Search Results (257)

The hydrogen evolution reaction (HER) is a cornerstone of green hydrogen production, yet its efficiency is constrained by the sluggish kinetics of water splitting. High-entropy catalysts (HECs), single-phase materials incorporating multiple principal elements, have emerged as a transformative solution. Their unique attributes including vast compositional flexibility, tunable electronic structures, and synergistic multi-element interactions, enable them to overcome the activity, stability, and cost limitations of conventional catalysts. Despite rapid performance advancements, the rational design of HECs is fundamentally hampered by critical knowledge gaps, particularly in identifying true active sites under operando conditions and predicting long-term stability. This work critically assesses these challenges, systematically summarizing the latest progress in HECs design, synthesis, and structure–activity relationships. By bridging fundamental principles with practical applications, we provide a forward-looking perspective on key research directions. Distinct from recent progress-focused reviews, this work establishes a strategic roadmap by systematically diagnosing seven grand challenges across the science-to-technology pipeline and proposing corresponding countermeasures. This framework aims to guide future research efforts toward the rational design and practical deployments of HECs for practical and cost-effective green hydrogen production. Full article

The widespread presence of ciprofloxacin (CIP) in aquatic environments threatens ecological and public health, yet conventional treatment processes fail to remove such persistent contaminants. Conventional solvothermal synthesis of Bi-doped g-C₃N₄ photocatalysts involves complicated procedures and low productivity. Herein, we employ a single-step, template-free and solvent-free green calcination method to construct Bi³⁺-modified g-C₃N₄ with strong Bi-N coordination interactions. A series of Bi/g-C₃N₄ photocatalysts with Bi-doping mass ratios of 0.09–0.34 wt% was prepared, and the structure–performance relationship as well as the surface–interface reaction mechanism for ciprofloxacin (CIP) degradation were systematically elucidated. Experimental results confirm that Bi³⁺ incorporates into the lattice via Bi-N coordination bonds with nitrogen in the g-C₃N₄ framework, which narrows the band gap, suppresses photogenerated carrier recombination, and constructs a loose porous morphology beneficial for increasing specific surface area and active sites. Under optimal conditions, 15Bi/g-C₃N₄ achieves 97.6% degradation of 15 mg L⁻¹ CIP within 90 min, which is 13.7% higher than that of pristine g-C₃N₄. The effects of catalyst dosage, initial pH, CIP concentration, common coexisting ions, and different real water matrices on the degradation performance were systematically investigated. Radical quenching experiments combined with ESR characterization confirm that h⁺ is the dominant reactive species responsible for CIP degradation. This green, simple and scalable method yields uniform products, and the resulting materials exhibit high efficiency, economic feasibility and environmental safety, demonstrating promising potential for antibiotic wastewater treatment. Full article

The CO₂ storage–regeneration (CO₂-SR) process represents a promising strategy for integrating CO₂ capture and catalytic conversion within a single cyclic operation using multifunctional catalysts. In this concept, CO₂ is first stored on basic sites and subsequently converted through methane activation, enabling the coupling of CO₂ capture and reforming reactions in a single reactor. In this work, a series of unsupported Ni–Ba catalysts were investigated as model multifunctional materials for the CO₂-SR process. Catalysts with different Ni/Ba ratios were prepared to analyze how the distribution of storage and catalytic sites influences the cyclic CO₂ capture–conversion behavior. In addition, Rh was introduced as a promoter either during synthesis by co-precipitation or ex situ by impregnation, allowing to evaluate the influence of Rh location and surface enrichment on the catalytic properties. Rh incorporation in the NiBa catalyst (Ni/Ba = 10/1 and Ni/Rh = 100/1) increased the specific surface area (BET area 64 m²·g⁻¹ vs. 55 m²·g⁻¹ for NiBa) and reduced the NiO crystallite size from 250.4 Å to 231.5 Å, indicating improved dispersion of the metallic phase. XPS analysis revealed the coexistence of Rh⁰ and Rh³⁺ species, suggesting that Rh acts as a redox mediator that facilitates hydrogen activation and promotes hydrogen spillover to neighboring Ni sites. Raman and CO₂-TPD results show that Ba-derived domains stabilize carbonate species responsible for CO₂ storage, while Rh enhances catalyst reducibility and modifies the kinetics of carbonate decomposition during the regeneration stage. Transient CO₂–CH₄ pulse experiments demonstrate that the CO₂-SR process proceeds through a dynamic surface cycle involving reversible carbonate formation on Ba-derived basic sites coupled with methane activation on Ni-containing interfacial sites. The results indicate that catalyst performance is governed by a hierarchical surface architecture composed of Ni–O–Ba interfacial domains, reversible Ba–O–Ba carbonate storage sites, and more stable Ba-rich domains. The distribution of these domains, controlled by the Ni/Ba ratio and the dispersion of the metallic phase, determines the reversibility of carbonate formation and the efficiency of the cyclic CO₂ storage–regeneration process. Full article

