Designed Synthesis of Fe/Zr Bimetallic Organic Framework to Enhance the Selective Conversion of H2S to Sulfur.

The development of stable and effective catalysts to convert toxic H2S into high value-added sulfur is essential for production safety and environmental protection. However, the inherent defects of traditional iron- and zirconium-based catalysts, such as poor activity, high oxygen consumption, and low sulfur selectivity, limit their further developments and applications. Herein, the Fe-Zr bimetallic organic framework FeUIO-66(x) with different cubic morphologies was synthesized via a facile solvothermal method. The results indicate that the introduction of Fe not only increases the specific surface area and weak L-sites of the catalyst without changing its crystal structure, which provides enough reaction space and more active sites for the adsorption and activation of H2S, but also reduces the activation energy of the reaction, significantly promoting the selective oxidation of H2S. As a result, the as-obtained FeUIO-66(1) catalyst exhibits the highest desulfurization activity and superior durability and water resistance stability, and its H2S conversion and sulfur selectivity within 50 h are 100 and 88%, respectively. More importantly, the structure of the catalyst after the desulfurization reaction is consistent with that of the fresh counterpart. The study offers new insights into the development of effective and stable bimetallic catalysts to eliminate H2S and recycle sulfur.

Interfacial Engineering Boosting the Activity and Stability of MIL-53(Fe) toward Electrocatalytic Nitrogen Reduction.

The electrochemical nitrogen reduction reaction (eNRR) has emerged as a promising strategy for green ammonia synthesis. However, it suffers unsatisfactory reaction performance owing to the low aqueous solubility of N2 in aqueous solution, the high dissociation energy of N≡N, and the unavoidable competing hydrogen evolution reaction (HER). Herein, a MIL-53(Fe)@TiO2 catalyst is designed and synthesized for highly efficient eNRR. Relative to simple MIL-53(Fe), MIL-53(Fe)@TiO2 achieves a 2-fold enhancement in the Faradaic efficiency (FE) with an improved ammonia yield rate by 76.5% at -0.1 V versus reversible hydrogen electrode (RHE). After four cycles of electrocatalysis, MIL-53(Fe)@TiO2 can maintain a good catalytic activity, while MIL-53(Fe) exhibits a significant decrease in the NH3 yield rate and FE by 79.8 and 82.3%, respectively. Benefiting from the synergetic effect between TiO2 and MIL-53(Fe) in the composites, Fe3+ ions can be greatly stabilized in MIL-53(Fe) during the eNRR process, which greatly hinders the catalyst deactivation caused by the electrochemical reduction of Fe3+ ions. Further, the charge transfer ability in the interface of composites can be improved, and thus, the eNRR activity is significantly boosted. These findings provide a promising insight into the preparation of efficient composite electrocatalysts.

Boosting N2 Conversion into NH3 over Ru Catalysts via Modulating the Ru-Promoter Interface.

Promoters are indispensable components of Ru-based catalysts to promote N2 activation in ammonia (NH3) synthesis. The rational addition and regulation of promoters play a critical role in affecting the NH3 synthesis rate. In this work, we report a simple method by altering the loading sequence of Ba and Ru species to modulate the Ru-promoter interface, thus significantly boosting the NH3 synthesis rate. The Ba-Ru/GC BM catalyst via the prior loading of Ba rather than Ru over graphitic carbon (GC) exhibits a high NH3 synthesis rate of 18.7 mmol gcat-1 h-1 at 400 °C and 1 MPa, which is 2.5 times that of the Ru-Ba/GC BM catalyst via the conventional prior loading of Ru rather than Ba on GC. Our studies reveal that the prior loading of Ba benefits the high dispersion of the basic Ba promoter over an electron-withdrawing GC support, and then Ba species serve as structural promoters to stabilize Ru with small particle sizes, which exposes more active sites for N2 activation. Additionally, the intimate Ba and Ru interface enables facile electron donation from Ba to Ru sites, thus accelerating N2 dissociation to realize efficient NH3 synthesis. This work provides a simple approach to modulating the Ru-promoter interface and maximizing promoter utilization to enhance NH3 synthesis performance.

Counting d-Orbital Vacancies of Transition-Metal Catalysts for the Sulfur Reduction Reaction.

The electrocatalytic sulfur reduction reaction (SRR) would allow the production of renewable high-capacity rechargeable lithium-sulfur (Li-S) batteries using sustainable and nontoxic elemental sulfur as a cathode material, but its slow reaction rate causes a serious shuttle effect and dramatically reduces the capacity. We found that a catalyst composed of Pd nanoparticles supported by ordered mesoporous carbon (Pd/OMC) had a high reaction rate in the SRR, and a Li-S battery assembled with this catalyst had a low shuttle constant of 0.031 h-1 and a high-rate performance with a specific capacity of 1527 mAh g-1 at 0.1 C which is close to the theoretical value. The high activity of Pd/OMC with a d-orbital vacancy of 0.87 e was predicted from a volcano relationship between the d charge for the metal and the adsorption activation entropy and reaction rate for the SRR by examining Pd, Au, Pt, Rh, and Ru transition-metal nanocatalysts. The strategy of using a single electronic structure descriptor to design high-efficiency SRR catalysts has suggested a way to produce practical Li-S batteries.

Boosting the ammonia synthesis activity of ceria-supported Ru catalysts achieved through trace Pr addition.

