Catalytic System Research Articles

Atomically Dispersed Iridium on Polyimide Support for Acidic Oxygen Evolution.

Designing a high-performing iridium (Ir) single-atom catalyst is desired for acidic water electrolysis, which shows enormous potential given its high catalytic activity toward acidic oxygen evolution reaction (OER) with minimum usage of precious Ir metal. However, it still remains a substantial challenge to stabilize the Ir single atoms during the OER operation without sacrificing the activity. Here, we report a high-performing OER catalyst by immobilizing Ir single atoms on a polyimide support, which exhibits a high mass activity on a carbon paper electrode while simultaneously achieving outstanding stability with negligible decay for 360 h. The resulting electrode (denoted as Ir1-PI@CP) reaches a 49.7-fold improvement in mass activity compared to the counterpart electrode prepared without polyimide support. Both our experimental and theoretical results suggest that, owing to the strong metal-support interactions, the polyimide support can enhance the Ir 5d states of Ir single atoms in Ir1-PI@CP, which can tailor the adsorption energies of intermediates and decrease the thermodynamic barrier at the rate-determining step of the OER, but also facilitate the proton-electron-transfer process and improve the reaction kinetics. This work offers an alternative avenue for developing single-atom catalysts with superior activity and durability toward various catalytic systems and beyond.

Selective Cleavage of Cβ-O-4 Bond for Lignin Depolymerization via Paired-Electrolysis in an Undivided Cell.

The cleavage of C-O bonds is one of the most promising strategies for lignin-to-chemicals conversion, which has attracted considerable attention in recent years. However, current catalytic system capable of selectively breaking C-O bonds in lignin often requires a precious metal catalyst and/or harsh conditions such as high-pressure H2 and elevated temperatures. Herein, we report a novel protocol of paired electrolysis to effectively cleave the Cβ-O-4 bond of lignin model compounds and real lignin at room temperature and ambient pressure. For the first time, "cathodic hydrogenolysis of Cβ-O-4 linkage" and "anodic C-H/N-H cross-coupling reaction" are paired in an undivided cell, thus the cleavage of C-O bonds and the synthesis of valuable triarylamine derivatives could be simultaneously achieved in an energy-effective manner. This protocol features mild reaction conditions, high atom economy, remarkable yield with excellent chemoselectivity, and feasibility for large-scale synthesis. Mechanistic studies indicate that indirect H* (chemical absorbed hydrogen) reduction instead of direct electron transfer might be the pathway for the cathodic hydrogenolysis of Cβ-O-4 linkage.

Bioinspired Self-Growing Layered Hydrogel Enabled by Catechol Chemistry-Mediated Interfacial Catalytic System.

Tissue-inspired layered structural hydrogel has attracted increasing attention in artificial muscle, wound healing, wearable electronics, and soft robots. Despite numerous efforts being devoted to developing various layered hydrogels, the rapid and efficient preparation of layered hydrogels remains challenging. Herein, inspired by the self-growth concept of living organisms, an interfacial catalytic self-growth strategy based on catechol chemistry-mediated self-catalytic system of preparing layered hydrogels is demonstrated. Typically, the tannic acid-metal ion (e.g., TA-Fe3+) complex embedded in the hydrogel substrate would catalytically trigger rapid solid-liquid interfacial polymerization to grow the hydrogel layer without bulk solution polymerization. The self-growth process can be finely controlled by changing the growth time, the molar ratio of Fe3+/TA, and so on. The strategy is applicable to prepare various layered hydrogels as well as complex layered hydrogel patterns, allowing the customization of the physicochemical properties of the hydrogel. In addition, the self-adhesive layered hydrogel was prepared and can be utilized as a wearable strain sensor to monitor physiological activities and human motions. The demonstrated interfacial catalytic self-growth strategy will provide a route to design and fabricate layered hydrogel materials.

