1,3-Butadiene (hereafter referred to as butadiene), an essential component in the petrochemical industry, has witnessed a consistent annual increase in demand. Ethanol, a plentiful biomass resource, has garnered significant attention due to its potential conversion into high-value-added chemicals. The synthesis of butadiene from ethanol is a significant research direction. Two distinct technical approaches have been identified for the synthesis of butadiene from ethanol: the one-step and the two-step methods. The one-step method involves the direct conversion of ethanol to butadiene through the use of suitable catalysts and reaction conditions, exhibiting advantages such as simplicity in reaction steps and high butadiene selectivity. Conversely, the two-step method necessitates an additional dehydrogenation of ethanol to acetaldehyde in the synthesis of butadiene. A critical evaluation of both methods reveals that each possesses distinct advantages and disadvantages, yet both demonstrate significant potential and feasibility. Catalyst selection, reaction mechanism, and process conditions are pivotal to the study of butadiene from ethanol. Through rigorous research and optimization, both the one-step and two-step methods are poised to assume a significant role in the realm of sustainable chemical industry.

Abstract Hydrogenated bisphenol A (H12BPA) serves as a high-performance alternative to bisphenol A (BPA) in polymer and electronic materials. However, the hydrogenation of BPA faces significant kinetic barriers, requiring high Ru loading and resulting in low selectivity and high cost. Herein, a continuous microreactor was employed to enhance multiphase mass transfer and improve reaction efficiency. After optimizing the reaction parameters, a 2.0 wt % Ru/C catalyst achieved 100% BPA conversion and 99.1% H12BPA selectivity at 130 °C and 3.0 MPa, maintaining stable performance over 700 h continuous operation. A kinetic network model well matched the experimental data, and the hydrogenation of the intermediate H6BPA to H12BPA is the rate-determining step. This work provides a scalable route for BPA hydrogenation and reliable kinetic parameters for continuous-flow process design.

The development of highly efficient and stable non-precious metal catalysts under mild conditions is highly desirable for NH3 synthesis. However, the competitive adsorption of N-2 and H-2 on the single site and strong NH3 adsorption greatly hinder the catalytic efficiency of catalysts under mild conditions. Herein, we propose the use of responsive alkali metal perrhenates (AMReO(4), AM = K, Na, or Cs) supports with scheelite-type structure that contains active Re metal and promoters to disperse cobalt (Co) species, constructing highly efficient catalysts by regulating the competitive reactant adsorption-activation pattern to a non-competitive mechanism. Our studies demonstrate that Co/KReO4 catalyst shows excellent catalytic performance for NH3 synthesis. Co and Re sites synergistically to promote the activation of N-2 molecules, while the adsorption and activation of H-2 primarily occur on Re sites of KReO4. The presence of Co species facilitates H-spillover that enables the migration of *H species from Re to Co sites, then cascade catalysis of hydrogen and dissociated nitrogen species to form NH3. Accordingly, the NH3 synthesis rate of Co/KReO4 (11.48 mmol(NH3) g(cat)(-1) h(-1)) is 3.2-fold higher than that of KReO4 (3.58 mmol(NH3) g(cat)(-1) h(-1)) at 400 degrees C and 1 MPa. This work emphasizes the significance of employing reactive supports containing promoters and active metals, in collaboration with non-precious Co sites, to enhance NH3 synthesis performance under mild conditions.< br /> (c) 2026, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

