ChemSusChem最新文献

Producing nitrogen-containing chemicals through the direct combination of by-products readily available from agricultural waste, including renewable aromatic building blocks from lignin, is a highly attractive approach for sustainable biorefining processes. Here, we describe a novel synthetic/catalytic route toward the production of the highly valuable β-adrenergic blocker esmolol. Our strategy consists of: 1) Reductive Catalytic Fractionation (RCF) of sugarcane lignocellulose mediated by copper porous metal oxides (Cu₂₀PMO) in MeOH, leading to the in situ formation of methyl 3-(4-hydroxyphenyl) propionate (1H) with good selectivity (>70%), followed by 2) the selective catalytic amination of glycerol carbonate (GlyC) with isopropyl amine via the borrowing hydrogen strategy, and 3) the subsequent utilization of the obtained amine intermediate as a phenol alkylating agent in combination with 1H to afford the desired β-adrenergic blocker esmolol (1Ha).

Layered high-entropy oxides represent a promising class of cathode materials for sodium-ion batteries (SIBs), owing to the sodium's natural abundance and advantageous electrochemistry. Conventional high-entropy designs, however, typically introduce multiple redox-active or inert elements, inevitably forcing a compromise between entropy-stabilized structural integrity and high specific capacity. Here, we demonstrate a dual-site modification approach for an O3-type Na_0.91Ca_0.02(Ni_0.3Li_0.05Fe_0.1Mn_0.4Ti_0.1Mg_0.05)O₂ cathode, by incorporating Ca²⁺ pillars in the Na layers and a high-entropy configuration within the transition-metal slab. The optimized cathode material exhibits a high reversible capacity of 145.2 mAh g⁻¹ at 0.1 C, remarkable rate performance (81.3% capacity retention at 2 C), and exceptional cycling stability (92.6% capacity retention after 800 cycles at 5 C) between 2.0 and 4.2 V. In situ X-ray diffraction and complementary kinetics analyses reveal that this design effectively suppresses the detrimental P3–OP2 phase transition above 4.0 V and promotes rapid Na⁺ transport. Our results establish that the synergistic entropy engineering and cationic substitution can reconcile high capacity with long-term cyclability, providing a strategic design route to practical high-energy cathode materials for SIBs.

Traditional sulfoxide synthesis often relies on toxic oxidants and harsh conditions. Photocatalytic oxidation using inorganic semiconductors provides a greener approach but is limited by low catalytic efficiency. Herein, we developed a heterostructure catalyst enriched with cadmium vacancies (denoted as Cd_vS_x/Ti₃CN). The optimized Cd_vS₄/Ti₃CN exhibited a high sulfoxide production rate of 21.85 mmol·g_cat^–1·h^–1, outperforming most reported catalytic systems. Comprehensive characterization revealed that sulfur dosage was precisely tuned during synthesis to generate abundant cadmium vacancies and expose active crystal facets. In particular, the presence of cadmium vacancies enhances substrate adsorption via unsaturated coordination sites, lowers the energy barrier for bond activation, and promotes the activation of O₂ into superoxide radicals. Moreover, Ti₃CN further facilitates photogenerated electron transfer and enhances superoxide radical concentration by enabling favorable band alignment with CdS. In addition, the catalyst demonstrates excellent substrate compatibility and recyclability. This work offers a new approach for improving the performance of CdS-based inorganic semiconductor catalysts in sulfoxide synthesis through Cd defect engineering.

This study introduces a novel modified dandelion-like CuWO₄/WO₃ heterojunction photoanode featuring NiCo-layered double hydroxide (NiCo-LDH) as a co-catalyst, fabricated through hydrothermal and drop casting methods. Morphological and photoelectrochemical assessments elucidate that the optimal dandelion-like CuWO₄/WO₃ heterojunction facilitates charge separation in a neutral solution. Additionally, electrochemical evaluations of the CuWO₄/WO₃ heterojunction decorated with LDHs co-catalysts reveal enhancements in photon-to-current conversion efficiency (IPCE), cathodic shift of the photocurrent onset potential, and an increase in photocurrent density to 0.17 mA cm⁻² at 1.23 V vs. RHE, which is twice that of the pristine photoanode under neutral pH conditions. The improved performance of the modified photoanode is attributed to the accelerated diffusion of reactants and products, as well as efficient proton-coupled electron transfer processes facilitated by the presence of LDHs.

SiO_x is a promising anode material for lithium-ion batteries (LIBs) due to its high theoretical capacity; nevertheless, its practical application is hampered by structural instability, poor conductivity, and uncontrolled solid electrolyte interface (SEI) growth. This study presents a systematic investigation of graphene oxide (GO) as a multifunctional additive integrated onto SiO_x/C anodes for LIBs, where the SiO_x/C was synthesized via a thermally induced sol–gel strategy to enhance uniformity and fabrication efficiency. GO loading facilitated the stabilization of the SEI layer, enhancing cycling stability while mitigating continuous electrolyte decomposition. The oxygen-containing functional groups in GO also helped with pseudocapacitive charge storage, which increased the overall capacity. Furthermore, GO acted as a structural binder, preventing SiO_x/C particle aggregation and preserving electrode integrity during prolonged cycling. The resulting 15% GO-SiO_x/C anode unveiled a high reversible capacity of 583.8 mAh g⁻¹ after 500 cycles at 0.5 A g⁻¹ and a sturdy cycle life of 498.3 mAh g⁻¹ after 350 cycles at 1 A g⁻¹. Post-cycling investigations verified the structural integrity of the GO-loaded electrode, underscoring the effectiveness of GO in mitigating volume expansion and fostering stable SEI generation.