Rational integration of MoSe2 and BN with TiO2 to design nanoengineered ternary heterojunctions for sustainable hydrogen energy: Experimental evidences and theoretical anticipations

Ternary MoSe2-BN/TiO2 and binary MoSe2–TiO2 heterostructures are epitomized as Tortoise and Hare nanocatalysts to outline the synergism between bilayered MoSe2-BN over pristine MoSe2 for their applicability in the photochemical and photo/-electrochemical water splitting operations. We report here the fabrication of MoSe2-BN integrated TiO2 catalytic systems and ascertained experimental and theoretical investigations of MoSe2-BN/TiO2 and MoSe2–TiO2 heterostructures that are directly proportional to their long-term applicability as the hydrogen evolution reaction (HER) catalysts. Optimized 5 wt% MoSe2-BN/TiO2 and 7.5 wt% MoSe2–TiO2 exhibited nearly 32-fold and 18-fold higher photochemical hydrogen evolution efficiency than bare TiO2 with 43.1% and 25.08% apparent quantum yield, respectively. Photo/-electrochemical studies verified the diversity of MoSe2-BN/TiO2 and MoSe2–TiO2 catalysts as applied potential values diminished drastically to attain benchmark 10 mA/cm2 current density for 5 wt % MoSe2-BN/TiO2 (0.31 V) and 7.5 wt% MoSe2–TiO2 (0.61 V). This work showcases the augmented HER activity of MoSe2-BN/TiO2 due to the shielding of MoSe2 grain boundaries via BN-encapsulation that impeded the degradation of MoSe2 in aqueous condition ascribed to its wide band energy in UV region making it the advanced tunnel barrier.

Machine Learning Interatomic Potentials for Catalysis.

Atomistic modeling can provide insights into the design of novel catalysts in modern industries of chemistry, materials science, and biology. Classical force fields andab initiocalculations have been widely adopted in molecular simulations. How- ever, these methods suffer from the drawbacks of either low accuracy or high cost. Recently, the development of machine learning interatomic potentials (MLIPs) has become more and more popular as they can tackle the problems in question and can deliver rather accurate results at significantly lower computational cost. In this review, the atomistic modeling of catalytic systems with the aid of MLIPs is discussed, showcasing recently developed MLIP models and selected applications for the modeling of catalytic systems. We also highlight the best practices, and challenges for MLIPs and give an outlook for future works on MLIPs in the field of catalysis.

Ene-Reductase-Catalyzed Aromatization of Simple Cyclohexanones to Phenols.

Direct aromatization of cyclohexanones to synthesize substituted phenols represents a significant challenge in modern synthetic chemistry. Herein, we describe a novel ene-reductase (TsER) catalytic system that converts substituted cyclohexanones into the corresponding phenols. This process involves the successive dehydrogenation of two saturated carbon-carbon bonds within the six-membered ring of cyclohexanones and utilizes molecular oxygen to drive the reaction cycle. It demonstrates a versatile and efficient approach for the synthesis of substituted phenols, providing a valuable complement to existing chemical methodologies.

Ene‐Reductase‐Catalyzed Aromatization of Simple Cyclohexanones to Phenols

Direct aromatization of cyclohexanones to synthesize substituted phenols represents a significant challenge in modern synthetic chemistry. Herein, we describe a novel ene‐reductase (TsER) catalytic system that converts substituted cyclohexanones into the corresponding phenols. This process involves the successive dehydrogenation of two saturated carbon‐carbon bonds within the six‐membered ring of cyclohexanones and utilizes molecular oxygen to drive the reaction cycle. It demonstrates a versatile and efficient approach for the synthesis of substituted phenols, providing a valuable complement to existing chemical methodologies.

