Search Results (25)

Asymmetric-atomic-structure catalysts can modulate the interactions between active sites and intermediates through their unique electronic filling states and asymmetric charge distribution, breaking the linear relationship between adsorption energy and activity, thereby enhancing the catalytic performance of the oxygen reduction reaction (ORR). By introducing heteroelements, vacancies, or clusters into symmetric-atomic-structure catalysts (e.g., M-N₄), asymmetric configurations (such as M-N_x, M-N_x-S/B/O, etc.) can be formed. These modifications substantially alter their internal structure, trigger charge redistribution, and create asymmetric sites to reduce reaction energy barriers, effectively regulating the adsorption strength of oxygen intermediates and significantly improving ORR performance. This review systematically summarizes recent advancements in asymmetric-atomic-structure catalysts for ORR, elucidating the intrinsic “structure–performance–application” relationships to provide theoretical guidance for developing high-performance asymmetric atomic catalysts. First, the ORR mechanisms, including the two-electron and four-electron pathways, are introduced. Furthermore, strategies to modulate catalyst selectivity and activity through doping with metallic/nonmetallic elements or introducing defects are discussed. Finally, prospects for asymmetric-atomic-structure catalysts in next-generation energy storage and conversion technologies are outlined, offering novel insights to overcome current ORR performance bottlenecks. Full article

Oxidative dehydrogenation (ODH) of ethanol to acetaldehyde is an important production process. However, it still suffers from low deactivation, selectivity, and high costs. Herein, we developed a new strategy for preparing mesoporous nitrogen-doped carbon catalysts by carbonization of phenolic resin with silica as a hard template. The catalyst demonstrated an impressive acetaldehyde selectivity of over 76% at 270 °C for 25 h during the ODH of ethanol to acetaldehyde. Mechanistic studies have shown that the two carbon atoms in adjacent C=O groups are replaced by nitrogen atoms in the N₀-Gra-O structural unit. The C=O functional group on the surface of the catalyst is the active center for the ODH of ethanol to acetaldehyde, and the introduction of nitrogen atoms can reduce the adsorption capacity of acetaldehyde molecules at the active site (ΔG values can be reduced by 0.11–0.45 eV), enabling rapid desorption of the product and avoiding the problem of excessive oxidation, thereby improving the selectivity of acetaldehyde. This work reveals the structure–activity relationship between active sites and selective regulation of nitrogen-doped carbon-based catalysts for the ODH of ethanol, providing a theoretical basis for the development of efficient non-metallic carbon-based catalysts. Full article

Advanced oxidation processes based on either peroxydisulfate (PDS) or peroxymonosulfate (PMS), collectively termed persulfate-based advanced oxidation processes (PS-AOPs), show potential in wastewater treatment applications. In this work, the nitrogen (N) and sulfur (S) co-doped biochar (NSBC) was prepared via a one-step pyrolysis of coffee grounds at 400 to 800 °C as a PMS activator for degrading paracetamol (PCT). The non-metallic NSBC demonstrated exceptional catalytic activity in activating PMS. In the NSBC-800/PMS system, 100% of PCT was completely degraded within 20 min, with a high reaction rate constant (k_obs) of 0.2412 min⁻¹. The system’s versatility was highlighted by its degradation potential across a wide pH range (3–11) and in the presence of various background ions and humic acids. The results of various experiments and characterization techniques showed that the system relied on an NSBC-800-mediated electron transfer as the main mechanism for PCT degradation. Additionally, there was a minor involvement of ¹O₂ in a non-radical degradation pathway. The graphitic N and thiophene-S (C-S-C) moieties introduced by N/S co-doping, as well as the carbonyl (C=O) groups of the biochar, were considered active sites promoting ¹O₂ generation. The total organic carbon (TOC) removal rate reached 37% in 120 min, while the assessment of the toxicity of the degradation products also affirmed the system’s environmental safety. This research provides a novel method for preparing environmentally friendly and cost-effective carbon-based catalysts for environmental remediation. Full article

Hydrogen peroxide (H₂O₂) is an environmentally friendly oxidant with a wide range of applications, and the two-electron pathway (2e⁻) of the oxygen reduction reaction (ORR) for H₂O₂ production has attracted much attention due to its eco-friendly nature and operational simplicity in contrast to the conventional anthraquinone process. The challenge is to design electrocatalysts with high activity and selectivity and to understand their structure–activity relationship and catalytic mechanism in the ORR process. Covalent organic frameworks (COFs) provide an efficient template for the construction of highly efficient electrocatalysts due to their designable structure, excellent stability, and controllable porosity. This review firstly outlines the design principles of COFs, including the selection of metallic and nonmetallic active sites, the modulation of the electronic structure of the active sites, and the dimensionality modulation of the COFs, to provide guidance for improving the production performance of H₂O₂. Subsequently, representative results are summarized in terms of both metallic and metal-free sites to follow the latest progress. Moreover, the challenges and perspectives of 2e⁻ ORR electrocatalysts based on COFs are discussed. Full article

