Conventional cutting fluids often rely on non-renewable mineral oils and hazardous additives, raising serious environmental and occupational safety concerns. Developing green, high-performance alternatives is therefore imperative for advancing sustainable manufacturing. Amphiphilic Fe3O4@SiO2-C12 core-shell nanoparticles were synthesized and used to stabilize vegetable oil-in-water Pickering emulsions as novel nano-cutting fluids. Systematic characterization confirmed the successful formation of superparamagnetic nanoparticles with tunable wettability. Response surface methodology (RSM) optimized the formulation to pH 8.9, 2.9 wt% cottonseed oil, and 0.18 wt% nanoparticles, achieving a zeta potential of −42.533 mV and wear scar diameter of 0.393 mm. The optimized Pickering emulsion demonstrated superior performance versus the commercial cutting fluid, including a low friction coefficient of 0.0666, a 17.09% reduction in wear scar diameter, a 10.21% decrease in tapping torque, and a 15.40% enhancement in thermal conductivity (0.645 W/(m·K)). X-ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM)-energy-dispersive spectroscopy (EDS) revealed a triple synergistic lubrication mechanism involving physical adsorption, tribochemical Fe2O3/FeO film formation, and nanoparticle-enabled micro-bearing and heat conduction. The Pickering emulsion also demonstrated excellent magnetic responsiveness, enabling rapid, magnetically controlled demulsification and oil-water separation for recycling. In this work, a high-performance and environmentally friendly cutting fluid was developed and evaluated for sustainable manufacturing applications.

The hydration of acetylene reaction represents a pathway with long-standing industrial strategic value in coal chemistry. However, the catalytic efficiency is hampered by inherent challenges such as the high inherent reactivity of acetylene, competitive adsorption on active sites, and an intricate network of parallel reactions that lead to byproducts. These factors make precise catalytic control over reaction selectivity paramount for achieving high target product yields. To address this, the classic metal-organic framework ZIF-8 and its pyrolytically derived Zn-N-C material were synthesized and systematically evaluated as catalysts for this transformation. Experimental results demonstrated that ZIF-8, featuring a Zn-N4 coordination structure, achieved an acetone selectivity of 87 %, whereas the Zn-NC material with a Zn-N3 coordination structure exhibited a acetaldehyde selectivity of 70 % under identical reaction conditions. XPS and XAFS analyses revealed that pyrolysis induced a transformation in the coordination environment of ZIF-8 from Zn-N4 to Zn-N3. DFT calculations further clarified the structure-selectivity relationship between coordination geometry and product distribution. Specifically, for ZIF-8 with Zn-N4 sites, beta-ketobutyraldehyde decarbonylation served as the rate-determining step, featuring a lower energy barrier that favors acetone formation. In contrast, for Zn-NC with Zn-N3 sites, acetylene activation becomes the rate-determining step, and its lower energy barrier promotes acetaldehyde production. This work underscores the critical role of local coordination structures in acetylene hydration and offers a novel strategy for enhancing catalytic selectivity through precise modulation of the metal active center coordination environment.

Developing high-performance, eco-friendly cutting fluids is essential for sustainable manufacturing. This work prepared a novel vegetable oil-based Pickering emulsion cutting fluid stabilized by Fe3O4@SiO2-C-8 core-shell nanoparticles, whose surface wettability was tailored via octylsilane grafting. A three-factor, three-level Box-Behnken design coupled with response surface methodology was employed to optimize the formulation using Friction Index and Cooling Index as dual responses. The regression models exhibited high prediction accuracy (R-2 > 0.98) and statistical significance (p < 0.0001). The optimal formulation was determined as contact angle 79.076 degrees, soybean oil content 5.381 wt%, and nanoparticle concentration 0.211 wt%. Under these conditions, the optimized emulsion achieved a coefficient of friction of 0.0787, wear scar diameter of 0.454 mm, and thermal conductivity of 0.602 W/(m & centerdot;K), corresponding to improvements of 11.38%, 5.88%, and 8.80% relative to a commercial fluid. Mechanistic analyses verified the formation of a robust Fe2O3/FeO-SiO2 composite tribofilm via tribochemical reactions, combined with nanoparticle micro-bearing effect and thermal bridge action. This green fluid provides a promising alternative to conventional petroleum-based cutting fluids.