The potential use of ammonia (NH3 ) as a hydrogen energy carrier has generated significant interest in developing efficient catalysts for producing NH3 under mild conditions. The main obstacles for NH3 synthesis are the activation of the N equivalent to N bond and the desorption of NH3 from the catalyst surface. Here, we report the use of C60 to overcome these challenges. Through electron transfer, migration, and feedback between C60 and Ru, there is a balance of electronic density at the Ru active sites and a shift in the d -band center. This simultaneously satisfies the electronic requirements for enhancing N2 activation while weakening NH3 adsorption, thereby circumventing the bottlenecks in NH3 synthesis under mild conditions. Meanwhile, anchoring of C60 accelerates hydrogen spillover and enhances the exchangeability of hydrogen species in the ZrH2 support, as well as expose a greater number of B5 sites of Ru entities, resulting in the co-optimization of hydrogen migration and nitrogen activation. As a consequence, the NH3 synthesis rate of the C60 -Ru/ZrH2 catalyst is approximately twice that of the Ru/ZrH2 catalyst at 400 degrees C and 1 MPa. This study shows that doping C60 represents a fundamentally different approach compared to traditional promoters for catalytic NH3 synthesis. We anticipate that this strategy may be generalized to generate widespread interest in the catalysis of NH3 synthesis. (c) 2026 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Ru-based catalysts have attracted increasing interest due to their high efficiency in NH3 synthesis, yet their performance is limited by the inability of single site to simultaneously activate both N2 and H2 molecules. To overcome this challenge, introducing different functional sites (e.g., C60 as an adsorption/activation site for H2) is vital to achieving highly efficient NH3 synthesis under mild conditions. However, how the relative positioning of the second functional site to the Ru site influences the local environment and subsequent catalytic performance is still elusive. Herein, we present a site-selective strategy for anchoring C60 at distinct locations on a single-site Ru catalyst. Compared to surface-anchored C60, embedded C60 substantially modifies the electronic structure of the Ru single-atom site and decreases the work function. By virtue of cascading different functional sites, embedded C60 facilitates hydrogen spillover to nitrogen species activated on Ru to form NH3. In contrast, despite the high capacity for H2 adsorption, surface-anchored C60 exhibits sluggish hydrogen spillover, which results in its inefficient catalytic performance. Therefore, the optimal single-site Ru catalyst with embedded C60 achieves a 1.4-fold increase in the NH3 synthesis rate compared to its counterpart with surface-anchored C60 at 400 degrees C and 1 MPa. This study sheds light on optimizing the positioning of second functional site in the design of highperformance NH3 synthesis catalysts.

The development of efficient catalysts for ammonia (NH3) synthesis under mild conditions is very significance. Although Ru-based catalysts supported on MgO exhibit promising activity in NH3 synthesis, the strong hydrogen adsorption and easy agglomeration of Ru metal can adversely affect both activity and stability. In this work, we employ a strategy of graphitic carbon (GC) modified MgO-supported Ru catalyst to enhance NH3 synthesis performance. The optimized K-Ru-15GC/MgO catalyst exhibits a NH3 synthesis rate of 18.1 mmol gcat 400 degrees C and 1 MPa, which is 1.8 times higher than that of the K-Ru/MgO catalyst. Characterizations reveal that GC modification improves Ru dispersion, and facilitates electrons transfer from promoter to Ru, both for promoting N2 activation. Moreover, hydrogen spillover from Ru to the GC layer alleviates hydrogen poisoning to realize efficient NH3 synthesis. This study offers new insights into the design of advanced Ru-based catalysts for NH3 synthesis under mild conditions.

The NiCu(2/1)/Mg 2 Al-LDO catalyst shows the highest performance.

The development of efficient catalysts enabling the Haber-Bosch ammonia (NH3) synthesis process under mild conditions is crucial. However, the competitive activation of co-adsorbates, that is, excessive N2 or H2 binding at a single active site, is detrimental to NH3 synthesis. Herein, we demonstrate that Fe2O3 mediated by fullerenes (C60/C70) with varying geometric configurations could facilitate efficient NH3 synthesis under mild conditions (<= 400 degrees C, <= 2 MPa). Our studies indicate that C70 exhibits a higher curvature than C60, which enhances electron transfer through Fe-O-C bridges. This curvature-driven electronic modulation, combined with the spatially separated activation of N2 (primarily on Fe sites) and H2 (mainly on C60/C70), synergistically enhances the dissociation of N2 and the desorption of NH3. As a consequence, the developed C70-Fe2O3 achieves an NH3 synthesis rate of 19.10 mmol g-1 h-1. This finding demonstrates a strategy for optimizing dual-functionality sites through selecting fullerenes with different geometric structures.

Molybdenum (Mo) serves as the key site in the nitrogenase enzyme, catalyzing the conversion of N-2 into NH(3 )under ambient conditions. However, the strong affinity of Mo sites for N-2 hinders H-2 adsorption due to the competitive nature of N-2 and H-2 on a single site, resulting in an unsatisfactory ammonia synthesis performance. Here, we propose an approach of intervening C-60 layer as a second site for H-2 adsorption on two-dimensional Mo2CTx. The C-60 layer thickness is readily tunable by varying its loading content. An optimal C-60 layer significantly enhances the electronic interaction between the C-60 layer and the Mo(2)CT(x )layer, leading to a remarkable decrease in the work function and an increase in the electron density of Mo atoms. Therefore, the separate adsorption of N-2 and H-2 on distinct sites is substantially facilitated. The present work offers insights into the correlation between structure and performance in NH(3 )synthesis catalysts.