The electrocatalytic production of ammonia has garnered considerable interest as a potentially sustainable technology for ammonia synthesis. Recently, non-metallic-doped materials have emerged as promising electrochemical catalysts for this purpose. This paper presents a comprehensive review of the latest research on non-metallic-doped materials for electrocatalytic ammonia production. Researchers have engineered a variety of materials, doped with non-metals such as nitrogen (N), boron (B), phosphorus (P), and sulfur (S), into different forms and structures to enhance their electrocatalytic activity and selectivity. A comparison among different non-metallic dopants reveals their distinct effects on the electrocatalytic performance for ammonia production. For instance, N-doping has shown enhanced activity owing to the introduction of nitrogen vacancies (NVs) and improved charge transfer kinetics. B-doping has demonstrated improved selectivity and stability, which is attributed to the formation of active sites and the suppression of competing reactions. P-doping has exhibited increased ammonia generation rates and Faradaic efficiencies, likely due to the modification of the electronic structure and surface properties. S-doping has shown potential for enhancing electrocatalytic performance, although further investigations are needed to elucidate the underlying mechanisms. These comparisons provide valuable insights for researchers to conduct in-depth studies focusing on specific non-metallic dopants, exploring their unique properties, and optimizing their performance for electrocatalytic ammonia production. However, we consider it a priority to provide insight into the recent progress made in non-metal-doped materials and their potential for enabling long-term and efficient electrochemical ammonia production. Additionally, this paper discusses the synthetic procedures used to produce non-metal-doped materials and highlights the advantages and disadvantages of each method. It also provides an in-depth analysis of the electrochemical performance of these materials, including their Faradaic efficiencies, ammonia yield rate, and selectivity. It examines the challenges and prospects of developing non-metallic-doped materials for electrocatalytic ammonia production and suggests future research directions. Full article

Hydrogen embrittlement (HE) of steel pipelines in high-pressure gaseous environments is a potential threat to the pipeline integrity. The occurrence of gaseous HE is subjected to associative adsorption of hydrogen molecules (H₂) at specific “active sites”, such as grain boundaries and dislocations on the steel surface, to generate hydrogen atoms (H). Non-metallic inclusions are another type of metallurgical defect potentially serving as “active sites” to cause the dissociative adsorption of H₂. Al₂O₃ is a common inclusion contained in pipeline steels. In this work, the dissociative adsorption of hydrogen at the $\mathsf{\alpha }\text{-}{\mathrm{A}\mathrm{l}}_2{\mathrm{O}}_3\left(0001\right)/\mathsf{\alpha }\text{-}\mathrm{F}\mathrm{e}\left(111\right)$ interface on the $\mathrm{F}\mathrm{e}\left(01\overline{1}\right)$ plane was studied by density functional theory calculations. The impact of gas components of O₂ and CH₄ on the dissociative adsorption of hydrogen was determined. The occurrence of dissociative adsorption of hydrogen at the Al₂O₃ inclusion/Fe interface is favored under conditions relevant to pipeline operation. Thermodynamic feasibility was observed for Fe and O atoms, but not for Al atoms. H atoms can form more stable adsorption configurations on the Fe side of the interface, while it is less likely for H atoms to adsorb on the Al₂O₃ side. There is a greater tendency for the occurrence of dissociative adsorption of O₂ and CH₄ than of H₂, due to the more favorable energetics of the former. In particular, the dissociative adsorption of O₂ is preferential over that of CH₄. The Al-terminated interface exhibits a higher H binding energy compared to the O-terminated interface, indicating a preference for hydrogen accumulation at the Al-terminated interface. Full article

The development of efficient and low-cost non-metallic catalysts is of great significance for the oxygen reduction reaction (ORR) in fuel cells. Heteroatom-doped carbon-based catalysts are one of the popular candidates, although their preparation method is still under exploration. In this work, single (CS)-, double (NCS)-, and triple (NBCS)-heteroatom-doped carbon-based catalysts were successfully prepared by a “cook-off” process. The morphology, elemental composition, and bonding structure of the catalysts were investigated by SEM, TEM, Raman spectra, BET, and XPS. ORR catalytic performance measurements suggested an activity trend of CS < NCS < NBCS, and NBCS demonstrated better methanol resistance and slightly higher stability than the commercial Pt/C catalyst, as evaluated with both rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) systems. The mechanism for the promoted performance was also proposed based on the conductivity of the catalysts. In this paper, the heteroatoms N, B, and S were co-doped into activated carbon using a simple, fast, and efficient preparation method with high electrical conductivity and also increased active sites, showing high electrocatalytic activity and good stability. This work provides a new approach to preparing highly active non-Pt catalysts for oxygen reduction reactions. Full article