Gold catalysts are considered the most promising non-mercury alternatives for the environmentally urgent replacement of toxic mercuric chloride (HgCl2/AC) catalysts in the industrial production of vinyl chloride monomer (VCM) via acetylene hydrochlorination. Their commercialization, however, is critically limited by rapid deactivation due to the reduction and agglomeration of active Au+ species. To develop a practical catalyst with industrial viability, we designed and synthesized a rubidium-promoted gold catalyst supported on activated carbon (AuRb/AC). This catalyst demonstrates exceptional and stable performance, achieving a C2H2 conversion of 88.3% with a VCM selectivity exceeding 99.9%, which is both superior to the conventional Au/AC catalyst and approaches the level required for industrial application. Most notably, the AuRb/AC catalyst shows outstanding operational stability, maintaining its initial activity without noticeable deactivation during a 110 h time-on-stream test (500 h-1), a key metric for process economics. Characterization reveals that the introduced Rb effectively stabilizes the active Au+ centers against reduction and sintering, while also promoting reactant activation. This work provides a robust and efficient catalytic solution, paving the way for the practical, industrial application of gold-based catalysts in acetylene hydrochlorination.

Ligand-protected encapsulated Cu@TS-1(2) with confined Cu nanoparticles delivers enhanced selectivity and stability, driven by Cu–N bonds for acetylene adsorption and synergistic CuO(111)/Cu(111) facets for formaldehyde activation.

Notwithstanding the breakthrough represented by the use of heteroatom-doped carbon materials in acetylene hydrochlorination, mimicking the mercury active site, problems such as activity decay due to carbon build-up in continuous operation have seriously constrained the industrialization process. In addressing this challenge, this study innovatively employed 3-aminophenol formaldehyde resin spheres as self-templates. Through a controlled oxidation-carbonization strategy under air atmosphere, a N-doped hollow carbon sphere catalyst (APF-A600N700) with a well-defined hollow structure was successfully constructed. This material exhibited exceptional performance in acetylene hydrochlorination: under the conditions of 220 degrees degrees C, an acetylene gas hourly space velocity of 40 h-1, and a V(HCl)/V(C2H2) ratio of 1.15, the acetylene conversion reached 98.8%. Furthermore, the activity decay rate was as low as 0.023%/h during a 100-hour continuous test. Systematic characterization revealed that air oxidation not only facilitated the transformation of the resin template into the hollow structure but also optimized the coordination environment of nitrogen species within the carbon framework. The resulting hollow cavity effectively alleviated mass transfer limitations during the reaction and significantly suppressed carbon deposition. By adopting a synergistic strategy of "structural design-heteroatom modulation", this study achieved simultaneous enhancement of catalytic activity and stability. This work not only provides a novel and efficient catalyst for the green synthesis of vinyl chloride but also provides a research idea for the structural design of functional carbon materials.

MoO 3 calcined under an oxidative atmosphere exhibits superior diethyl oxalate selectivity, which depends critically on the presence of Lewis acidic Mo 6+ species and their cooperative interaction with Brønsted acidic Mo–OH sites.

Electrocatalytic nitrate reduction (NO3RR) presents a promising approach for sustainable NH3 synthesis and wastewater treatment. However, its efficiency in neutral media is hindered by sluggish reaction kinetics and competitive hydrogen evolution reaction. Here, a strategy to construct a highly active Cu0/Cuδ+ interface via oxygen-vacancy-triggered local amorphization was proposed, by which the Ov-CuxO/NF catalyst was obtained. Experimental and theoretical results reveal that this interfacial architecture optimizes the electronic distribution, modulates the built-in electric field to stabilize the active Cuδ+, synergistically enhancing NO3- adsorption and activation while facilitating H2O dissociation to provide *H. Moreover, Cuδ+ associated with oxygen vacancies facilitate a dual-spillover effect of *NO2- and *H between Cu0 and Cu+ sites. Consequently, Ov-CuxO/NF achieves exceptional NO3RR performance in neutral media, with a NH3 FE of 98.5% at -0.6 V vs. RHE, a yield rate of 15.66 mg·h-1·cm-2, and stable operation over 21 cycles. The catalyst also demonstrates robust applicability in simulated wastewater treatment, catalyst regeneration, electrode upscaling, solar energy application and the further conversion of produced NH3 into high-purity struvite. This work highlights defect engineering and interface design as effective strategies for developing efficient and stable copper-based NO3RR catalysts.

