individual ion contributions impact reaction pathways, catalytic activity, and product selectivity. For HER and OER, we discuss the interplay between acidic and alkaline environments, the effects of specific ions, interfacial electric fields, and catalyst stability. In ORR, we highlight pH-dependent activity, selectivity, and the roles of cations and anions in steering 2e⁻ versus 4e⁻ pathways. The CO₂RR and NRR sections explore how the electrolyte composition, local pH, buffering capacity, and proton sources influence activity and the product distribution. We also address challenges in electrolyte optimization, such as managing competing reactions and maximizing Faradaic efficiency. By comparing the electrolyte’s effects across these reactions, this review identifies general trends and design guidelines for enhancing electrocatalytic performance and outlines key open questions and future research directions relevant to practical energy technologies. Full article

The catalytic activity of monolayer and bilayer boron-doped edge black phosphorene nanoribbons (BPNRs) as electrocatalysts for the nitrogen reduction reaction (NRR) was investigated using first-principles calculations based on density functional theory (DFT). The results indicate that boron incorporation facilitates effective N₂ adsorption at specific BPNR edges, thereby achieving superior NRR electrocatalytic performance. Through NRR screening criteria, six candidate edges (B@ZZ₃-1, B@ZZ₄-1, B@AC₀-1, B@ZZ₀^AA-1, B@ZZ₁^AB-3, and B@ZZ₄^AA-3) were identified. Electronic property analysis revealed that boron doping significantly reduces the bandgap of BPNRs and enhances catalytic activity by promoting electron accumulation at boron sites. Free energy pathway calculations demonstrated that B@AC₀-1, B@ZZ₀^AA-1, and B@ZZ₁^AB-3 exhibit overpotentials of 0.19 V, 0.28 V, and 0.15 V, respectively, during the NRR process, outperforming other phosphorus-based catalysts in activity. Full article

The electrocatalytic reduction of nitrate is an efficient and green method for NH₃ production. In this study, a Co-containing MOF with a stable three-dimensional carbon framework that offers abundant metal active sites is prepared as a precursor to a Co-N-C electrocatalyst. Facile pyrolysis of the three-dimensional MOF affords the desired Co-N-C electrocatalyst, which exhibits excellent stability, an NH₃ yield of 1.12 mmol h⁻¹ mg⁻¹, and faradaic efficiency of 86.7% at −0.23 V in a 0.1 M KOH/0.1 M KNO₃. The excellent activity and durability are ascribed to the highly exposed active centres, large surface area, and high porosity structure. N doping allows the electronic properties to be modulated and provides outstanding stability owing to the strong interaction between the nitrogen-doped carbon support and Co nanoparticles. This study presents a simple and efficient synthesis strategy for the production of non-noble-metal electrocatalysts with abundant active sites for the nitrate reduction reaction. Full article

The N₂ reduction reaction (NRR) under ambient conditions is highly desirable because of its potential to replace the energy-consuming Haber-Bosch process for ammonia production. In recent years, much attention has been devoted to transition metal-based catalysts. However, the development of metal-free electrocatalysts remains a great challenge. Here, the electrocatalytic performance of bilayer borophene is systematically studied based on first-principles calculations. It was found that bilayer borophene has high activity with an overpotential of 0.21 V via the enzymatic mechanism. Bond elongations of nitrogen bond are observed in end-on and side-on patterns, where the bond lengths are stretched to 1.13 and 1.21 Å, respectively. Around 0.36 e⁻ is transferred to the adsorbed N₂ with the contribution of bottom boron atoms. Our results propose bilayer borophene as a novel metal-free catalyst for nitrogen reduction, thus providing an avenue to explore highly efficient electrocatalysts for ammonia production under ambient conditions. Full article