Traditional crystalline ZnO is widely used for hydrogen production through the ethanol dehydrogenation peo cess, however its catalytic activity is considerably low when compared with Co-based catalysts. Herein, amor phous 20 with exceptional high-temperature stability was synthesized for the first time ming malamine at additive. The resulting amerphous Zno displays higher catalytic activity towards ethanol dehydrogenation, with the ethanol conversion up to 99,99% and the hydrogen yield reaching 12.40 mmolegasha at 400 C, which is 3.8 time higher than crystalline ZnO. The ruccessful synthesis of amorphous ZnO can be primarily attributed to the sim caneous presence of both oxygen vacancies and zinc vacancies within the ZnO structure. These ruc tural defen play a crucial role in enhancing its catalytic activity, which attribute to the increased Lewis acidity and Lewis barinity of amorphous ZnO.

The hydrogenation of fatty acids to fatty alcohols, alongside the hydrogenation of CO2 to methanol, represents crucial pathways for addressing the depletion of fossil resources and achieving carbon neutrality. However, the catalytic conversion rates of these two reactions remain low under mild conditions. In this study, we discovered an innovative approach that couples stearic acid (C17COOH) hydrogenation with CO2 hydrogenation in a one-pot catalytic tandem process using the optimized CuZn2ZrOx/C-N catalyst. This method significantly enhances the yields of methanol and fatty alcohol under mild reaction conditions of 200 degrees C, 3 MPa, 6 h, with a H2:CO2 ratio of 3:1. The reaction mechanism revealed that stearic acid methyl ester (C17COOCH3) acts as a key intermediate in the coupling process. Specifically, the in situ methanol produced from CO2 hydrogenation is converted by C17COOH into C17COOCH3, which is then hydrogenated to form stearic alcohol. This coupling reaction offers important insights for the simultaneous utilization of CO2 and biomass-derived fatty acids in producing valueadded chemicals. Furthermore, our findings could inspire the design of more synergistically coupled catalytic reactions that leverage dual-promotional effects for the hydrogenation of CO2 and carboxylic acid compounds. This approach not only enhances the efficiency of these transformations but also aligns with the broader goals of sustainability and resource efficiency in chemical processes.

Achieving green ammonia (NH3) synthesis requires developing effective catalysts under mild conditions. However, the competitive adsorption of N2 and H2, as well as the strong binding of N-containing intermediates on the catalyst, greatly inhibits the active sites for efficient NH3 synthesis. Here, we constructed a series of ZrH2-modified Fe catalysts with dual active sites to address these issues and realized efficient NH3 synthesis under mild conditions. Our study shows that ZrH2 can not only provide active sites for H2 activation but also transfer electrons to Fe sites for accelerating N2 activation. The interaction between Fe and ZrH2 over 40ZrH2-Fe leads to a decrease in work function and a downward shift of the d-band center, which is conducive to N2 activation and NH3 desorption, respectively. The utilization of distinct sites for activating different reactants can avoid the competitive adsorption of N2 and H2, leading to excellent NH3 synthesis activity of the 40 wt.

The development of advanced catalysts is critical to realize efficient ammonia (NH3) synthesis under mild conditions. However, the activation of an inert N equivalent to N bond in N2 molecules is the primary hindrance to NH3 synthesis, and hydrogen poisoning is another major and a serious problem, especially in Ru-based catalysts. Here, we develop an H-ZSM-5-supported Ru-based catalyst (Ce-Ru/HZ) via decorating with a CeO2 promoter to realize efficient NH3 synthesis. Our study shows that the Ce species can serve as an electron donor to enrich the electron density of Ru sites, thus accelerating N2 activation for NH3 synthesis. Meanwhile, the interaction of Ru and Ce can alleviate the effect of hydrogen poisoning on Ru sites. Consequently, the 16 wt % Ce-promoted Ru/HZ catalyst displays a superior NH3 synthesis rate and long-term stability of more than 550 h at 400 degrees C and 1 MPa.