Ammonia is indispensable to the fertilizer and chemical industries, yet its manufacture still relies predominantly on the energy-intensive Haber–Bosch process operated at 400–500 °C and 150–250 bar, with a substantial carbon footprint. Single-atom catalysts (SACs) and sub-nanometric clusters have recently emerged as promising alternatives for thermocatalytic ammonia synthesis under milder conditions because they maximize metal utilization and enable precise control of the active site environment. This review first summarizes how the transition from conventional Fe and Ru nanoparticles to isolated or few-atom sites fundamentally alters the kinetic landscape, favoring associative N₂ activation pathways that lower apparent activation energies and alleviate H₂ poisoning. We then discuss Ru-based SACs and SAAs supported on zeolites, carbons, ceria, and MXenes, highlighting how strong metal–support and promoter interactions, tandem single-atom/nanoparticle motifs, and alloying strategies tune N₂ and H₂ binding to deliver high NH₃ productivities at 200–400 °C and ≤30 bar. In parallel, we review emerging non-noble systems based on Fe and Co, including high-loading Fe–N₄ sites prepared via MOF-derived post-metal-replacement routes and Co single atoms or Co₂ clusters on N-doped carbons, which already rival or surpass Ru benchmarks under similar conditions. Collectively, these studies show that tailoring the number of atom metal sites, coordination, and support polarity around isolated metal sites provides a useful tool to mitigate some aspects of volcano and scaling-relation limitations, indicating that SACs could contribute to low-temperature ammonia synthesis when combined with appropriate process design. Full article

We report the synthesis of Fe/N/C ORR electrocatalysts by an original collinear CO₂ laser pyrolysis of liquid aerosol droplets in various configurations and compared them to a catalyst synthesized in the classical perpendicular one. While the precursors were always injected at the bottom side of the reactor, two collinear configurations of the laser entry into the reactor are considered: by the Top Side (T.S.) or by the Bottom Side (B.S.). The two corresponding catalysts sets show significant different ORR performances. An in-depth XPS analysis and fitting of the N1s spectra allowed for drawing the ORR performance as a function of FeN_x sites components. An original approach considering the energy delivered to a quantity of precursors in J.g⁻¹, linked to the flame temperature feature, evidenced very different conditions for perpendicular CO₂ laser pyrolysis and each of the two collinear configurations. This mass-weighted energy delivered in the classical perpendicular configuration is too low to allow for the formation of FeN_x sites and the resulting ORR performance is extremely poor, suggesting a marginal role of nitrogen species without interaction with iron atoms. In contrast, the delivered mass-weighted energies are sufficient in both collinear configurations to produce FeN_x sites. The ORR performance for catalysts produced in these both configurations is positively correlated with the amount of energy deposited on the precursors. The ORR performance in the T.S. laser configuration is positively correlated to the amount of FeN_x sites. The best performing catalysts obtained in the B.S. configuration show an opposite variation. These trends, and the ORR performance degradation of B.S. catalysts under prolonged chronoamperometry are discussed in light of the effect of temperature on the formation of the various kind of FeN_x sites. A tentative explanation is given, considering that N1s XPS fitting with a single FeN_x component may hinder the fact that Pyridinic sites components may contain a part of FeN_x sites, as suggested by theoretical calculation from the literature. The best catalysts obtained in this work by collinear configuration show similar performances to those obtained by double stage perpendicular pyrolysis previously reported with an ORR onset potential of ~860 mV. Full article