Ionic Liquids Functionalized Copper Catalytic Systems for Electrocatalytic Carbon Dioxide Reduction

The extensive combustion of fossil fuels results in excessive release of carbon dioxide (CO2), causing a global environmental crisis. It is imperative to develop sustainable methods for converting CO2 into renewable energy sources. Electrochemical reduction of CO2 (CO2RR) offers the potential to generate valuable chemicals, including C1 products (e.g., carbon monoxide, methane, etc.) and C2+ products (e.g., ethene, ethanol, acetic acid, propyl alcohol, etc.). Copper‐based (Cu‐based) catalysts show promise for producing value‐added C2+ products, but they face challenges like low selectivity and stability. The catalytic performances of Cu‐based catalysts can be promoted through electronic structure adjustment, selective crystal face exposure, as well as molecular additive approaches. Ionic liquids (ILs), known for their strong CO2 adsorption capacity, adjustable hydrophobicity, and wide chemical window, hold significant promise for addressing the current challenges associated with Cu‐based catalysts. This review provides a comprehensive overview of the structural characterization and catalytic mechanisms of ILs used in Cu‐based CO2RR catalytic systems. Additionally, it offers suggestions for future research avenues regarding IL‐functionalized Cu catalysts.

Acid-activated α-MnO2 for photothermal co-catalytic oxidative degradation of propane: Activity and reaction mechanism

In order to further reduce the energy consumption of the conventional thermal catalytic oxidation system and improve the degradation efficiency of pollutants, photothermal synergistic catalytic oxidation (PTSCO) system was constructed in this paper with propane as simulated pollutant representing VOCs, and then the modified α-MnO2 catalysts were prepared by using the acid activation method, which were used for the catalytic oxidation of propane in PTSCO. The α-MnO2 with appropriate acid concentration possessed excellent low-temperature reducibility, abundant active oxygen species, fast oxygen migration rate and a large number of acid sites. The optimal catalyst, H0.05-MnO2, had a T90 of 204 °C in the PTSCO system, which reduced by more than 30 °C relative to the α-MnO2 (T90 of 235 °C). Moreover, H0.05-MnO2 demonstrated excellent water resistance and long-term stability (T = 45 h). It was shown that the combination of photocatalysis and thermocatalysis can improve propane degradation by examining the kinetics of propane degradation in the PTSCO system and the conformational relationship of propane degradation by catalysts. Furthermore, a multi-pathway synergistic mechanism between photocatalysis and thermocatalysis in the PTSCO system was proposed. This work provided a theoretical basis for the preparation of high-performance catalysts and the catalytic degradation of propane.

Design of Cr-Based Molecular Electrocatalyst Systems for the CO2 Reduction Reaction.

ConspectusHuman influence on the climate system was recently summarized by the sixth Intergovernmental Panel on Climate Change (IPCC) Assessment Report, which noted that global surface temperatures have increased more rapidly in the last 50 years than in any other 50-year period in the last 2000 years. Elevated global surface temperatures have had detrimental impacts, including more frequent and intense extreme weather patterns like flooding, wildfires, and droughts. In order to limit greenhouse gas emissions, various climate change policies, like emissions trading schemes and carbon taxes, have been implemented in many countries. The most prevalent anthropogenic greenhouse gas emitted is carbon dioxide (CO2), which accounted for 80% of all U.S. greenhouse gas emissions in 2022. The reduction of CO2 through the use of homogeneous electrocatalysts generally follows a two-electron/two-proton pathway to produce either carbon monoxide (CO) with water (H2O) as a coproduct or formic acid (HCOOH). These reduced carbon species are relevant to industrial applications: the Fischer-Tropsch process uses CO and H2 to produce fuels and commodity chemicals, while HCOOH is an energy dense carrier for fuel cells and useful synthetic reagent. Electrochemically reducing CO2 to value-added products is a potential way to address its steadily increasing atmospheric concentrations while supplanting the use of nonrenewable petrochemical reserves through the generation of new carbon-based resources. The selective electrochemical reduction of CO2 (CO2RR) by homogeneous catalyst systems was initially achieved with late (and sometimes costly) transition metal active sites, leading the field to conclude that transition metal complexes based on metals earlier in the periodic table, like chromium (Cr), were nonprivileged for the CO2RR. However, metals early in the table have sufficient reducing power to mediate the CO2RR and therefore could be selective in the correct coordination environment. This Account describes our efforts to develop and optimize novel Cr-based CO2RR catalyst systems through redox-active ligand modification strategies and the use of redox mediators (RMs). RMs are redox-active molecules which can participate cocatalytically during an electrochemical reaction, transferring electrons─often accompanied by protons─to a catalytic active site. Through mechanistic and computational work, we have found that ligand-based redox activity is key to controlling the intrinsic selectivity of these Cr compounds for CO2 activation. Ligand-based redox activity is also essential for developing cocatalytic systems, since it enables through-space interactions with reduced RMs containing redox-active planar aromatic groups, allowing charge transfer to occur within the catalyst assembly. Following a summary of our work, we offer a perspective on the possibilities for future development of catalytic and cocatalytic systems with early transition metals for small molecule activation.