1,3-Butadiene (hereinafter referred to as butadiene), as an important organic intermediate in the chemical industry, has a wide range of uses in the petroleum and rubber industries. Using ethanol as raw material to produce butadiene can solve the non-renewable problem of raw materials, so it has received more and more attention. In this paper, catalysts were hydrothermally synthesized by using SBA-15 as the support, nitrate as the oxide precursor, and nitrogen-containing organic compounds as the additive. And then, the relationship between catalytic performance (ethanol conversion and butadiene yield) and the acid-base properties of catalysts was explored in the synthesis of butadiene from ethanol. Specifically, we used melamine (M), cyanuric acid (Ma), 1,10-phenanthroline (Pm), imidazole (Im), and 1,3,5-triazine (St) as nitrogen-containing additives for the preparation of Zn-Zr/SBA-15+X catalysts. Through the activity evaluation of the catalysts, the activities of ethanol dehydrogenation and dehydration, acetaldehyde condensation, and Meerwein-Ponndorf-Verley (MPV) reactions were calculated. Then, by analyzing the dependence of these activities and butadiene yield on the acidity and basicity (the strength and number of acidic/basic sites) of catalysts, we found that appropriate amounts of weak acid (0.022 mmol center dot g(-1)), moderate acid (0.078 mmol center dot g(-1)), moderate base (0.055 mmol center dot g(-1)), and strong base (0.056 mmol center dot g(-1)) are helpful for the ethanol dehydrogenation, whereas excess amount of weak acid and moderate acid will lead to the ethanol dehydration. Appropriate amounts of moderate acid (0.078 mmol center dot g(-1)) and moderate base (0.055 mmol center dot g(-1)) will favor the acetaldehyde condensation and MPV reactions. The butadiene yield is closely related to the activities of acetaldehyde condensation and MPV. The melamine-modified catalyst (Zn-Zr/SBA-15+M) has the optimum amounts of weak acid, moderate acid, moderate base, and strong base in accordance with the above quantities, resulting in the best catalytic performance: 99.5% conversion of ethanol, 65.5% selectivity of butadiene, and 0.45 gBD center dot g(cat)(-1)center dot h(-1) of butadiene productivity.

The effects of promoters on Ru nanoparticles (>= 2 nm) catalysts for NH3 synthesis have been extensively elaborated, but their roles on ultrasmall Ru nanoclusters (NCs, 1-2 nm) remain largely unknown and need to be further uncovered. Herein, a series of K-promoted MgO supported Ru NCs were synthesized and investigated for NH3 synthesis. The addition of 5wt.%K onto Ru/MgO NCs leads to a significantly high NH3 synthesis rate of 21.7 mmol(NH3) g(cat)(-1)h(-1) at 400 degrees C and 0.2 MPa, close to the thermodynamic equilibrium. Out studies reveal that anchoring K onto Ru NCs can increase the electron density and cause an upshift of the d-band center of Ru entities. Moreover, the addition of K regulates the hydrogen affinity and accelerates the migration of hydrogen from the Ru NCs surface to MgO support, which is crucial in avoiding the hydrogen poisoning effect on Ru NCs. With the synergistic effect of the Ru NCs sites bridged by H-spillover, makes the K-mediated Ru/MgO NCs catalysts efficient for NH3 synthesis at mild conditions.

The development of a bimetallic catalyst for ammonia synthesis using nonprecious metals such as Co, Fe, and Mo has attracted wide attention. In this work, because of the enhancement of the exposed Co species on the surface of the Co-Fe bimetallic catalyst through the introduction of Co into Fe-CeO2 by the impregnation method, the amount of hydrogen adsorbed on the metal surface would enhance, and the hydrogen spillover could strengthen. As a result, the as-prepared sample shows much higher ammonia synthesis activity than other Co-Fe bimetallic catalysts or monometallic samples. This finding not only provides a way for the development of bimetallic catalysts using nonprecious metals for ammonia synthesis but also helps design other bimetallic catalysts for hydrogen-involving reactions.

