The conversion of biomass-derived ethanol into C6-12 alcohols offers a sustainable route for producing fine chemicals such as plasticizers and surfactants, but is hindered by challenges in enhancing and matching complex reaction rates that involve dehydrogenation/hydrogenation and C-C coupling. Herein, we design a hydroxyapatite-supported multifunctional catalyst system (Cu/HAP+Y/HAP) that efficiently converts ethanol into C6-12 alcohols, achieving selectivity of 71.8% and yield of 38.1% at 250 degrees C, which is superior to that of reported catalysts in the literature. The introduction of Y3+ increased the C-C coupling rate to 26.9 mmol center dot gCat. - 1 center dot h- 1 on HAP, matching the Cu0 enhanced hydrogenation/dehydrogenation rates of HAP. Specifically, by combining physical structure and chemical state analysis, we reveal that the active hydrogen generated at Cu0 sites migrates to HAP and Y3+ sites, thereby promoting surface-mediated hydrogenation of the C--C bond in butenal to butanal. The resulting butanal is subsequently generated into long-chain aldehydes by self-coupling or cross-coupling at the Y3+ site and the HAP basic site, and finally hydrogenated to form C6-12 alcohols. This study develops an efficient strategy for the targeted conversion and valorization of ethanol by precisely matching the rates of dehydrogenation/hydrogenation, coupling through catalytic system engineering, providing a valuable reference for catalyst design in high-value chemical conversion.

The rational design of single-atom catalysts (SACs) requires precise control over the local coordination environment. Yet the curvature of the supports, an intrinsic and tunable geometric parameter, is often overlooked. Herein, we present a high-throughput computational study combined with machine learning methods to unravel the effect of carbon support curvature on the catalytic performance of SACs for the CO2 reduction reaction (CO2RR). By investigating 28 transition metals (TMs) anchored on carbon nanotubes (CNTs) with different curvatures, we reveal that increasing curvature with higher surface energy universally enhances the thermodynamic and chemical stability of single atoms by strengthening metal-support interactions. Surprisingly, the support curvature can break the linear scaling relationship that the same metal species generally have identical adsorption trends for different species, by adjusting which the competitive hydrogen evolution reaction (HER) can be effectively suppressed. Additionally, machine learning reveals the d-band center as a key factor governing the curvature sensitivity of different metals. This work establishes support curvature as a controllable and intrinsic design dimension and proposes a general "curvature-engineering" strategy for developing efficient catalysts.

Acetic acid (AA) has a growing market with wide applications within the food industry and chemical intermediates. Conventional AA production processes rely heavily on fossil-based feedstocks and noble metal catalysts, resulting in high energy consumption and cost with poor environmental sustainability. Synthesis of AA using CO2 is of great importance and presents a promising avenue for addressing environmental challenges and advancing sustainable energy solutions. In this short review, we systematically summarize and discuss the development of AA synthesis from CO2 since the 1990s, and we manage to provide an in-depth analysis of the recent evolutions and corresponding catalytic systems for AA production from CO2. The review scrutinizes three ways (four routes) for the conversion of CO2 to AA, catalytic systems and reaction mechanisms, and offers a future direction for harnessing CO2 conversion to AA. Readers can acquire a thorough grasp of AA synthesis from CO2, revealing its promise as a sustainable route for chemical synthesis.

Wearable pressure sensors are in urgent practical demand for health monitoring and human-computer interaction, yet synergistically achieving high sensitivity, a broad detection range, and integrability within a lightweight configuration remains a major challenge. Herein, we propose an innovative integration of template-assisted electrospinning and ultrasonic dispersion to construct MXene-coated nanofibrous membranes with ordered microprotrusion array structures, establishing an effective strategy for high-performance flexible pressure sensors. The preferential stress concentration effect at the micro-protrusion tips efficiently promotes the formation, connection, and disconnection of MXene conductive pathways during loading-unloading cycles, thus enabling highly sensitive and stable pressure-sensing behavior. This structural effect endows the pressure sensor with the integration of high sensitivity (293.7 kPa−1), a broad detection range (350 kPa), and excellent cyclic durability, while retaining ultra-thin, lightweight, and flexible characteristics. These superior characteristics enable the flexible wearable pressure sensor array to precisely and real-timely monitor human motions, allowing accurate identification of various sitting postures under practical application conditions. Furthermore, the integration of deep learning algorithms enables accurate recognition of diverse sitting postures, offering a promising route for the practical deployment of intelligent wearable systems in multiple frontier fields.