A novel catalyst, Tm₂FeSbO₇, was synthesized by employing the solid-phase high-temperature sintering method, and, for the first time, it was utilized to create a Z-type heterojunction with BiYO₃. A direct Z-scheme Tm₂FeSbO₇/BiYO₃ heterojunction photocatalyst (TBHP) was successfully produced by employing the ball-milling technique. X-ray diffraction analysis results indicated that Tm₂FeSbO₇ crystallized in a cubic pyrochlorestructure which owned the Fd-3m space group, with a unit cell parameter of 10.1769 Å, whereas BiYO₃ displayed a fluorite structure in the Fm-3m space group, with a unit cell parameter of 5.4222 Å. The Mossbauer spectrum of Tm₂FeSbO₇ showed that Fe³⁺ ions might locate at octahedral sites. The measured bandgap widths for the TBHP, Tm₂FeSbO_7, and BiYO₃ were 2.14 eV, 2.21 eV, and 2.30 eV, respectively. Multiple experimental results demonstrated that the TBHP exhibited a higher valence band ionization potential, a narrower band gap width, and a higher removal efficiency of the sulfamethoxazole (SMX) compared with the Dy₂TmSbO₇/BiHoO₃ heterojunction photocatalyst. Under visible-light irradiation (VISLI) of 115 min, the TBHP showcased exceptional photocatalytic elimination performance; therefore, the elimination rate of the SMX and the total organic carbon (TOC) mineralization rate reached 99.51% and 98.10%, respectively. In contrast to single-component Tm₂FeSbO₇, BiYO_3, or conventional nitrogen-doped titanium dioxide (N-TiO₂) catalyst, the TBHP exhibited removal efficiency enhancement for degrading the SMX by 1.17 times, 1.31 times, or 4.06 times. Simultaneously, the matching mineralization rate for removing the TOC density by employing the TBHP was 1.20 times, 1.34 times, or 4.73 times higher than that by employing Tm₂FeSbO₇, BiYO₃, or conventional N-TiO₂. Above experimental results indicated that the mineralization efficiency for removing TOC density by employing the TBHP was higher than that by employing Tm₂FeSbO₇, BiYO₃, or N-TiO₂. Radicals trapping experiments and the electron paramagnetic resonance spectroscopy results revealed that hydroxyl radicals, superoxide anions, and photoinduced holes were the primary active species during the catalytic elimination course of the SMX by employing the TBHP under VISLI. The results demonstrated that the direct Z-scheme TBHP, which was developed in this study, exhibited the maximal removal efficiency for degrading the SMX in contrast to Tm₂FeSbO₇, BiYO₃, or N-TiO₂. Additionally, the possible elimination routes and elimination mechanisms of the SMX were proposed. Therefore, an important scientific foundation for developing high-performance heterojunction catalysts was established. Full article

Catalytic ozonation often suffers from a low ozone utilization rate and incomplete mineralization of organic pollutants. To address these challenges, we designed and prepared a novel catalyst via a one-step thermal polymerization method, anchoring single-atom manganese on a glucose-derived carbon network-modified C₃N₅ framework (Mn/C-C₃N₅). Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) on an FEI Titan Themis Z microscope confirmed the atomic dispersion of Mn sites, while Raman spectroscopy using a Renishaw inVia Reflex laser micro-Raman spectrometer verified the successful incorporation of a graphitic carbon network within the C₃N₅ matrix. Moreover, electrochemical analyses, including electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) performed on a Bio-Logic SP-150 electrochemical workstation, demonstrated that the integration of the conductive carbon matrix substantially enhanced the interfacial charge transfer capability. The optimized Mn/C-C₃N₅ catalyst demonstrated exceptional performance in phenol mineralization, achieving a 97% total organic carbon (TOC) removal within 60 min, a remarkable improvement compared to pristine C₃N₅ (30%). Furthermore, the catalyst exhibited excellent operational stability, preserving more than 95% of its original activity over five repeated runs. Mechanistic investigations, including electron paramagnetic resonance (EPR) spectroscopy and radical quenching experiments, revealed that the Mn/C-C₃N₅ system accelerated the generation of multiple oxidizing radicals (•O₂⁻, ¹O₂, and •OH), with •OH identified as the predominant reactive species responsible for complete mineralization. This work establishes an integrated catalytic platform and provides fundamental insights into electronic structure modulation for designing advanced oxidation catalysts. Full article

