EES catalysis最新文献

The development of low-cost transition metal catalysts for use in alkaline water electrolysis (AWE) at high current densities is essential for achieving high-performance water splitting. Here, we reported a CrSb–MnO₂ catalyst, which shows a low overpotential of 263 mV at 100 mA cm⁻² and outstanding stability with only a small degradation of the catalyst after 100 h of operation at 1 A cm⁻² (1 M KOH). In addition, the catalyst also achieved excellent performance in AWE (1.69 V@1 A cm⁻²). This enhanced performance is not only due to lattice-strain engineering, which effectively modulates the electronic configurations of the active sites, but also due to bimetallic synergy, which improves the dynamics of metal–metal charge transfer. In situ differential electrochemical mass spectrometry (DEMS) and Fourier-transform infrared (FTIR) analyses revealed that the CrSb–MnO₂ catalyst preferred the adsorbate evolution mechanism (AEM) during the alkaline OER. This preference contributes to sustained stability under high current conditions in alkaline media. This work offers a novel approach for designing membrane electrodes that can operate efficiently and stably under large currents.

We would like to take this opportunity to thank all of EES Catalysis’s reviewers for helping to preserve quality and integrity in chemical science literature. We would also like to highlight the Outstanding Reviewers for EES Catalysis in 2024.

The development of a synergistic coupling catalyst at the atomic scale for slurry-phase hydrogenation of vacuum residue (VR) is extremely challenging. Herein, we designed and constructed a robust coupling catalyst comprising Mo single atoms and MoS₂ (Mo SAs–MoS₂) using a reaction induction transformation strategy. The spontaneous generation of Mo SAs–MoS₂ synergistically promoted H₂ activation and enhanced local active hydrogen concentration in the hydrogenation of VR. Benefiting from the strong hydrogen concentration distribution in MoS₂ and Mo SAs, the catalyst revealed remarkable hydrogenation performance toward VR with a TOF_T of up to 0.39 s⁻¹, liquid product yield of 92 wt%, and coke content of 0.6 wt%. Theoretical calculations revealed that the synergistic action of Mo SAs–MoS₂ facilitated electron transfer between Mo species and reactants, reducing the desorption energy barriers for H₂ and anthracene and thereby promoting the hydrogenation of VR. This work provides a novel idea for the design of efficient coupling catalysts for strengthening local active hydrogen concentration in the hydrogenation of VR, and this concept can be applied to other hydrogenation systems.

Developing efficient strategies that convert industrial waste hydrogen sulfide (H₂S) into value-added products is meaningful for both applied environmental science and industrial chemistry. Here we report a series of heterogeneous N-doped carbon catalysts with synergistic C–N sites that enable the nucleophilic addition of H₂S into aromatic nitrile compounds (PhCN) under mild conditions to produce thiobenzamide (PhCSNH₂). The as-designed C–N sites achieve a high thioamide production rate of 26 400 μmol_PhCSNH2 L⁻¹ h⁻¹ and a notable selectivity of ca. 80% at 60 °C within a short 2-hour timeframe. Additionally, the catalyst exhibits easy recyclability and maintains high stability over ten cycles during a 6-month period. Systematic microscopic and in situ spectroscopic characterization, combined with theoretical calculations, reveal that C-pyridinic N coordination sites effectively lower the adsorption energy barrier of the crucial intermediate *PhCSHNH, offering a dynamically favorable pathway for PhCSNH₂ production. Furthermore, the protocol demonstrates excellent compatibility with various substituted substrates, providing access to a diverse range of thioamides.