A highly dispersed Rh catalyst supported on nitrogen-doped carbon nanotubes (CNTs) was prepared using a one-pot method and exhibited highly catalytic performance in the hydroformylation of olefin.

CO2 hydrogenation to C2+OH is highly attractive but remains a great challenge due to low C2+OH productivity and poor catalyst stability. Herein, we report efficient CO2 hydrogenation to C2+OH over a Ni- and K-co-modified Fe-based catalyst (1Ni-4K/Fe), achieving a promising space-time yield (STY) of 317.0 mg/g/h and catalytic stability over 300 h. Systematic investigations reveal that the addition of Ni promotes the formation of surface alkyl intermediates, while K mitigates the undesired deep hydrogenation of these alkyl intermediates. Both effects facilitate coupling between *CO and *CHx, thereby enhancing the production of C2+OH. Moreover, the synergistic effect between K and Ni expedites the formation of Fe5C2 and the recarburization of in situ oxidized Fe species during the reaction, resulting in enhanced stability of the 1Ni-4K/Fe catalyst. Additionally, by introduction of Rh-1/POP (for the hydroformylation of olefins to aldehydes) and Cu@SiO2 (for the hydrogenation of aldehydes to alcohols) catalysts to establish a 1Ni-4K/Fe||Rh-1/POPs||Cu@SiO2 triple-tandem system, an excellent C2+OH STY of 980.5 mg/g/h can be achieved, along with a C2+OH selectivity of 55.0% and a high proportion of C3+OH (75.6%) in the alcohol products.

The development of effective and stable non-precious catalysts for hydrogenation of ester to diols remains a challenge. Herein, the catalytic hydrogenation of ethyl lactate (EL) to 1,2-propanediol (1,2-PDO) with supported Co catalysts derived from layered double hydroxides (LDHs) is investigated. Catalytic tests reveal that LDH-derived Co catalysts exhibit the best catalytic performance with 98 % of EL conversion and >99 % of 1,2-PDO selectivity at mild conditions, compared with other Co catalysts (supported on Al2O3, and TiO2) and LDH-derived Cu catalysts. Due to the strong interaction among Co and Al matrix, the main composition is metallic Co0 and CoO after reduction at 600 °C. Besides, the catalyst shows good recyclability in the liquid phase hydrogenation. The superior catalytic performance can be attributed to the synergistic effect between Co0 and CoO, in which H2 molecule is activated on Co0 and EL is strongly adsorbed on CoO via hydroxyl groups.

As a typical atomically dispersed catalyst, single -atom catalysts (SACs) aroused enormous research interest in heterogeneous catalysis. In recent years, by incorporating one or several metal atom(s) into the first and/or outer coordination shells of single atoms, the structure of metal has evolved to densely populated single atoms, dual -metal pairs, and multi-atom ensembles. The inter-site or inter-atom synergetic interactions between adjacent metal atoms in these structures boost the adsorption and activation of reactants, potentially leading to improved catalytic performances as compared with corresponding SACs. This perspective highlights the structural advantages of densely populated single atoms, dual -metal pairs, and multi-atom ensembles using many of the successful examples, aiming to shed light on the design of novel catalysts at atomic level.