Biochar-based catalysts have emerged as sustainable alternatives for biodiesel production, achieving high yields (up to 99%) from various feedstocks. This study aimed to utilize Spirulina-derived biochar as a bifunctional green catalyst for biodiesel synthesis from waste cooking oil (WCO) through transesterification and assess its green performance metrics. Biochar synthesized by carbonization (324 °C) was modified with calcium and sulfuric acid, featuring dual acid-base sites. Energy dispersive spectra revealed impregnation of calcium (11.11%) compared to the raw biomass (2.34%), followed by peaks of methoxy group and methylene group, and with methylene and β-carbonyl protons shown by nuclear magnetic spectroscopy. Thus, the biochar catalyst tested on WCO achieved a 93.27% yield under optimized conditions (65 °C, 1:15 methanol-to-oil ratio, 3% catalyst, 3.5 h) via central composite design. Catalyst reusability was maintained over four cycles with an average biodiesel yield (90%). Further, green metrics validate their eco-friendliness with a single-cycle reaction mass efficiency (RME) of 60.8%. When the initial catalyst mass is amortized over four cycles, the cumulative biodiesel yield per initial catalyst input reaches the equivalent of 243% of a single-batch theoretical yield (catalyst productivity = 3.12 g FAME/g catalyst). E-Factor at 0.67 (reduced to 0.17) and mass intensity at 1.68 (down to 0.42), contrasting with business-as-usual scenarios such as sulfuric acid catalysis (RME 70.0%, E-Factor 0.25) using 8.85 g H₂SO₄ vs. ~5 g H₂SO₄/kg biochar. Our results demonstrate that bio-based catalysts minimize non-benign inputs, supporting a circular economy from algal waste. Full article

3-Acetyl-1-propanol (3-AP) is a key intermediate in the pharmaceutical and pesticide industries, which can be synthesized from the biomass derivative 2-methylfuran (2-MF) through a one-step hydrogenation process with significant economic and environmental benefits. Zeolite-supported metal catalysts showed feasible application, but simply regulating the acidic sites was difficult to break the activity–selectivity balance. Traditional single-metal Pd-based catalysts still suffer from low dispersion. This study constructed the PdZn/TS-1 catalyst for the efficient conversion of 2-MF into 3-AP. The low electronegativity of Zn facilitates the electron transfer from Zn to Pd, forming an electron-rich Pd active center. A small amount of Zn embedded in the Pd lattice causes lattice contraction, optimizing the spatial configuration of active sites. The synergy between the electronic and structural effects significantly improves catalytic performance. Under optimized conditions, the conversion rate of 2-MF reached 80.6%, and the yield of 3-AP reached 69.1%, providing a new paradigm for the design of catalysts for the directed hydrogenation of furan derivatives. Full article

Mechanistic interpretation in transition metal electrocatalysts for water splitting, particularly for the oxygen evolution reaction (OER), remains challenging despite major advances in operando spectroscopy, isotope labelling, and electrochemical analysis. Mechanistic claims are frequently supported by incomplete or overinterpreted evidence, leading to persistent ambiguity in active site identification, rate-limiting step assignment, and pathway discrimination. This review adopts a claim-centric framework that organises experimental approaches around the specific mechanistic assertions they aim to support, rather than cataloguing catalyst classes or performance metrics, and formalises this perspective as a decision-guided framework for mechanistic validation. We critically assess how techniques such as isotope labelling, operando spectroscopy, and electrokinetic analysis can and cannot substantiate claims related to adsorbate-versus lattice-oxygen-mediated pathways, reconstruction-defined active phases, and dynamic surface behaviour. Application of this framework to common mechanistic archetypes in OER electrocatalysis shows that surface reconstruction and condition-dependent pathway switching limit static mechanistic assignments, and that single-technique interpretations are rarely definitive. By clarifying the minimum evidentiary standards required for common mechanistic claims, this review aims to promote more rigorous, transparent, and falsifiable mechanistic analysis, supporting durable progress beyond descriptor-driven correlations and isolated performance benchmarks. Full article

For Co-N-C materials prepared under high-temperature calcination conditions, the formation of Co nanoparticles occurs when the metal loading exceeds 2%. Typically, CoNx is regarded as the primary active site of the catalyst, while Co nanoparticles are considered to possess limited catalytic activity. Consequently, within Co-N-C materials, Co nanoparticles are often likened to ‘ballast stone’ in a catalyst. In the model reaction of formic acid dehydrogenation, we incorporated boron into the precursor, thereby enhancing the electronic metal-support interactions (EMSI) between Co nanoparticles and carbon carriers. Consequently, this modification resulted in a catalytic performance of Co nanoparticles that was comparable to that of Co single-atom catalysts (SACs). Full article