The practical implementation of electrocatalytic nitrate reduction reaction (NO3RR) for ammonia synthesis is critically hindered by its inherent sensitivity to temperature fluctuations, which leads to unpredictable selectivity shifts among NO3RR, nitrite reduction reaction (NO2RR), and the hydrogen evolution reaction (HER). Using Cu2O as a model catalyst, the temperature-dependent competition among different pathways within the 10-40 degrees C range was elucidated. An atomically dispersed Co-doped Cu2O catalyst (Co-Cu2O) was then designed to function as a thermal-adaptive platform. Mechanistic studies reveal that the atomically dispersed Co sites not only enhance the intrinsic hydrogenation capability but also dynamically stabilize key N-H intermediates (*NOH, *NH2, and *NH3) against temperature variations. This synergistic effect stabilizes the reaction pathway toward NH3, enabling robust and selective ammonia production under thermal perturbations. As a result, the Co-Cu2O catalyst maintains a Faradaic efficiency (FE) for NH3 above 90 % across the entire 10-40 degrees C temperature window and achieves a remarkable NH3 production rate of 53.79 mg h-1 mgcat-1 at 40 degrees C. This work provides fundamental insights into temperature-mediated catalysis and establishes an effective design strategy for wide-temperature electrocatalysts.

The impact of electron-donating groups (EDGs) at the ortho-phenoxy position of phosphino-phenolate nickel catalysts on ethylene polymerization and copolymerization with polar monomers was systematically investigated. Three phosphino-phenolate catalysts based on EDG (Ni1, -OMe; Ni2, -OH; Ni3, -CH2OH) were designed and synthesized, which are moderately active single-component catalysts for ethylene polymerization at elevated temperatures (up to 150 degrees C), producing high molecular weight linear polyethylene with a melting point as high as 136.0 degrees C. The reduced electron-donating ability of EDG decreased the activity and molecular weight. Most importantly, a single crystal of the Ni-Li heterobimetallic complex, based on Ni1 and a lithium Lewis acid unit, was confirmed by X-ray diffraction analysis. Besides, Ni1 and Ni2 demonstrated superior performance in ethylene/polar monomers copolymerization, achieving 1.9-mol% polar monomer incorporation, resulting in excellent surface properties of the copolymer. The impact of ortho-phenoxy EDGs in phosphino-phenolate nickel catalysts is explored, revealing their high thermal stability and activity in ethylene polymerization to yield high molecular weight linear polyethylene. Notably, these catalysts exhibit excellent performance in ethylene copolymerization with polar monomers, significantly enhancing copolymer surface properties.

Electrocatalytic nitrate reduction reaction (NO3RR) offers sustainable ammonia synthesis from industrial flue gases, yet SO2-induced sulfur poisoning hinders catalyst activity. Herein, we engineer Cu-doped BiFeO3 (Cu-BFO) with optimized oxygen vacancies, demonstrating NH3 Faradaic efficiency (FE) of 92.1 +/- 0.27% and NH3 yield rate of 36.2 +/- 1.86 mg mg(cat)(-1) h(-1) at -0.6 V vs.RHE. In-situ analysis and Density Functional Theory (DFT) calculations confirm NO3RR pathway and mechanism. Within the SO32-/NO3- ratio range from 0.1 to 1, the NH3 FE kept higher than 79.3% and 88.8% for NO3RR and NO2RR, respectively. The Cu-BFO maintains 64-h stability and > 80% FE at -0.6 V vs.RHE under 0.05 M SO32- conditions. Electrolyte refreshment recovers slightly attenuated activity. Catalyst reconstruction induces phase separation, re-exposing Cu sites and regenerating NO3RR activity. This work provides insights into catalytic interface design for high SO2 resistance through defect engineering. This paper deepens the understanding of SO2 poisoning mechanism and regeneration methods during electrocatalytic nitrate reduction.

In the development of mercury-free catalysts for acetylene hydrochlorination, Ru-based catalysts are among the most promising candidates, yet their large-scale application remains limited by severe deactivation due to carbon deposition. In this work, a ruthenium catalyst supported on nitrogen-doped activated carbon (Ru/NC) was developed, which exhibited excellent performance in the acetylene hydrochlorination reaction. The Ru/NC catalyst achieved a C2H2 conversion of 93.0%, approximately 2.2 times and 1.3 times higher than those of the Ru/AC and Ru/AC-Ar catalysts, respectively. Stability tests further confirmed that the Ru/NC catalyst possesses significantly higher durability compared to the Ru/AC and Ru/AC-Ar catalysts. Characterization results reveal that Ru species are highly dispersed on the nitrogen-doped carbon support, and the incorporation of nitrogen species plays a key role in stabilizing the Ru active sites, enhancing HCl activation, and improving the surface reaction kinetics.