AbstractRegulating interfacial electronic structure of oxide-metal composite catalyst for the selective transformation of biomass or plastic waste into high-value chemicals through specific C–O bond scission is still challenging due to the presence of multiple reducible bonds and low catalytic activity. Herein, we find that the inverse catalyst of 4CeOx/Ni can efficiently transform various lignocellulose derivatives and polyether into the corresponding value-added hydroxyl-containing chemicals with activity enhancement (up to 36.5-fold increase in rate) compared to the conventional metal/oxide supported catalyst. In situ experiments and theoretical calculations reveal the electron-rich interfacial Ce and Ni species are responsible for the selective adsorption of C–O bond and efficient generation of Hδ− species, respectively, which synergistic facilitate cleavage of C–O bond and subsequent hydrogenation. This work advances the fundamental understanding of interfacial electronic interaction over inverse catalyst and provides a promising catalyst design strategy for efficient transformation of C–O bond.

The catalytic upgrading of renewable ethanol to C4-10 alcohols via C-C coupling offers a green and negative-carbon-emission pathway toward value-added compounds. The manipulation of catalysts' surface basic and acidic properties is the key to achieve high-selectivity C4-10 alcohols. In this study, we present a solvent-free mechanochemical approach for the synthesis of hydroxyapatite (HAP) catalysts with enhanced basicity. The selectivity for a total C4-10 alcohols reaches 97.8% with a yield of 53.9% at 325 degrees C and 0.1 MPa, surpassing previously reported catalysts in the literature. The mechanochemically synthesized HAP catalysts extend along the c-axis and expose the (002) crystal plane with enriched strong basic [Ca-O-P] sites. CO2-TPD and XPS analyses demonstrated that the hydrogen bonds between the oxygen atoms of adjoining phosphate groups enhance the basic property of the catalyst surfaces. The kinetic measurements have demonstrated that the abundance of strong basic sites facilitates the adsorption of ethanol molecules and accelerates the rate of C-C coupling reactions, which is responsible for a high yield of C4-10 alcohols. This work offers a sustainable approach for synthesizing such alcohols and stimulates the advancement of environmentally friendly catalysts.

A series of Mo/Sn (1:20, molar ratio) catalysts were prepared by two-step hydrothermal synthesis method, and the effect of calcination temperature of tin precursors on the reaction performance of methanol oxidation to dimethoxymethane (DMM) was investigated. The crystal structure, surface properties, redox property and valence change of molybdenum species of the catalyst were characterized by XRD, Raman, FT-IR, XPS, NH3-TPD and H2-TPR. The results showed that Mo1Sn20-600°CSn catalyst exhibited better performance than other catalysts, achieving DMM selectivity of 90% with methanol conversion of 30% at 140 °C. From the characterization results, the surface properties of the tin precursors affected the structure of catalyst, the degree of molybdenum oxide dispersion and valence of molybdenum species, and further influenced the performance of the catalysts. The high temperature calcination of tin precursors is more favorable for the generation of Mo6+ in the Mo1Sn20 catalyst.

Ni-based catalysts have been widely studied in the hydrogenation of CO2 to CH4, but selective and efficient synthesis of higher alcohols (C-2+OH) from CO2 hydrogenation over Ni-based catalyst is still challenging due to successive hydrogenation of C1 intermediates leading to methanation. Herein, we report an unprecedented synthesis of C2+OH from CO2 hydrogenation over K-modified Ni-Zn bimetal catalyst with promising activity and selectivity. Systematic experiments (including XRD, in situ spectroscopic characterization) and computational studies reveal the in situ generation of an active K-modified Ni-Zn carbide (K-Ni(3)Zn(1)C(0.)7) by carburization of Zn-incorporated Ni-0, which can significantly enhance CO(2 )adsorption and the surface coverage of alkyl intermediates, and boost the C-C coupling to C2+OH rather than conventional CH4. This work opens a new catalytic avenue toward CO2 hydrogenation to C2+OH, and also provides an insightful example for the rational design of selective and efficient Ni-based catalysts for CO2 hydrogenation to multiple carbon products.