The construction of a surface-frustrated Lewis pairs (SFLPs) structure is expected to break the single electronic state restriction of catalytic centers of P-region element materials, due to the existence of acid-base and basic active canters without mutual quenching in the SFLPs system. Herein, we have constructed eight possible SFLPS structures on the In₂O₃ (110) surface by doping non-metallic elements and investigated their performance as electrocatalytic nitrogen reduction catalysts using density functional theory (DFT) calculations. The results show that P atom doping (P@In₂O₃) can effectively construct the structure of SFLPs, and the doped P atom and In atom near the vacancy act as Lewis base and acid, respectively. The P@In₂O₃ catalyst can effectively activate N₂ molecules through the enzymatic mechanism with a limiting potential of −0.28 eV and can effectively suppress the hydrogen evolution reaction (HER). Electronic structure analysis also confirmed that the SFLPs site can efficiently capture N₂ molecules and activate N≡N bonds through a unique “donation-acceptance” mechanism. Full article

Ternary transition metal phosphides (TTMPs) with two-dimensional heterointerface and adjustable electronic structures have been widely studied in hydrogen evolution reactions (HER). However, single-phase TMPs often have inappropriate H* adsorption energy and electronic transfer efficiency in HER. Herein, we utilized the heterogeneity in the crystal structure to design an efficient and stable catalyst from the NiCoP nanowire@NiCoP nanosheet on nickel foam (NW-NiCoP@NS-NiCoP/NF) for HER. Layered double hydroxides (LDHs) with a heterogeneous matrix on crystal surfaces were grown under different reaction conditions, and non-metallic P was introduced by anion exchange to adjust the electronic structure of the transition metals. The hierarchical structure of homologous NiCoP/NF from the LDH allows for a larger surface area, which results in more active sites and improved gas diffusion. The optimized NW-NiCoP@NS-NiCoP/NF electrode exhibits excellent HER activity, with an overpotential of 144 mV, a Tafel slope of 84.2 mV dec⁻¹ at a current density of 100 mA cm⁻² and remarkable stability for more than 500 h in 1.0 M KOH electrolyte. This work provides ideas for elucidating the rational design of structural heterogeneity as an efficient electrocatalyst and the in situ construction of hierarchical structures. Full article

In recent years, non-Pt-based ORR catalysts have been developing rapidly and have achieved performance comparable to or even surpassing Pt precious metal catalysts in specific reactions, offering new possibilities for Pt-based catalyst replacement and showing great promise for application. This paper reviews the recent research progress of non-Pt-based fuel cell ORR catalysts. The latest research progress of non-Pt-based ORR SACs (including single metal active site ORR SACs, multi-metal active site ORR SACs, and non-Pt-based noble metal catalyst ORR SACs), non-metallic ORR catalysts, alloy-based ORR catalysts, high-entropy alloy ORR catalysts, and other non-Pt-based fuel cell ORR catalysts are presented in detail. This paper discusses in detail the synthesis methods, characterization means, optimization of performance, and application prospects of these non-Pt-based ORR catalysts. In addition, this review details the excellent performance of these catalysts in terms of compositional and structural controllability, electrical conductivity, and chemical stability, as well as their ability to exhibit ORR activity comparable to that of commercial Pt/C catalysts. This field is full of opportunities and challenges. In summary, non-Pt-based fuel cells show great potential in ORR. With the continuous improvement of preparation and characterization technologies, catalysts have broad application and market prospects. In addition, the development trend of non-precious metal fuel cell catalysts is reviewed. Full article

The harmful effects on the human body from p-phenylenediamine (PPD) in hair dyes can cause allergies and even cancer. Therefore, it is particularly important to accurately control and detect the content of PPD in our daily products and environment. Here, a small amount of non-metallic elemental P doped in perovskite oxide of SrCoO_3−δ (SC) forms a good catalytic material, SrCo_0.95P_0.05O_3−δ (SCP), for PPD detection. The improved performance compared with that of the parent SC can be attributed to three contributing factors, including a larger amount of highly oxidative oxygen species O²²⁻/O⁻, better electrical conductivity, and more active sites on the P⁵⁺-oxygen bonds of SCP. Moreover, the lattice oxygen mechanism (LOM) with highly active species of lattice O vacancies and adsorbed –OO for electrocatalytic oxidation of PPD by the SCP/GCE (glass carbon electrode) sensor is proposed in our work. More importantly, the SCP/GCE sensor exhibits good stability, a low limit of detection, and high reliability (error < 5.78%) towards PPD determination in real samples of hair dyes, suggesting the substantial research potential for practical applications. Full article