Developing non-mercuric catalysts for acetylene hydrochlorination to vinyl chloride monomer (VCM) in the chemical industry is imperative. Gold-based catalysts are promising alternatives but suffer from low conversion rate. Herein, we systematically investigate the promotion effect of alkali metals (Li, Na, K, Rb) on Au/AC catalysts. Catalytic activity positively correlates with the atomic number of the alkali metal promoter. Characterizations confirm that alkali metals stabilize active Au+ species and boost the activation of C2H2 and HCl. This work identifies Au+ content as a key performance descriptor for alkali metal promoted Au catalysts, providing a rational design principle for non-mercuric VCM synthesis.

Synthesis of cyclohexylamine via reductive amination of biomass-derived phenol aligns with sustainable chemistry principles. However, the structure-activity relationships governing catalytic performance remain unexplored, which is crucial for regulating the product selectivity. In this work, an effective Ni3Al1O x catalyst was developed for reductive amination of phenol to cyclohexylamine, achieving excellent yields. Both Ni0 and Ni2+ species are essential, and the best Ni2+/Ni0 ratio is 2.86. The optimal Ni2+/Ni0 ratio of the Ni3Al1O x -600 catalyst is favorable for the adsorption of phenol and NH3 and the desorption of cyclohexylamine, which is key for achieving superior catalytic activity and selectivity.

Traditional mineral oil-based cutting fluids are increasingly incompatible with sustainable manufacturing due to their environmental and health impacts. To solve these challenges, this work presented a green and scalable strategy for a high-performance nano-cutting fluid by constructing a plant-based Pickering emulsion. This system innovatively utilized cottonseed oil as the base oil, stabilized by oleylamine (OA) modified MoS2 nanosheets (MoS2-OA) at the oil-water interface. The formulation was rationally designed and optimized by response surface methodology (RSM) to synergistically enhance emulsion stability, lubrication, and heat dissipation. The resulting Pickering emulsion is demonstrated to possess a unique combination of significantly reduced friction and wear, along with improved thermal conductivity, outperforming a commercial cutting fluid. Mechanistic analysis revealed that MoS2-OA nanosheets formed a multifunctional interfacial film, which synergistically served as a “lubrication film” for low friction and a “thermal bridge” for efficient heat dissipation. Thus, a novel paradigm for developing sustainable metalworking fluids is established by leveraging the synergistic potential of non-edible plant oils and functional nanomaterials.

The preparation of dimethyl oxalate (DMO) through syngas coupling followed by deep hydrogenation to produce ethanol (EtOH) represents a crucial approach for the clean utilization of coal in the chemical industry. However, designing highly active catalysts under low-temperature and low-pressure conditions remains a significant challenge. This study presents the design and development of a bimetallic iron-nickel nitride catalyst for the hydrogenation of DMO to EtOH, achieving an EtOH yield of 97.5% at 220 degrees C and atmospheric pressure. Results indicate that nitridation at 400 degrees C leads to the formation of more FeNi3N active phases with an increased number of acidic sites. These phases exhibit enhanced H2 and DMO adsorption capacities, thereby significantly improving catalytic activity. In-situ DRIFTS analysis reveals that DMO undergoes activation through C--O and C-O bonds, which facilitates its reaction to form EtOH. DFT simulations demonstrate that the electron-rich nitrogen environment promotes electron transfer to the metal active site, enhancing DMO activation and H2 dissociation. This interaction reduces both the catalytic reaction and H2 dissociation energy barriers, substantially boosting the catalyst's activity. This work represents the first demonstration of high EtOH yield via low-temperature hydrogenation of DMO under atmospheric pressure, offering a new strategy for developing highly active catalysts for ester hydrogenation under mild conditions.