As a new generation of metal‐free carbon catalyst, the sp 3 @ sp 2 ‐hybridized bucky nanodiamond (ND) is competitive even compared to the traditional metal catalysts in many oxidative reactions. However, the application of the carbon catalyst in reduction reaction is barely conducted and the mechanism of this kind of reaction is generally unknown. To develop a wider scope of carbon catalysts and achieve an industrial promising activity of the metal‐free catalyst, here a series of sp 3 @ sp 2 ‐hybridized bucky ND for catalyzing a model reduction reaction of 4‐nitrophenol to 4‐aminophenol is developed, in which a quite satisfying metal‐free catalytic performance (better than many metal catalysts) is obtained and the discipline of getting better activities for the reduction reaction is revealed. The oxygen functionality and sp 3 / sp 2 hybridized carbon ratio are confirmed to be the important influential factors. The similarity of the carbon catalyzing the reduction and oxidation reactions might bring a uniform concept for redox reactions with carbon catalysts.

Supported Cu nanoparticle catalysts are the main players in hydrogenation of CO2 to methanol, however, the challenges in selectivity and catalyst stability have not been properly addressed due to the reverse water-gas shift reaction initiated by Cu nanoparticles and their sintering/oxidation. Here, we have developed a series of Cu,Zn-codoped ZrO2 catalyst, in which Cu and Zn are highly dispersed into the matrix of ZrO2. The optimal Cu,Zn-codoped ZrO2 catalyst demonstrates outstanding performance compared with Cu-doped ZrO2, Zn-doped ZrO2 and Cu-doped ZnO catalysts. Chemisorption, H2-D2 exchange and in situ diffuse reflectance infrared Fourier transform spectroscopy analyses reveal that the synergy interaction between the doped Zn and Cu plays a crucial role in boosting the selective production of methanol synthesis via promoting CO2 adsorption and H2 dissociation. This study provides an intriguing example for the development of selective and stable Cu-catalyst for the CO2 hydrogenation via metal-doping strategy.

A fundamental problem of catalytic hydrogenation is the activation of H-2, which is usually believed to occur through the interactions between H-2 and the active center of a catalyst. In the present study, we show that H-2 can be activated by chemisorbed C2H2 acting as a substrate molecule. This mechanism can occur when it is unfavorable for H-2 to approach the metal-center of the catalyst, which is caused by relatively strong adsorption C2H2. We demonstrate the proposed mechanism on various single/dual atom catalysts to establish a linear scaling relation generalizing the trend of H-2 activation by C2H2. We also show that Ir-doped graphene is a promising catalyst for the semi-hydrogenation of C2H2 where H-2 is preferably activated by the chemisorbed C2H2. The calculated turnover frequency reaches 0.076/s at 423 K and the selectivity to C2H4 approaches 100 %. The present study sheds light on mechanistic study of heterogeneous hydrogenation catalysts.

Engineering the surface microenvironment by tuning the binary interactions between a supported metal with a secondary metal oxide (MOx) or support has been a common method for improving the catalytic performance of supported metal catalysts. However, few studies have investigated the ternary interactions among the metal, MOx, and support. Here, we report for the first time the formation of metal-MOx-support interaction (MMSI) in reducible TiO2-supported PtReOx catalysts, affording 87% yield and 100% ee in the tandem hydrogenation of an aqueous chiral cyclohexane-1,2-dicarboxylic acid into the corresponding diol; the catalytic activity is eight times higher than that obtained with non-reducible support counterparts in the same reaction via traditional batch synthesis with multiple steps and unfriendly reagents. Detailed experimental and computational studies suggest that the TiO2 crystalline phase-dependent density of the oxygen vacancies induces different Pt-ReOx-TiO2 interactions, which dominate the electron transfer therein and tune the adsorption strength of the carbonyl moiety of the substrate/intermediate, thus promoting the hydrogenation activity and selectivity. In addition, the strong MMSI endows the optimal rutile TiO2 supported PtReOx catalyst with an outstanding lifetime of 400 h in a fixed-bed reactor under acidic aqueous conditions and ensures efficient applications in the selective hydrogenation of aliphatic dicarboxylic acids and functional carboxylic acids. This work provides a promising strategy for the development of efficient and stable supported catalysts for the selective hydrogenation of diverse C–O and C=O bonds.