Finding alternatives to platinum that exhibit high activity, stability, and abundant reserves as oxygen reduction electrocatalysts is crucial for the advancement of fuel cells. In this study, we first mixed FeCl₂·4H₂O, 1,10-phenanthroline, and Vulcan XC-72, followed by pyrolysis in a nitrogen atmosphere, to obtain FeNC. Subsequently, we combined FeNC with MXene produce FeNC/MXene composites. The FeNC/MXene catalyst achieved a half-wave potential of 0.857 V in an alkaline medium, exhibiting better oxygen reduction reaction (ORR) activity and durability than commercial Pt/C catalysts. The layered structure of MXene endows the material with a high specific surface area and facilitates efficient electron transfer pathways, thereby promoting rapid charge transfer and material diffusion. The cleavage of Ti-C bonds in Ti₃C₂ at elevated temperatures results in the transformation of MXene into TiO₂, where the coexistence of anatase and rutile phases generates a synergistic effect that enhances both the mass transfer rate and the electrical conductivity of the catalytic layer. Additionally, the unique electronic structure of the FeN_x sites simultaneously optimizes electrocatalytic activity and stability. Leveraging these structural advantages, the FeNC/MXene composite catalysts demonstrate exceptional catalytic activity and long-term stability in oxygen reduction reactions. Full article

Electrochemical nitrogen reduction reaction (NRR) has emerged as a promising approach for sustainable ammonia synthesis under ambient conditions, offering a low-energy alternative to the traditional Haber–Bosch process. However, the development of efficient and sustainable electrocatalysts for NRR remains a significant challenge. Noble metals, known for their exceptional chemical stability under electrocatalytic conditions, have garnered considerable attention in this field. In this study, we report the successful synthesis of nanoporous CuAuPtPd quasi-high-entropy alloy (quasi-HEA) prism arrays through “melt quenching” and “dealloying” techniques. The as-obtained alloy demonstrates remarkable performance as an NRR electrocatalyst, achieving an impressive ammonia synthesis rate of 17.5 μg h⁻¹ mg⁻¹ at a potential of −0.2 V vs. RHE, surpassing many previously reported NRR catalysts. This work not only highlights the potential of quasi-HEAs as advanced NRR electrocatalysts but also provides valuable insights into the design of nanoporous multicomponent materials for sustainable energy and catalytic applications. Full article

The electrocatalytic reduction of O₂ via two-electron reaction (2e-ORR) to H₂O₂ represents a promising alternative to the current anthraquinone process, since it is advantageous in the sustainable and decentralized production of H₂O₂. Herein, we report the development of oxygen and nitrogen-rich few-layered graphene-like materials (ms-dcda) by the one-step carbonization of biomass-sourced monosaccharides (D-glucose, D-fructose, D-galactose, D-ribose, D-xylose, L-arabinose, and D-mannose) with the aid of dicyandiamide for electrochemical O₂ reduction to H₂O₂. The ms-dcda materials were porous and possessed wrinkled morphology typical of graphene nanosheets. In H₂O₂ production via 2e-ORR in an acidic electrolyte, these ms-dcda materials were all active and stable catalysts, among which glu-dcda derived from D-glucose and dicyandiamide displayed the lowest onset potential of 0.553 V and the highest selectivity of up to 91.6%. The catalyst was also highly stable in chronoamperometric tests. Selective chemical titration of the C–OH and C=O groups revealed that the latter is far more active and selective than the former in 2e-ORR. Moreover, a positive correlation between the contents of C=O and pyrrolic N and the H₂O₂ partial current suggests that the pyrrolic N group also contributes to 2e-ORR. This work affords a facile strategy for the sustainable fabrication of metal-free carbon-based catalysts efficient for H₂O₂ electrosynthesis. Full article