There is a non-local energy wave reality that rules our local observable experiences, which is non-observable directly using quantum mechanics based on continuous functions in space-time. Thus, wavefunctions start the transition from a classical deterministic realm to a probabilistic and discrete one. The principles of quantum mechanics fundamentally diverge from classical intuitions; thus, quantum materials have emerged as materials that cannot be described in terms of semiclassical particles and low-level approximations of quantum mechanics. Quantum materials have unique properties including non-weak (strong) electronic correlations and some type of electronic orders, such as superconducting and spin–orbital (magnetic) orders, and multiple coexisting interdependent phases, which are associated with new perceptions such as superposition and entanglement. Examples of quantum materials include superconductors, topological materials, Moiré superlattices, quantum dots and magnetically ordered materials. Many (solid) catalysts show distinctive quantum behaviours, which are frequently associated with open-shell orbital configurations. Thus, this perspective aims to show that the literature is already full of quantum catalysts, and it is necessary to distinguish them and adapt/improve their theoretical models for better understanding. Part of this work is focused on clarifying the complex language of many-body quantum physics, isolating the approximations that are not fundamentally complete, and connecting the non-classical interactions with more familiar concepts in chemistry. This approach is also valuable for the physics community, since it gives a more chemical view to the properties of quantum materials, with its adapted terminology. In this case, we aim to go beyond mathematics to try to explain the possible meaning and plausible real interpretation of quantum correlations. Only the understanding of true quantum potentials and their interplay within the transition state theory would enable a complete conceptual description of the most relevant electronic interactions in catalysis. Consequently, there is almost no new science in this article; it is mainly a collection of examples of quantum catalysts and the origin of the successful theoretical models that predicted the results. Finally, a perspective on the status of this emerging field is presented, emphasizing the imminent significant role of quantum correlations. Currently, the advanced incorporation of the fundamental principles of orbital physics in solid-state quantum catalysts is leading the technological transition towards a greener and more sustainable economy. Quantum correlations unify catalysis and embrace advanced physics, because the rivalry between quantum interactions is likewise the reference electronic background that explains the properties of quantum materials.

This study compares thermal and post-plasma catalysis for dry reforming of methane (DRM) using nickel–alumina catalyst spheres. The optimum catalyst loading was first determined by thermo-catalytic performance testing and characterization. The selected catalyst spheres (4 wt% Ni loading) were introduced to a novel post-plasma-catalytic bed, designed to utilize the sensible heat from the plasma reactor and boost the DRM reaction without additional heating. A parametric scan of inlet CH₄ fractions (10–50 vol%) consistently shows improved CH₄ conversion in the presence of a catalyst. The CO and H₂ production rates reach peak values of ca. 24.4 mol mol_Ni⁻¹ min⁻¹ with 40 vol% CH₄ at the inlet, at a minimum energy cost (EC) of around 0.24 MJ per mol of reactant mixture. Interestingly, the addition of catalyst does not benefit the EC, but instead results in an improved syngas (H₂/CO) ratio for 10–30 vol% CH₄. In addition, a long-run post-plasma-catalytic test (6 h) demonstrates stable conversion and syngas ratio values. The EC obtained in this study is by far the lowest reported in post-plasma-catalytic DRM to date, and the insulated bed design reduces the heat loss from the bed and enables a more stable output. The successful coupling of a thermo-catalytic catalyst selection process with implementation in a post-plasma-catalytic bed demonstrates the coupling potential that can be realized between both research domains.

Driven by renewable energies, electrocatalytic CO₂ reduction (eCO₂R) in acidic media using membrane electrode assemblies (MEAs) has emerged as a highly promising approach for large-scale CO₂ utilization with economic viability. Nevertheless, the practical implementation faces significant challenges, including competing hydrogen evolution reaction, salt precipitation, and water flooding, which collectively undermine the long-term faradaic efficiency and operational durability. In this work, we develop an innovative asymmetric porous bipolar membrane (BPM) architecture by integrating electrospun anion-exchange nanofibers with a planar cation-exchange membrane, and configure it in the forward-bias mode (f-BPM) within MEAs to enable efficient acidic eCO₂R. The biphasic anion-exchange nanofibers, comprising polycationic piperidinium copolymer and hydrophobic polyvinylidene difluoride, are engineered to simultaneously optimize ion conductivity, membrane swelling, and mechanical integrity, thereby effectively regulating cation migration, electrochemical impedance, and water and gas transport properties. The optimized f-BPM configuration demonstrates exceptional performance, maintaining stable operation for 325 hours in acidic conditions, while achieving an average CO faradaic efficiency of 88% and a remarkable single-pass CO₂ conversion efficiency of 67% at a current density of 300 mA cm⁻² with a CO₂ flow rate of 15 sccm. Furthermore, the scalability of this technology is successfully demonstrated through the fabrication of a larger 5 × 5 cm² f-BPM, showcasing a stable operation over 110 hours with an energy efficiency of 34.2%. This breakthrough represents a significant advancement in acidic MEA technology, marking a crucial step toward industrial-scale implementation of eCO₂R.