As a sustainable, environmentally friendly, and economically viable way to produce 1,3-butadiene, the ethanol-to-butadiene (ETB) process has received increasing attention recently. This ETB process normally requires catalysts with suitable acidity and basicity, namely an acid-base balance. However, the origin of acid-base balance has not yet been elucidated. Herein, we demonstrate that by finely coordinating the interaction of ZnO and ZrO2, a butadiene productivity of 0.33 g(BD) g(cat)(-1) h(-1) at low WHSV and 1.39 gBD g(cat)(-1) h(-1) at high WHSV can be achieved. In contrast, pure ZnO prefers ethanol dehydrogenation to acetaldehyde and pure ZrO2 favors ethanol dehydration to ethylene and diethyl ether. Through a variety of characterization techniques, we found that the interaction of ZnO and ZrO2 alters the acidity and basicity of catalysts, resulting in volcanic shapes of ethanol conversion, butadiene selectivity, and butadiene yield in the ETB process. These findings provide in-depth insights into the understanding of the ETB process and may also apply to other reaction systems using ZnO-ZrO2 as catalytically active components.

Ammonia (NH3) is an excellent candidate for hydrogen storage and transport. However, producing NH3 under mild conditions is a long-term, arduous task. Atomic cluster catalysts (ACCs) have been shown to be effective for catalytic N2-to-NH3 conversion, opening the door to the development of efficient catalysts under mild conditions. Still, ACC formation with thermally stable catalytic sites remains a challenge because of their high surface free energy. Herein, we report anchoring Ba and/or Ce onto Ru ACCs (2 wt% Ru atomic clusters supported on N-doped carbon) to form so-called clusters–metal oxide promoters electronic interaction (CMEI) to stabilize the Ru atomic clusters. The resulting Ba/Ce/Ru ACCs significantly boost the NH3 synthesis rate to 56.2 mmolNH3 gcat−1 h−1 at 400 °C and 1 MPa, which is 7.5-fold higher than that of Ru ACC. The strengthened CMEI between the Ba/Ce and Ru atomic clusters across the Ba/Ce/Ru ACC enables electron transfer from Ba and/or Ce to Ru atomic clusters. As such, the electron-enriched Ru atom could facilitate electron transfer to N≡N bond π* orbitals, which would weaken the N≡N bond and drive the eventual conversion of N2 to NH3. This study offers insight into the role of CMEI in Ru ACCs and provides an effective approach for designing stable atomic cluster catalysts for NH3 synthesis.

The upgrading of ethanol to produce n-butanol and other >C-4 alcohols is a promising reaction. However, the development of efficient catalysts for this reaction has been slow. In this study, we prepared a series of Pd@UiO66-X catalysts using ligands functionalized with electron-donating groups (-NH2 and -CH3) and electronaccepting groups (-H and -NO2). These functional groups play two roles in mediating the microenvironment of the Pd metal. Firstly, they regulate the electronic properties of the Pd metal, and secondly, they alter the hydrophilicity/hydrophobicity surrounding the Pd metal. The intrinsic electronic properties of the Pd metal significantly influence ethanol conversion, while the hydrophilicity/hydrophobicity surrounding the Pd metal is an extrinsic factor. As a result, the Pd@UiO-66-CH(3 )catalyst with a hydrophobic microenvironment around the electron-rich Pd metal exhibits the highest ethanol conversion and n-butanol yield among all the Pd@UiO-66-X catalysts. It also achieves an impressive >C-4 alcohols yield of up to 47.7 %, which is the highest reported to date.

Self-assembly of polyoxometalate (POM) clusters offers a viable method for constructing nanostructures with tailored properties. Over the past few decades, POMs-based nanostructures of varying dimensions, such as nanowires, nanobelts, nanosheets, and other superstructures, have been constructed. Additionally, these nanostructures show broad prospects in optical, electrochemical, catalytic, and mechanical applications. Particularly noteworthy are surface modifications, such as surfactant encapsulation, which yield amphiphilic POMs. These modifications render the POMs compatible with organic systems, significantly broadening their morphological and functional applicability. This concept provides an overview of recent advancements in nanostructures based on self-assembly of surfactant encapsulated POM clusters, encompassing one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) structures. Through surfactant encapsulation, POM clusters can be rendered compatible with various solvents, facilitating the formation of hybrid assemblies with diverse morphologies and unique properties. The structures, formation mechanisms, and properties of these sub-nanometer assemblies are discussed from both experimental and theoretical perspectives. This concept aims to provide a new insight into the design and fabrication of nanostructures based on POM clusters. This concept focuses on the construction of surfactant-encapsulated polyoxometalates into nanostructures of different dimensions, including one-dimensional single chains, two-dimensional layered structures, and three-dimensional polyhedral structures. These POMs-based components are highly ordered, with well-defined structures and unique properties. image