Perovskite oxides have emerged as promising electrocatalysts for the oxygen evolution reaction (OER) due to their cost-effectiveness, tunable structure, excellent stability, and intrinsic activity. However, their low specific surface area and poor electronic conductivity limit their large-scale water electrolysis applications. Herein, we construct Fe-based metal-organic framework (Fe-MOF) and iron oxyhydroxide (FeOOH) layers on a self-supported La0.7Sr0.3CoO3-δ/nickel foam (LSC/NF) to comparatively investigate their interfacial coupling effects on OER performance. Fe-MOF@LSC/NF exhibits superior OER performance in 1 mol L−1 KOH, with low overpotentials of 218 mV and 268 mV at current densities of 10 mA cm−2 and 50 mA cm−2, respectively, and a Tafel slope of 30.0 mV dec−1, outperforming FeOOH@LSC/NF, RuO2, and pristine LSC/NF. Even in harsh oilfield wastewater electrolyte, Fe-MOF@LSC/NF maintains excellent catalytic performance. Mechanistic studies reveal that Fe-MOF forms strong chemical Fe-O-Co interfacial bridges with LSC, whereas FeOOH primarily physically adsorbs. This robust chemical coupling optimizes electronic structure, enhances conductivity, and stabilizes oxygen vacancies, leading to accelerated reaction kinetics. This study elucidates the critical role of interfacial bonding in perovskite-based electrocatalysts, offering insights for designing efficient, durable non-precious metal OER catalysts.

Background The acetylene hydration process for acetaldehyde production represents a well-established and strategically significant pathway in coal chemistry. Nevertheless, this reaction encounters several challenges, such as the high reactivity of acetylene, competitive adsorption among reactants, and intricate reaction networks that lead to by-product formation. The remarkable porosity and exceptional chemical stability of metal-organic frameworks endow them with immense potential for the preparation of porous carbon materials. Methods Herein, the sulfur-modified ZIF-8 materials in situ were synthesized through a one-pot method and further prepared a N, S co-doped porous carbon Zn-based catalyst by thermal decomposition. The catalytic performance of N, S co-doped porous carbon Zn-based materials results showed that the Zn-NSC-600 exhibited excellent catalytic performance. Significant Findings The X-ray absorption fine structure (XAFS) and X-ray photoelectron spectroscopy (XPS) results revealed the presence of zinc species in N, S co-doped porous carbon Zn-based materials as Zn-N3 structure, while sulfur atoms were embedded into the carbon support via C-S-C bonds. The TEM and EDS results revealed an evident carbon shell on the surface of the Zn-NSC-600 material, with the active metal Zn exhibiting excellent dispersibility. Additionally, the addition of S-atoms could effectively stabilize the material structure and suppress the loss of active Zn species. Meanwhile, the DFT calculations indicated that the activation of acetylene was the rate-determining step for the Zn-NSC materials. The introduction of sulfur atoms could significantly decrease the activation energy of acetylene, which is more favorable for the reaction. This study not only presented a novel N, S co-doped porous carbon Zn-based catalysts with superb catalytic efficiency but also proposed a strategy to enhance and control the heteroatom doping of Zn-based catalysts for acetylene hydration.

Heterogeneous polymerization represents a widely employed method in the polyolefin industry. In recent years, various heterogenization strategies for late transition metal catalysts have been developed, enabling effective control of polymer morphology and optimization of catalytic performance. However, while most studies have focused on designing anchoring groups and advancing support approaches, systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts. In this work, we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl2 supports. The ethylene polymerization behavior of these catalysts was then investigated. By precisely adjusting the alkyl alcohol chain length, the distance between the catalytically active metal center and the support surface was modulated. This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.

Regulating the dynamic evolution of active sites is key to improving the stability of Cu-based catalysts for acetylene hydrochlorination. Herein, we report a strategy to boost catalytic stability by in-situ tuning the Cu0/Cuδ+ dual-site ratio. Using copper oxalate as a precursor, the 10% CuC2O4/AC-900 catalyst is prepared via carbothermal reduction. By controlling HCl-activation time, the surface chemical state of Cu species can be finely modulated to construct an optimal Cu0/Cuδ+ pair. Activation for 40 min yields excellent reaction stability, as it optimizes the concentration of active Cuδ+ species and establishes a dynamic balance between activity and stability. Additionally, we propose a hydrogen-assisted stabilization mechanism: introducing trace H2 into the reaction atmosphere prevents deep chlorination and deactivation of Cu sites, stabilizes the Cu0/Cuδ+ dual-site structure, and significantly prolongs catalyst lifetime. This work deepens fundamental understanding of active sites in acetylene hydrochlorination and provides theoretical insights and practical guidelines for designing stable mercury-free catalysts.