Essential features of weak current for excellent enhancement of NOx reduction over monoatomic V-based catalyst

Human society is facing increasingly serious problems of environmental pollution and energy shortage, and up to now, achieving high NH3-SCR activity at ultra-low temperatures (<150 °C) remains challenging for the V-based catalysts with V content below 2%. In this study, the monoatomic V-based catalyst under the weak current-assisted strategy can completely convert NOx into N2 at ultra-low temperature with V content of 1.36%, which shows the preeminent turnover frequencies (TOF145 °C = 1.97×10−3 s−1). The improvement of catalytic performance is mainly attributed to the enhancement catalysis of weak current (ECWC) rather than electric field, which significantly reduce the energy consumption of the catalytic system by more than 90%. The further mechanism research for the ECWC based on a series of weak current-assisted characterization means and DFT calculations confirms that migrated electrons mainly concentrate around the V single atoms and increase the proportion of antibonding orbitals, which make the V-O chemical bond weaker (electron scissors effect) and thus accelerate oxygen circulation. The novel current-assisted catalysis in the present work can potentially apply to other environmental and energy fields.

Water disinfection: Advances in photocatalysis and piezo/triboelectric catalysis with progressively enhanced energy utilization

AbstractIncreasing climate‐related extreme weather events and conflicts hinder safe water sanitation for vulnerable populations. In developing areas, centralized water systems are impractical due to high costs and poor infrastructure. Thus, technologies utilizing renewable energy like solar and mechanical energy for water treatment hold promise. It is critical to develop photocatalysts and piezoelectric/triboelectric catalysts that capture solar energy as well as mechanical energy to generate disinfectants to maximize energy utilization. The latest advancements in principles, materials, and processes utilizing solar and mechanical energy for water disinfection are highlighted in this review. First, we elucidate both direct and indirect mechanisms of sunlight‐mediated water disinfection, discuss the evolution of photocatalysts from simple UV absorption to visible‐light utilization, and even near‐infrared light exploitation to enhance solar spectrum utilization efficiency. Furthermore, we delve into the fundamental principles of piezoelectricity and triboelectricity relying on mechanical energy conversion as well as summarize the development of piezo/triboelectric catalysts from being driven by high‐frequency energy to utilizing low‐frequency mechanical energy from the environment. Finally, challenges and directions for efficient systems are outlined to inspire rational design strategies and accelerate the production of superior catalytic systems applicable across a broad range.

Dehydrosilylation of Alcohols Using Gold Nanoparticles Deposited on Citric Acid-modified Fibrillated Cellulose

The development of an effective catalytic system for the dehydrogenative coupling of hydrosilanes with alcohols remains an ongoing challenge, particularly for alcohol protection applications. In this study, we report the development and optimization of a highly efficient gold catalyst supported on fibrillated cellulose modified with citric acid (F-CAC). The catalyst exhibited remarkable catalytic activity under mild conditions with 0.01–0.05 mol% of Au loading, facilitating the formation of silyl ethers with excellent yield. Notably, our catalytic system overcomes the need for excess alcohol typically required in such reactions, making it highly practical for alcohol protection applications. This work represents a significant advancement in the field of dehydrosilylation catalysis, offering a sustainable, efficient, and environmentally friendly approach for the synthesis of functional silanol-based materials and alcohol protection applications. The scope of substrates and the utility of the catalyst have been thoroughly studied.