The search for low-cost, high-performance, and robust stability bifunctional electrocatalysts to substitute noble metals-based counterparts for overall water splitting to generate clean and sustainable hydrogen energy is of great significance and challenges. Herein, a high-efficient bi-functional nickel–iron phosphide on NiFe alloy foam (denoted as e-NFP/NFF) with 3D coral-like nanostructure was controllably constructed by means of alkali etching and the introduction of non-metallic atoms P. The unique superhydrophilic coral-like structure can not only effectively facilitate the exposure of catalytic active sites and increase the electroactive surface area, but also accelerate charge transport and bubble release. Furthermore, owing to the synergistic effect between the bicomponent of nickel–iron phosphides as well as the strong electronic interactions of the multiple metal sites, the as-fabricated catalyst behaves with excellent bifunctional performance for the hydrogen evolution reaction (overpotentials of 132 and 286 mV at 10 and 300 mA·cm⁻², respectively) and oxygen evolution reaction (overpotentials of 181 and 303 mV at 10 and 300 mA·cm⁻², respectively) in alkaline electrolytes. Impressively, cells with integrated e-NFP/NFF electrodes as a cathode and anode require only a low cell voltage (1.58 V) to drive a current density of 10 mA·cm⁻² for overall water splitting, along with remarkable stability in long-term electrochemical durability tests. This study provides a tunable synthetic strategy for the development of efficient and durable non-noble metal bifunctional catalysts based on the construction of an elaborate structure framework and rational design of the electronic structure. Full article

The quest for improved heterogeneous catalysts often leads to sophisticated solutions, which are expensive and tricky to scale up industrially. Herein, the effort to upgrade the existing inorganic nonmetallic materials has seldom been prioritized by the catalysis community, which could deliver cost-effective solutions to upgrade the industrial catalysts catalog. With this philosophy in mind, we demonstrate in this work that alloyed palladium-lead (Pd-Pb) deposited on novel precipitated calcium carbonate (PCC) supports could be considered an upgraded version of the industrial Lindlar catalyst for the semi-hydrogenation of phenylacetylene to styrene. By utilizing PCC supports of variable surface areas (up to 60 m²/g) and alloyed Pd-Pb loading, supported by material characterization tools, we showcase that achieving the “active-site isolation” feature could be the most pivotal criterion to maximize semi-hydrogenated alkenes selectivity at the expense of prohibiting the complete hydrogenation to alkanes. The calcite phase of our PCC supports governs the ultimate catalysis, via complexation with uniformly distributed alloyed Pb, which may facilitate the desired “active-site isolation” feature to boost the selectivity to the preferential product. Through this work, we also advocate increasing research efforts on mineral-based inorganic nonmetallic materials to deliver novel and improved cost-effective catalytic systems. Full article

The hydrogen evolution reaction (HER) plays a crucial role in hydrogen gas production. Layers of transition-metal dichalcogenides (TMDs) possess adjustable electronic structures, and TMDs with H-phase structures have been proposed as substitute HER catalysts. Nonetheless, there are few systematic theoretical analyses of the HER catalytic properties of TMDs with T’-phase structures. Using a DFT calculation, we investigated the electrocatalytic properties of W-based dichalcogenides (WS₂, WSe₂, and WTe₂) through defect engineering. It was found that the interaction of H atoms with the basal plane can be tuned using non-metallic atomic doping, especially with P, thereby enhancing catalytic activity. Furthermore, the computation results demonstrated that high P-doping concentrations can enhance the number of active sites and exhibit a suitable ΔG_H*. Full article

In this paper, density functional theory (DFT) was used to study the possibility of low-dimensional (2D, 1D, 0D) boron nitride nanomaterials to catalyze acetylene acetate reaction, and further explore the possible source of this catalytic activity. It is found that the catalytic activity of boron nitride nanomaterials for acetylene acetate reaction will change with the change of the geometric structure (dimension) and reaction site of the catalyst. From the geometric structure, the reaction components and the zero-dimensional BN catalyst can form chemical bonds and form complexes, while only physical adsorption occurs on the surface of the one-dimensional and two-dimensional BN catalysts. From the reaction site, the properties of different C sites on the B₁₂N₁₂NC-C₂H₂ complexes are different. Namely, a C atom connected with a B atom is more likely to have an electrophilic reaction with H⁺, and a C atom connected with an N atom is more likely to have a nucleophilic reaction with CH₃COO⁻. Through the study of three kinds of BN nanomaterials with low dimensions, we found that the zero-dimensional B₁₂N₁₂ nanocage broke the inherent reaction inertia of BN materials and showed good catalytic activity in an acetylene acetate reaction, which is very likely to be a non-metallic catalyst for the acetylene gas-phase preparation of vinyl acetate. Full article