Phenolic oligomers, abundant by-products from phenol and methanol alkylation and lignin valorization processes, contain resistant interunit C–C bonds that hinder their further utilization. Herein, we report a green and efficient catalytic system for the C–C bond cleavage of phenolic dimers over tartaric acid-modified HY zeolite, enabling the upcycling of phenolic wastes into valuable phenolic monomers. Moderate tartaric acid treatment (0.1 M) effectively removes both extra-framework and a portion of the framework aluminum species, generating secondary mesopores and exposing more accessible Brønsted acid sites on the external surface and within mesopores. Among the catalysts tested, 0.1 TA-HY exhibits the best performance, increasing the phenolic dimer conversion from 52.6
Integrated CO2 capture and conversion technology through coupling oxidative dehydrogenation of ethane (iCCC-ODHE) offers a promising economic pathway for carbon neutrality due to its high-value-added ethylene product without external hydrogen consumption. However, further industrial application is hindered by the low single-pass CO2 conversion efficiency. Herein, we demonstrate a synergistic C-H and C=O bond activation strategy to simultaneously promote both ethane and CO2 conversion efficiency through the construction of a dual-active-site of CoOx-VOx with proper spatial separation. The coloading of CoOx and VOx on the ZrO2 support successfully decouples the competition activations of C-H bond and C=O bond on one-active-site into simultaneous activations on dual-active-sites to facilitate the ODHE performance. Experimental characterizations, supported by DFT calculations, suggest that CoOx favors C2H6 activation, while VOx is more relevant to the CO2 activation, thus promoting the overall ODHE performance. When the optimized Co0.5V0.25-ZrO2 catalyst is integrated with a CO2 adsorbent of Ca4MgO5 in a dual-bed configuration at 675 degrees C, a superior record-high 92% single-pass CO2 conversion efficiency is achieved, with a 9.8 mmol/g of CO2 capture capacity, 49.5% ethane conversion efficiency, and 27.1% ethylene yield. Ten continuous iCCC-ODHE cycles demonstrate its excellent stability. Accordingly, this spatially separated dual-active-site strategy provides a rational catalyst design paradigm for complex consecutive reactions and practically advances the iCCC technology.
2,6-Diisopropylnaphthalene (2,6-DIPN) is a critical precursor for high-performance polymers. However, its synthesis via naphthalene isopropylation over HY zeolites is often limited by suboptimal selectivity and a susceptibility to coke deactivation, primarily due to restricted diffusion and uneven acid distribution. Herein, commercial HY zeolite was treated with aqueous citric acid solutions of different concentrations at 80°C, followed by washing, drying, and calcination, to regulate its pore structure and acidic microenvironment. Under the initial test conditions (180 °C, 0.7 MPa propene, 7 h), the naphthalene conversion and 2,6-DIPN selectivity over the 0.1 mol·L⁻¹ citric acid-modified HY zeolite were 97.65% and 29.55%, respectively. Upon further condition optimization (180 °C, 0.7 MPa, 5 h), the 0.1 CA-HY catalyst delivered optimal performance, achieving a naphthalene conversion of 97.37% while increasing the 2,6-DIPN selectivity to 34.6%. Comprehensive characterizations indicate that mild citric acid treatment modifies the aluminum coordination environment and promotes the removal of accessible aluminum-containing species, accompanied by the formation of a secondary mesoporous network. This hierarchical structural evolution effectively enhances the spatial accessibility of Brønsted acid sites and optimizes the Brønsted/Lewis (B/L) acid ratio. Furthermore, the 0.1 CA-HY catalyst exhibits favorable regenerability, retaining over 90% of its initial activity following a facile thermal treatment. This strategy provides a viable approach to balance micropore shape selectivity, mesopore mass transfer, and acidity regulation, presenting a promising catalytic system for arene alkylation.
Transition metal catalyzed [2+2+2] cycloaddition reactions between three alkynes, a diyne and an alkyne, or a triyne offer a straightforward and typical protocol toward all kinds of polysubstituted benzens. Herein, the synthesis of polysubstituted aromatics through electrochemical nickel catalyzed cyclotrimerization of alkynes is developed. The regio‐divergent cyclotrimerization of terminal alkynes is achieved by judicious choice of ligands, and tributylphosphine, sterically hindered bipyridine, or β‐diketone ligands delivered 1,2,4‐ and 1,3,5‐substituted aromatics with high regioselectivities, respectively. Besides, the semi‐intermolecular [2+2+2] cycloaddition between diynes and alkynes are also amenable under this catalytic system. This approach operates without metal reductant, exhibits wide functional groups tolerance, ease of scalability, and furnishes 75 examples with moderate to good yields, including some biorelevant compounds. Mechanistic experiments and density functional theory calculation reveal the catalytic pathways of 1,3,5‐ and 1,2,4‐cyclotrimerizations, and the origin of the ligand controlled regioselectivity.