This article presents a thorough review of perovskite solar cells (PSCs) thermal management. It starts with an analysis of solar cells’ temperature coefficients, emphasizing temperature's substantial effect on PSCs’ performance. The review includes a comparison of thermal coefficients across various solar cells: monocrystalline silicon, CIGS, perovskite, and tandem perovskite/silicon cells. The temperature sensitivity of PSCs is linked to perovskite materials’ thermal instability and temperature-sensitive components like the organic hole transport layer. The review explores the negative effects of high temperatures on PSCs’ performance, such as thermal stress, thermal decomposition, and phase transition behavior. To tackle these issues, diverse thermal management strategies are assessed, including passive cooling (radiative cooling, phase change materials, heat pipe cooling, and passive evaporative cooling) and active cooling methods (fluid circulation cooling, jet impingement cooling, and spectral filtering). The review also underlines the significance of thermal management for PSCs in various applications, such as extreme space conditions, reverse solar cells, and building-integrated photovoltaics. Furthermore, it discusses the potential of machine learning in aiding thermal management and the prospects of thermophotovoltaic cells. The review concludes by underscoring the crucial role of effective thermal management in improving PSCs’ efficiency and stability, which is vital for their large-scale energy production.

Electrocatalytic CO₂ reduction (ECO₂R) to high-value chemicals is a promising method to upcycle emitted CO₂, but it is also a fascinating scientific challenge. Catalyst materials, as well as cell configurations, play a pivotal role in the efficacy and efficiency of the ECO₂R reaction, which also dictates reaction pathways and product selectivity. In this work, we employ the isotopological Zr- and Ce-based UiO-67 metal–organic frameworks (MOFs) that contain Pd species in a zero-gap gas diffusion cathode electrode configuration, where the water content, i.e., relative humidity (RH) level, in the CO₂ gas stream can be varied. We show that only UiO-67-based MOFs containing Pd embedded in their pores can produce syngas, while the product selectivity can be controlled by varying the RH levels in the gas stream. The pristine MOFs (precatalysts) undergo chemical and structural transformation during the ECO₂R reaction, forming the active catalysts toward CO₂ electroreduction to syngas. Our work highlights the effect of water content on the selectivity during ECO₂R, but also the need for predictive catalyst design for effective electroreduction of CO₂ to high-value chemicals.

Nonthermal plasma (NTP)-assisted ammonia synthesis is an emerging catalytic method using plasma technology to activate reactants. It can operate at room temperature and atmospheric pressure, significantly boosting reaction activity and improving ammonia synthesis efficiency. However, standalone plasma systems still face limitations ammonia yield and energy efficiency, highlighting the need for synergistic effects from efficient catalysts to improve overall performance. In this study, a CoNi bimetallic catalyst supported on SBA-15 was designed and synthesized to optimize metal dispersion, increase the exposure of active surface sites, and enhance plasma activation efficiency. SBA-15 was synthesized hydrothermally, and Co and Ni were loaded by impregnation to obtain high-performance catalysts. Under room temperature and atmospheric pressure, the plasma-assisted ammonia synthesis achieved a yield of 228 μmol/(min·g_-cat). Comprehensive structural and surface characterizations (SEM, TEM, XRD, BET, NH₃-TPD, and XPS) revealed that the incorporation of Co significantly improved the dispersion of Ni, reduced the metal particle size, and strengthened the interaction between the metal and the support. These improvements contributed to enhanced adsorption and activation of reactive intermediates. This work provides insights into the design of efficient bimetallic catalysts for plasma-assisted ammonia synthesis and contributes to sustainable nitrogen utilization within the framework of a circular nitrogen economy.

Artificial photosynthesis using earth abundant resources water and oxygen to give a green oxidant hydrogen peroxide (H₂O₂) has drawn extensive attention. Targeted designing photocatalysts for efficient H₂O₂ synthesis remains a fundamental and technological challenge. In this regard, thiophene-derived structural motifs with unique conjugation systems and electron-rich properties often serve as building blocks for synthesis of metal-free porous organic semiconductors (POSs). These semiconductors have advantages for instance broad light absorption range, efficient charge separation and transfer, superior mass transportation, and good stability, along with flexible synthesis and functionalization, which exhibit excellent performance in H₂O₂ photosynthesis. This review summarizes the recent key advances in the synthesis of thiophene-derived POSs and their applications for H₂O₂ synthesis, which poses the current bottlenecks in this area. A general perspective on the future effort on this topic is provided.

In this work, we investigated the pyrolysis of sinapic acid (SA) as a lignin S-units model compound on the nanoceria catalyst. We employed various techniques to unravel the pyrolysis mechanism, including temperature-programmed desorption mass spectrometry, thermogravimetric, and IR spectroscopic techniques, complemented with atomistic simulations. From spectroscopic data and atomistic models, we report that SA interacts with the catalyst via its carboxyl group and aromatic functional groups; the amounts of various surface complexes depend on the acid concentration. Conformational analysis revealed that parallel adsorption on ceria was preferred over the perpendicular one (ΔE₀ = −154 kJ mol⁻¹). The main pyrolysis products are associated with transformations of phenolate complexes, with the predominant formation of syringol and with decarboxylation of carboxylates, forming 4-vinyl syringol, well known as canolol, thanks to its exceptional antioxidant properties. Modeling the transition state between the SA and its vinyl analog, canolol, displayed an additional intramolecular decarboxylation pathway with an activation energy barrier of +189 kJ mol⁻¹. This is consistent with the activation energy E^≠ = 194 kJ mol⁻¹ calculated from experimental kinetic data, and complements other established decarboxylation pathways. Methyl-syringol, cresol, phenol, toluene, benzene, and other aromatics were found among the catalytic pyrolysis products of SA.