The electrocatalytic reduction of nitrate (ERN) to ammonia offers a promising route to address energy shortages and environmental pollution, but its practical application is hindered by low selectivity due to complex eight-electron transfer pathways and high energy consumption (EC) from the kinetically sluggish oxygen evolution reaction (OER). This study proposes a dual strategy: (1) designing a multi-functional self-supported ANP electrode via vapor deposition to enhance ERN activity and (2) replacing the OER with thermodynamically favorable anodic reactions (urea oxidation reaction (UOR), sodium metabisulfite oxidation reaction (S(IV)OR), sulfite and urea oxidation reaction (S(IV)/UOR)) to reduce EC. The ANP cathode achieved a nitrate removal rate (R%) of 97.7%, ammonia selectivity (SE%) of 91.8%, and Faradaic efficiency (FE) of 97.3% at −1.2 V, with an ammonia yield of 0.0616 mmol h⁻¹ mg⁻¹ and an EC of 8.239 kWh/kg, while in situ-generated atomic hydrogen (*H) was identified as key to improving nitrate removal and selectivity. Replacing the OER with alternative anodic reactions significantly improved system efficiency: the UOR reduced EC by 17.5%, S(IV)OR saved 27.6% energy with 7.1% higher ammonia yield, and a hybrid S(IV)/UOR system achieved a 32.1% lower EC and a 12.6% greater ammonia yield than the OER. These differences stemmed from variations in cell voltage and ammonia production rates. This work provides a viable approach for selective nitrate-to-ammonia conversion and guides the design of energy-efficient electrocatalytic systems for sustainable nitrogen recovery. Full article

Two-dimensional carbon materials and their derivatives are widely applied as promising electrocatalysts and supports of single-atom sites. Theoretical investigations of 2D carbon materials are usually based on planar models, yet ignore local curvature brought on by possible surface distortion, which can be significant to the exact catalytic performance as has been realized in latest research. In this work, the curvature-influenced electrocatalytic nitrogen reduction reaction (NRR) reactivity of heme-like FeN₄ single-atom site was predicted by a first-principle study, with FeN₄-CNT(m,m) (m = 5~10) models adopted as local curvature models. The results showed that a larger local curvature is favored for NRR, with a lower limiting potential and higher N₂ adsorption affinity, while a smaller local curvature shows lower NH₃ desorption energy and is beneficial for catalyst recovery. Using electronic structures and logarithm fitting, we also found that FeN₄-CNT(5,5) shows an intermediate-spin state, which is different from the high-spin state exhibited by other FeN₄-CNT(m,m) (m = 6~10) models with a smaller local curvature. Full article

The electrocatalytic reduction of nitric oxide and nitrogen dioxide (NOx) remains a significant challenge due to the need for stable, efficient, and cost-effective materials. This study presents a novel support system for NOx reduction in alkaline media, composed of ZrO₂-WO₃-C (ZWC), synthesized via coprecipitation. Platinum nanoparticles (10 wt.%) were loaded onto ZWC and Vulcan carbon support, using similar methods for comparison. Comprehensive physicochemical and electrochemical analyses (N₂ physisorption, XRD, XPS, SEM, TEM, and cyclic and linear voltammetry) revealed that PtZWC outperformed PtC and commercial PtEtek in NOx electrocatalysis. Notably, PtZWC exhibited the highest total electric charge for NOx reduction. At the same time, the hydrogen evolution reaction (HER) was shifted to more negative cathodic potentials, indicating reduced hydrogen coverage and a modified dissociative Tafel mechanism on platinum. Additionally, the combination of WO₃ and ZrO₂ in ZWC enhanced electron transfer and suppressed HER by reducing NO and hydrogen atom adsorption competition. While the incorporation of WO₃ and ZrO₂ lowered the surface area to 96 m²/g, it significantly improved pore properties, facilitating better Pt nanoparticle dispersion (3.06 ± 0.85 nm, as confirmed by SEM and TEM). XRD analysis identified graphite and Pt phases, with monoclinic WO₃ broadening PtZWC peaks (20–25°). At the same time, XPS confirmed oxidation states of Pt, W, and Zr and tungsten-related oxygen vacancies, ensuring chemical stability and enhanced catalytic activity. Full article