The development of highly efficient catalysts for the selective hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG) is an important step in the conversion of syngas into high-value chemicals, which is of great significance for reducing dependence on petroleum and facilitating the transformation of energy structures. Herein three Ag nanoparticles with different size distributions were supported on mesoporous silica nanospheres (MSNS) with uniform center-radial mesopore channels (∼7 nm). The effects of the electronic and crystal structures of Ag nanoparticles on the adsorption and activation of DMO and H₂ were studied. The characterization results reveal that amino-functionalization of the support enables the silver–silicon catalyst to possess easily accessible highly dispersed Ag active components, lattice defects which are conducive to the adsorption, activation and diffusion of H₂, as well as electron-rich Ag^δ− species beneficial for the adsorption and activation of DMO, thereby endowing it with high activity, selectivity, and stability. In the reaction of DMO to MG, under the conditions of P = 2.0 MPa, T = 220 °C, H₂/DMO molar ratio = 80, and LHSV = 1.0 h⁻¹, the best catalytic state achieved a DMO conversion of 100%, a MG selectivity of 96.6%, a TOF as high as 207, and the MG yield could still remain above 95% after a 250 h lifetime investigation. Our research highlights a promising route for the development of high-performance Ag catalysts used in the syngas to MG process.

To address the increasingly serious problem of water pollution, photoelectrocatalysis (PEC), one of the advanced oxidation processes (AOPs), has gained significant attention due to its ability to utilize sunlight and its low energy consumption. In PECs, TiO₂ is the most widely used and established photoanode; however, non-TiO₂-based photoanodes have increasingly become a focus for improving visible light utilization and meeting the requirements of specific reactions. The performance of these non-TiO₂-based photoanodes in wastewater treatment varies based on different synthesis strategies and structures. Therefore, this paper critically reviews the synthesis, evaluation and characterization methods of non-TiO₂-based photoanodes used in wastewater treatment. Specifically, it reveals the application potential of various non-TiO₂-based photoanodes (such as WO₃, ZnO, g-C₃N₄, and BiVO₄), compares the costs and electrode stability of different synthesis methods from a practical application-oriented perspective, elucidates the synthesis–structure–mechanism–activity relationship, proposes an evaluation framework for PEC wastewater treatment based on multiple dimensions (including pollutant removal, electrode stability, light utilization efficiency, and environmental applicability), and introduces frontier theoretical simulations and characterization techniques of PEC wastewater treatment in depth according to the reaction process. Finally, an outlook on the preparation, evaluation and characterization of non-TiO₂-based photoanodes is proposed, covering perspectives from the atomic level to large-scale applications. This work aims to provide a comprehensive understanding of these ‘rising stars’ and guide the synthesis of photoanodes with enhanced performance, as well as more accurate evaluation and characterization.

Efficient metal-free heterogeneous photocatalysts, using visible light from the sun, continue to be a design challenge for use in chemical synthesis. Compared to metal-free photocatalysts involving a fundamental redox process, multi-dimensional photocatalytic systems with enhanced performance are limited. In this contribution, we demonstrated a general three-in-one approach to construct a donor–acceptor (D–A)-based porous organic polymer via connecting the most applied porphyrin with heptazine into a porous framework structure. Herein, a cooperative excitation process for O₂ activation was established, where porous organic polymers can not only generate ¹O₂ under light irradiation via a triplet state, but also capture O₂ and reduce it to O₂˙⁻. This synergistic effect dramatically improved the photocatalytic performance, as exemplified in the context of several important aerobic oxidative transformations, including sulfur mustard simulant degradation, oxidative coupling of primary amine molecules, and oxidative conversion of sulfides. Our work, therefore, paves a new way for the development of highly efficient heterogeneous photocatalysts.