Product Selection Toward High-Value Hydrogen and Bamboo-Shaped Carbon Nanotubes from Plastic Waste by Catalytic Microwave Processing.

The escalating levels of plastic waste and energy crises underscore the urgent need for effective waste-to-energy strategies. This study focused on converting polypropylene wastes into high-value products employing various iron-based catalysts and microwave radiative thermal processing. The Al-Fe catalysts exhibited exceptional performance, achieving a hydrogen utilization efficiency of 97.65% and a yield of 44.07 mmol/g PP. The gas yields increased from 19.99 to 94.21 wt % compared to noncatalytic experiments. Furthermore, this catalytic system produced high-value bamboo-shaped carbon nanotubes that were absent in other catalysts. The mechanism analysis on catalytic properties and product yields highlighted the significance of oxygen vacancies in selecting high-value products through two adsorption pathways. Moreover, the investigation examined the variations in product distribution mechanisms between conventional and microwave pyrolysis, in which microwave conditions resulted in 4 times higher hydrogen yields. The technoeconomic assessment and Monte Carlo risk analysis further compared the disparity. The microwave technique had a remarkable internal rate of return (IRR) of 39%, leading to an income of $577/t of plastic with a short payback period of 2.5 years. This research offered sustainable solutions for the plastic crisis, validating the potential applicability of commercializing the research outcomes in real-world scenarios.

Photocatalytic Hantzsch Ester-Mediated Pinacol-Type Coupling of Aldehydes and Ketones.

We have developed a photocatalyst-free reaction system that uses Hantzsch esters as photoreducing agents to promote the coupling of carbonyl compounds to 1,2-diols. The system fully utilizes the single electron transfer and proton donor roles of Hantzsch esters. The system shows a wide range of substrate application. Aromatic ketones, aliphatic ketones, and aldehydes can be applied to the catalytic system. Both self-coupling and cross-coupling can achieve ideal results.

Base Metals Induced Oxygen Migration and Adjustable Performance in Multifunctional Oxide Heterojunction Devices

AbstractThe chemical and electronic interactions at metal/oxide heterojunctions is pivotal in determining the electronic properties of oxide devices utilized in microelectronics, catalysis, and photovoltaic systems. In this study, interfacial oxidation migrations within a model heterostructure system, consisting of a La0.7Sr0.3MnO3 film overlaid by various metallic (Ti, Al, Cu, Ag, and Au) ultrathin layers are systematically investigated. It is experimentally demonstrated that at elevated deposition temperature, the oxygen‐active ultrathin overlayers of base metals such as Ti and Al significantly derive oxygen from the underlying La0.7Sr0.3MnO3 film, inducing a perovskite to brownmillerite phase transition in the underlying functional oxide film. Conversely, no structural transitions are observed for La0.7Sr0.3MnO3 film when it is capped by noble metals (Au, Ag), which possess relative high oxidation formation energy. These observations are crucial for the development of novel crystalline and electronic architectures in metal/oxide heterostructures, offering a refined approach to modulate interfacial reactivity without compromising the functionality of oxide‐based heterojunction devices.

Pd/Cu-Cocatalyzed Enantio- and Diastereodivergent Wacker-Type Dicarbofunctionalization of Unactivated Alkenes.