This study proposes a novel strategy to enhance the catalytic performance of USY zeolites through selective aluminum extraction using tartaric acid and cerium substitution, with a focus on their application in the condensation of aniline with diphenylamine. A comprehensive characterization approach encompassing XRD, BET, and SEM analysis revealed that treatment with 0.1 mol/L tartaric acid led to the effective removal of aluminum atoms from the zeolite framework, concurrently generating new micropores. This process resulted in a substantial enhancement in the accessibility of the reactants. Infrared spectroscopy of pyridine confirmed that the addition of 5
USY zeolite was used as the main raw material for the aniline condensation reaction using alkali and rare earth element (cerium) modification. The texture properties were characterized by nitrogen adsorption, X-ray diffraction, and Fourier transform infrared. The results showed that alkali treatment and rare earth element combined modification had a synergistic effect, which effectively improved the conversion rate of aniline. The 0.25 M NaOH-5% Ce-USY catalyst demonstrated a conversion rate approximately 50% higher than the unmodified zeolite. Alkali treatment of the zeolite generated additional micropores, enhancing the catalyst's surface area and reactant accessibility. The dispersion of cerium species modulated the zeolite's hydroxyl groups, optimizing both acidity and catalyst performance. Density functional theory calculations elucidated the underlying reaction mechanism. This advancement not only provides a catalyst for aniline condensation but also offers insights into the modification of acid-catalyzed reaction catalysts.
Kitchen waste has become a significant environmental concern worldwide. Red mud, an industrial solid waste characterized by its porous structure and high iron oxide content, exhibits potential as a conductive conduit in the direct interspecies electron transfer (DIET) pathway. In this study, red mud pretreatment of kitchen waste was conducted to enhance anaerobic digestion (AD). The effect and mechanism of enhancing kitchen waste AD by red mud pretreatment was studied for the first time. Results indicated that red mud pretreatment could accelerate the hydrolysis of organic compounds and alleviate the acid inhibition. Consequently, the methane production rate was increased from 260.7mL/g VS to 402.3mL/g VS, i.e., up to 54.3%. And volatile solids removal efficiency was increased from 53.9% to 73.1%, i.e., up to 35.6%. Furthermore, microbial community analysis revealed the enrichment of electrochemically active bacteria (Synergistaceae), acetogenic bacteria (Syntrophomonadaceae) and methanogens (Methanobacterium and Methanosarcina), which played essential roles in interspecies hydrogen transfer (IHT) and DIET. This study showed that red mud pretreatment has the potential to enhance kitchen waste AD which contributes to carbon mitigation. It also threw the potential new insights to the relative mechanism.
Organohalide-respiring bacteria (OHRB) have been found in various environments and play an indispensable role in the biogeochemical cycling and detoxification of halogenated organic compounds (HOCs). Currently, few ORHB have been reported to perform reductive dechlorination under high salinity conditions, indicating a knowledge gap on the diversity of OHRB and the survival strategy of OHRB in saline environments (e.g., estuarine, marine). This study reports the characterization of an enrichment culture dominated by a new Dehalogenimonas population strain W derived from estuarine sediments, which demonstrates the capability to dechlorinate 1,2-dichloroethane (1,2-DCA) to ethene under elevated salinity (≥5.1% NaCl, w/v). Metagenomic and proteomic analyses revealed that the distinctive high-salinity dechlorination of strain W is primarily attributed to a putative reductive dehalogenase (RDase) DdeA, which shares >91.4% amino acid identity with the dihaloeliminating RDase DcpA from other Dehalogenimonas strains. Additionally, ectoine biosynthesis enzymes (EctABC) contribute to the strain's salt tolerance. These findings underscore the potential of OHRB, particularly Dehalogenimonas, to detoxify HOCs in high-salinity environments, such as estuarine and marine ecosystems, by employing compatible solutes as an adaptive mechanism.
The heterogeneous nanoparticles-nanorod Ni- NiMoO4 nanostructures grown in situ on nickel foam (Ni- NiMoO4/NF) were rationally engineered as efficient electrocatalysts. The morphological and compositional features cooperatively propel high-performance electrocatalysis to hydrogen evolution reaction (eta 10, eta 100, and eta 200 values are 26/84/113 mV in fresh water and 27/101/132 mV in seawater), urea oxidation reaction (eta 10, eta 100, and eta 200 values are 1.321/1.340/1.356 and 1.329/1.344/1.361 V in fresh/seawater). The Ni- NiMoO4/NF nanostructures therefore perform a low cell voltage of 1.506/1.509@10 mA cm-2 in fresh/sea water. Specifically, the record cell voltage even drops to as low as 1.339/1.361 V in fresh/sea water for overall urea splitting (OUS) reaction with a long-term stability for 240 h@100 mA cm-2 toward OUS in seawater. More importantly, to realize a green manner, we also evaluated a solar-driven H2 production. Even in seawater, H2 gas was collected in high speed under solar illumination on a commercial solar panel.