The widespread occurrence of pharmaceutical contaminants in aquatic environments poses significant risks to ecosystems and public health, necessitating the development of efficient and sustainable treatment technologies. Herein, a visible-light (VL)–active zinc single-atom catalyst supported on biochar (SAZn@BC) was synthesized via pyrolysis and applied for the degradation of ibuprofen (IBP), sulfamethoxazole (SMX), trimethoprim (TMP), and carbamazepine (CBZ) in water. Structural characterization confirmed the presence of g-C₃N₄ domains, abundant oxygen-containing functional groups, and atomically dispersed Zn sites with a Zn–N₄ coordination environment. Under VL irradiation, SAZn@BC achieved degradation efficiencies of 43.9%, 64.4%, and 61.9% for IBP, SMX, and TMP, respectively, within 30 min, while CBZ exhibited limited removal. Mechanistic investigations combining quenching experiments, electrochemical analyses, and X-ray photoelectron spectroscopy revealed that superoxide and hydroperoxyl radicals were the dominant reactive oxygen species, with hydroxyl radicals and singlet oxygen contributing to a lesser extent. In addition, a nonradical pathway involving direct interfacial electron transfer between oxygen functional groups on the biochar support and pharmaceutical molecules played a critical role, mediated by single-atom Zn sites and enhanced under VL irradiation. These findings demonstrate that SAZn@BC enables synergistic radical and nonradical pathways for pharmaceutical degradation and represents a promising strategy for water treatment applications. Full article

D-Tagatose is a rare sugar of interest as a low-calorie sweetener, and enzymatic isomerization of D-galactose is a practical production route. L-arabinose isomerase (L-AI; EC 5.3.1.4) is a promising catalyst for the above process, but many characterized L-AIs perform best at alkaline pH and high temperature and often require substantial divalent metal supplementation (e.g., Mn²⁺/Co²⁺), which complicates food-grade processing. Lactic acid bacteria (LAB) are attractive sources of food-compatible enzymes, yet structural information for LAB-derived L-AIs has been limited. Here, we report the 2.6 Å X-ray crystal structure of L-AI from Latilactobacillus sakei 23K (LsAI) and define its oligomeric assembly. Although the asymmetric unit contains a single monomer, crystallographic symmetry reconstructs a D₃-symmetric homohexamer composed of two face-to-face trimers, consistent with a higher-order assembly in solution. Interface analysis shows predominantly polar interaction networks, and normalized B-factor mapping reveals localized flexibility near active-site-proximal regions. These findings provide a structural basis for understanding LAB-derived L-AIs and support structure-guided engineering toward food-grade, low-metal biocatalysts for rare-sugar production. Full article

Metallaphotoredox catalysis merges the powerful bond-forming abilities of transition metal catalysis with unique electron or energy transfer pathways accessible in photoexcited states, injecting new vitality into organic synthesis. However, most transition metal catalysts cannot be excited by visible light. Thus, prevalent metallaphotoredox catalytic systems require dual catalysts: a transition metal catalyst and a separate photosensitizer. This leads to inefficient electron transfer between these two low-concentration catalytic species, which often limits overall photocatalytic performance. Single-atom site catalysts (SASCs) offer a promising solution, wherein isolated and quasi-homogeneous transition metal sites are anchored on heterogeneous supports. When semiconductors are employed as the support, the photosensitive unit and transition metal catalytic site can be integrated into one system. This integration switches the electron transfer mode from intermolecular to intramolecular, thereby significantly enhancing photocatalytic efficiency. Furthermore, such heterogeneous catalysts are easier to separate and reuse. This review summarizes recent advances in the application of SASCs for photocatalytic organic synthesis, with a particular focus on elucidating structure–activity relationships of the single-atom sites. Full article

In this study, a novel Bi₂O₃/BiOBr_0.9I_0.1 (BO0.9−BBI0.1) composite photocatalyst was successfully synthesized via a single-pot solvothermal method for the efficient degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) under visible light. The structure, morphology, and optical properties of the photocatalyst were characterized through X-ray diffraction (XRD), Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectra (DRS), Steady-state photoluminescence (PL), and Electrochemical Impedance Spectroscopy (EIS). The composite exhibits a 3D hierarchical morphology with increased specific surface area and optimized pore structure, enhancing pollutant adsorption and providing more active sites. Under visible light irradiation, BO0.9−BBI0.1 achieved a 92.4% removal rate of 2,4-D within 2 h, with a reaction rate constant 5.3 and 4.6 times higher than that of pure BiOBr and BiOI, respectively. Mechanism studies confirm that photogenerated holes (h⁺) and superoxide radicals (·O₂⁻) are the primary active species, and the Z-scheme charge transfer pathway significantly promotes the separation of electron-hole pairs while maintaining strong redox capacity. The catalyst also demonstrated good stability over multiple cycles. This work provides a feasible dual-modification strategy for designing efficient bismuth-based photocatalysts for pesticide wastewater treatment. Full article