The Wacker and Wacker-type reactions are some of the most fundamental and powerful transformations in organic chemistry for their ability to efficiently produce valuable chemicals. Remarkable progress has been achieved in asymmetric oxy/aza-Wacker-type reactions; however, asymmetric Wacker-type dicarbofunctionalization remains underdeveloped, especially for the concurrent construction of two stereocenters. Herein, we report a Pd/Cu-cocatalyzed enantio- and diastereodivergent Wacker-type dicarbofunctionalization of alkene-tethered aryl triflates with imino esters. A series of 2-indanyl motifs bearing adjacent carbon stereocenters could be easily synthesized in moderate to excellent yields and with good to excellent diastereo- and enantioselectivities (up to >20:1 dr and >99% ee). Density functional theory calculations revealed that the origin of diastereoselectivity in this Pd/Cu synergistic catalytic system is jointly determined by both the intermolecular anti-carbopalladation of alkenes and the reductive elimination processes, in accordance with the Curtin-Hammett principle.

Iodine-Catalyzed [5 + 1] Carbonylation of 2-Alkenyl/Pyrrolylanilines with CS2 as the Carbonylating Reagent.

Novel metal-free iodine (I2)-catalyzed [5 + 1] carbonylation of 2-alkenyl/pyrrolylanilines with carbon disulfide (CS2) as the carbonylating reagent has been developed. This innovative method allows for the synthesis of valuable derivatives such as 4-aryl-2-quinolinones and pyrrolyl-fused quinoxalinones. Notably, this work represents the first instance where CS2 has been utilized as a carbonylating reagent source. The protocol demonstrates the utilization of various substrates, leading to diverse reactions that afford excellent yields under mild conditions. The method also shows good compatibility with functional groups present in the substrates, further enhancing its synthetic utility. Importantly, the developed reaction exhibits scalability, enabling gram-scale synthesis, and shows promise for the synthesis of druglike molecules. In this catalytic system, CS2 serves as the carbonyl source, while dimethyl sulfoxide plays multiple roles, including acting as an oxidant and a solvent. Mechanistic studies have been conducted to elucidate the underlying processes, with the formation of quinolone-2-thiones identified as crucial intermediates, facilitating the carbonylation annulation process.

Enhanced syngas production from wood biomass by the catalytic packed bed of dolomite, limestone and olivine

Wood biomass was a promising renewable energy source that achieved carbon neutrality and alleviated the energy crisis. To enhance the conversion efficiency of wood to hydrogen, the catalytic combustion system of natural ores (dolomite, limestone and olivine) and wood chips was established. And the effects of the type, location, calcination temperature, content and diameter of catalysts were investigated on the temperature distribution and gas production. The results indicated that the combustion temperature of the hybrid bed was significantly increased with the catalyst addition. The dolomite and limestone particles promoted the hydrogen production, and the mole fractions of hydrogen were improved by 75% and 42%, respectively. When the dolomite was located above the wood layer, the hydrogen fraction was greatly higher than that of mixing with the wood. As the dolomite content increased, both of the hydrogen mole fraction and release time were enlarged obviously. Furthermore, the wood chips and dolomite particles with smaller diameters contributed to syngas production. And the hydrogen decreased with the increasing of air velocity when dolomite addition, which achieved the maximum of 11.2% at the velocity of 2 cm/s.

In Situ Characterization Techniques for Electrochemical Nitrogen Reduction Reaction.

The electrochemical reduction of nitrogen to produce ammonia is pivotal in modern society due to its environmental friendliness and the substantial influence that ammonia has on food, chemicals, and energy. However, the current electrochemical nitrogen reduction reaction (NRR) mechanism is still imperfect, which seriously impedes the development of NRR. In situ characterization techniques offer insight into the alterations taking place at the electrode/electrolyte interface throughout the NRR process, thereby helping us to explore the NRR mechanism in-depth and ultimately promote the development of efficient catalytic systems for NRR. Herein, we introduce the popular theories and mechanisms of the electrochemical NRR and provide an extensive overview on the application of various in situ characterization approaches for on-site detection of reaction intermediates and catalyst transformations during electrocatalytic NRR processes, including different optical techniques, X-ray-based techniques, electron microscopy, and scanning probe microscopy. Finally, some major challenges and future directions of these in situ techniques are proposed.