Review Life Cycle Assessment of Microalgal Carbon Fixation and Torrefaction for Carbon Neutralization: A State-of-the-Art Review Congyu Zhang *, Jin Fang, Yong Zhan, Xin Wang, Tao Chen, Kuifeng Hao, Jiaqi Ma and Yuting Wang School of Resources and Environment, Northeast Agricultural University, Harbin 150030, China * Correspondence: ztdw7727@163.com Received: 23 May 2024; Revised: 12 August 2024; Accepted: 5 September 2024; Published: 10 September 2024 Abstract: In the past decades, a series of phenomena such as global warming, glacier melting, sea level rise, and haze weather caused by the greenhouse effect have been reported, which seriously threaten the future of humans. To address this challenge, several countries have initiated interventions to prevent climate change, such as carbon neutralization. Given the current economic, social development and environmental protection requirements, microalgal carbon fixation appears to be a suitable approach to achieve carbon net zero emission while also promoting microalgal biofuel production. This promotes the realization of energy structure transformation and optimization of carbon neutralization. This article provides a comprehensive and state-of-the-art review of research progress on microalgal carbon capture and solid biofuel production via the torrefaction process, with focus on the efficiency and capacity of microalgal carbon fixation, as well as the principle and application of microalgal torrefaction. The detailed review includes the practical value and development prospect of microalgal torrefied biochar, fuel performance conversion, and mechanism in the torrefaction process. Furthermore, the environmental impact of microalgal carbon fixation and torrefaction process are discussed to evaluate the overall environmental benefits of microalgal utilization via life cycle assessment (LCA) method. The technical difficulties of microalgal carbon fixation and torrefaction process are also discussed. This review paper is beneficial to guide the scheme demonstration and specific implementation of microalgal carbon neutralization and thus lead to the efficient establishment of microalgal carbon reduction, biomass accumulation, and biofuel production techniques.
Figure S2: IL-18 receptor (IL-18R) expression in pancreatic cancer tissues and cell lines.
Raw data for "Lithium carbonate-promoted mixed rare earth oxides as a generalized strategy for oxidative coupling of methane with exceptional yields"
Cisplatin resistance remains a major obstacle limiting the effectiveness of chemotherapy in cervical cancer. However, the underlying mechanism of cisplatin resistance is still unclear. In this study, we demonstrate that vacuolar protein sorting 13 homolog C (VPS13C) deficiency promotes cisplatin resistance in cervical cancer. Moreover, through an RNA sequencing screen, VPS13C deficiency was identified as negatively correlated with the high expression of glutathione S-transferase pi gene (GSTP1). Mechanistically, loss of VPS13C contributes to cisplatin resistance by influencing the expression of GSTP1 and inhibiting the downstream c-Jun N-terminal kinase (JNK) pathway. In addition, targeting GSTP1 with the inhibitor NBDHEX effectively rescued the cisplatin resistance induced by VPS13C deficiency. Overall, our findings provide insights into the underlying mechanisms of VPS13C in cisplatin resistance and identify VPS13C as a promising candidate for the treatment of chemoresistance in cervical cancer.
Several tables contain the nucleotide sequences, antibodies information, the correlation between NRBP2 and clinicopathological features and the mass spectrometric analysis results.
High solid anaerobic digestion (AD) has been considered as a promising and sustainable technology for treating kitchen waste. To enhance AD of kitchen waste, alkali pretreatment and bentonite addition treatment (AP/Be) was performed on kitchen waste, and microbial community was investigated at different total solids (TS) content (10%, 13%, 19%, 22% and 25%). The results indicated that after AP/Be treatment, methane yield was as high as 198 mL CH4/g volatile solid (VS), which increased by 236% as the control. Moreover, microbial community analysis revealed that AP/Be treatment enriched bacterial microbial diversity. At TS of 10%, AP/Be treatment enhanced the hydrogenotrophic methanogens (Methanobacterium) significantly. In addition, the dominant methanogenic pathways changed at different TS content. These results demonstrated AP/Be treatment had a positive effect on methanogenesis during kitchen waste anaerobic digestion process. This study threw new insights towards enhancing kitchen waste anaerobic digestion, as well as the microbial mechanism.
Figure S1: IL-18 is higher in PC tissues and correlates with poorer survival. Immunohistochemical (IHC) staining of IL-18