Artificial zeolite was modified by nano-Fe3O4 for development of functional adsorbents. Subsequently, adsorbents such as calcium cross-linked nano-Fe3O4 microspheres (Ca-MS), calcium cross-linked nano-Fe3O4 modified zeolite microspheres (Ca-MZS) and iron cross-linked nano-Fe3O4 modified zeolite microspheres (Fe-MZS) were prepared and compared for their adsorption performance. The effects of adsorbent dosage, solution pH, initial concentration and ion content on the removal of Cu2+ from wastewater are investigated, and the adsorption kinetics and isotherms for the adsorbent materials were analyzed. The experimental results indicate that for the initial concentration of Cu2+ of 30 mg/L, the adsorption is noted to be most stable. The optimal initial pH for adsorbing Cu2+ is observed to be 5.5. At an optimal dosage of Ca-MZS of 900 mg/L, the adsorption capacity is measured to be 28.25 mg/g, along with the removal rate of 72.49%. The addition of Na+ and K+ affects the adsorption of Cu2+. For the Na+ and K+ concentration of 0.2 mmol/L, the Cu2+ removal rate by Ca-MZS drops to 11.94% and 22.12%, respectively. As compared with the adsorbents such as Natural Zeolite (NZ), Ca-MS and Fe-MZS, Ca-MZS demonstrates the best removal effect in solution, where the removal rate reaches 84.27%, with the maximum adsorption capacity of 28.09 mg/g. The Cu2+ adsorption kinetics of Ca-MZS is observed to follow the Elovich kinetic model, with the adsorption isotherm data fitting the Freundlich isotherm model by using the non-linear method.

Single-atom metal-nitrogen-carbon (M-N-C) catalysts have sparked intensive interests, however, the development of an atomically dispersed metal-phosphorus-carbon (M-P-C) catalyst has not been achieved, although molecular metal-phosphine complexes have found tremendous applications in homogeneous catalysis. Herein, we successfully construct graphitic phosphorus species coordinated single-atom Fe on P-doped carbon, which display outstanding catalytic performance and reaction generality in the heterogeneous hydrogenation of N-heterocycles, functionalized nitroarenes, and reductive amination reactions, while the corresponding atomically dispersed Fe atoms embedded on N-doped carbon are almost inactive under the same reaction conditions. Furthermore, we find that the catalytic activity of graphitic phosphorus coordinated single-atom Fe sharply decreased when Fe atoms were transformed to Fe clusters/nanoparticles by post-impregnation Fe species. This work can be of fundamental interest for the design of single-atom catalysts by utilizing P atoms as coordination sites as well as of practical use for the application of M-P-C catalysts in heterogeneous catalysis.

为了提高硝化菌和反硝化菌在沸石表面的附着性能,达到高效处理初期屋面雨水中氨氮及延长挂膜沸石使用寿命的目的,进行了酰基高丝氨酸内脂类信号分子(AHLs)强化沸石挂膜实验研究.实验结果表明:添加2.0μmol/L C12-HSL能够显著提高硝化菌WGX5、WGX13在沸石表面的附着能力,使其生物附着量分别提高了89％和94％,但是对反硝化菌HF2、HF8的附着能力提高幅度有限.调控碳氮比为4时投加2.0μmol/L C12-HSL不仅可以提高硝化菌WGX5、WGX13的附着能力,也可显著提高反硝化菌HF2和HF8的附着性能,使HF2和HF8的生物附着量相比碳氮比为2、投加2.0μmol/L C12-HSL时分别提高了1.3倍和1.6倍.该条件下制备的挂膜沸石可长期有效去除初期屋面雨水中的氨氮(5轮实验中氨氮去除率均高达91％ ～98％),此外还可去除部分化学需氧量(chemical oxygen demand,COD)(5轮实验中COD去除率可达61％ ～70％).强化挂膜后沸石的原位再生率由34％提高至83％,因此,有效延长了沸石的使用寿命,5轮实验中强化挂膜沸石均能有效去除屋面雨水中的氨氮.