The amount of dopant used in conventional cases for improving catalytic performance is higher than 5%. In this work, a strategy to enhance the ammonia synthesis performance of a Ru/CeO2 catalyst by using trace Pr (0.1 mol%) is reported. Owing to the improvement of oxygen defects, Ce3+ concentration and interfaced Ru species, the hydrogen adsorption was enhanced, and the desorption of hydrogen species would be promoted. As a result, Ru/CeO2 with 0.1 mol% Pr shows 1.4 times higher ammonia synthesis rate and excellent stability compared to Ru/CeO2 or the sample with high Pr loading (50 mol% Pr). This study provides a new idea for the design of high-efficiency ammonia synthesis catalysts.

Elucidation of Anti-Hypertensive Mechanism by a Novel Lactobacillus rhamnosus AC1 Fermented Soymilk in the Deoxycorticosterone Acetate-Salt Hypertensive Rats.

Dietary intake of fermented soymilk is associated with hypotensive effects, but the mechanisms involved have not been fully elucidated. We investigated the anti-hypertensive effects of soymilk fermented by L. rhamnosus AC1 on DOCA-salt hypertension from the point of view of oxidative stress, inflammatory response and alteration of the gut microbiome. The antioxidant assays in vitro indicated the ethanol extract (EE) of L. rhamnosus AC1 fermented soymilk showed better antioxidative effects than the water extract (WE). Those extracts displayed a hypotensive effect using a tail-cuff approach to measuring blood pressure and improved nitric oxide (NO), angiotensin II (Ang II), tumor necrosis factor-α (TNF-α) and interleukin factor-6 (IL-6) on DOCA-salt hypertensive rats. Furthermore, cardiac and renal fibrosis were attenuated by those extracts. The gut microbiota analysis revealed that they significantly reduced the abundance of phylum Proteobacteria, its family Enterobacteriaceae and genus Escherichia-Shigella. Moreover, metabolomic profiling revealed several potential gut microbiota-related metabolites which appeared to involve in the development and recovery of hypertension. In conclusion, fermented soymilk is a promising nutritional intervention strategy to improve hypertension via reducing inflammation and reverting dysbiotic microbiota.

Gas-template directed in situ synthesis of highly nitrogen-doped carbon nanotubes with superior sulfur compatibility and enhanced functionalities.

Herein, we develop a low temperature gas template route for in situ growth of highly nitrogen-doped (5.68 wt%), multi-walled carbon nanotubes (N-MWCNTs). The N-MWCNTs exhibit superior sulfur compatibility in hydrogen sulfide (H2S) resource utilization, thus resulting in their enhanced functionality as Li-S cathodes with high sulfur-specific capacity and retention rate.

Spatially revealed perfluorooctane sulfonate-induced nephrotoxicity in mouse kidney using atmospheric pressure MALDI mass spectrometry imaging.

Perfluorooctane sulfonate (PFOS), an emerging environmental persistent pollutant, has attracted extensive attention due to its potential nephrotoxicity. However, little is known about the spatial variations of lipid metabolism associated with PFOS exposure. In this study, atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry imaging (AP-MALDI MSI) was used to reveal the spatial distributions of PFOS and its adverse effect on lipid metabolism directly in mouse kidney sections. We have observed that PFOS accumulated in the renal pelvis and outer cortex regions, with some found in the medulla and inner cortex regions. Hematoxylin and eosin (H&E) staining results also demonstrated that the accumulation of PFOS caused damage to the mouse kidney, which was consistent with AP-MALDI MSI results. Furthermore, a total of 42 lipids were shown to be significantly different in the spatial distribution patterns and variations between control and PFOS exposure mice groups, including the significant down-regulation of lyso-glycerophospholipids (Lyso-GPs), phosphatidic acids (PA), phosphatidylcholines (PC), phosphatidylethanolamines (PE), phosphatidylserines (PS) sphingomyelins (SM) and sulfatides (ST) in renal medulla or cortex region of mouse kidney sections, and remarkable up-regulation of cholesterol and phosphatidylinositols (PI) in the cortex regions of mouse kidney sections. The AP-MALDI MSI provides a new tool to explore spatial distributions and variations of the endogenous metabolites for the risk assessment of environmental pollutants.

The Role of Fecal Microbiota in Liver Toxicity Induced by Perfluorooctane Sulfonate in Male and Female Mice.

BACKGROUND: Perfluorooctane sulfonate (PFOS) is a persistent organic pollutant that can cause hepatotoxicity. The underlying toxicological mechanism remains to be investigated. Given the critical role of fecal microbiota in liver function, it is possible that fecal microbiota may contribute to the liver toxicity induced by PFOS. OBJECTIVES: We aimed to investigate the role of liver-fecal microbiota axis in modulating PFOS-induced liver injury in mice. METHODS: Male and female mice were exposed to PFOS or vehicle for 14 d. In this investigation, 16S rDNA sequencing and metabolomic profiling were performed to identify the perturbed fecal microbiota and altered metabolites with PFOS exposure. In addition, antibiotic treatment, fecal microbiota transplantation, and bacterial administration were conducted to validate the causal role of fecal microbiota in mediating PFOS-induced liver injury and explore the potential underlying mechanisms. RESULTS: Both male and female mice exposed to PFOS exhibited liver inflammation and steatosis, which were accompanied by fecal microbiota dysbiosis and the disturbance of amino acid metabolism in comparison with control groups. The hepatic lesions were fecal microbiota-dependent, as supported by antibiotic treatment and fecal microbiota transplantation. Mice with altered fecal microbiota in antibiotic treatment or fecal microbiota transplantation experiments exhibited altered arginine concentrations in the liver and feces. Notably, we observed sex-specific lower levels of key microbiota, including Lactobacillus, Enterococcus, and Akkermansia. Mice treated with specific bacteria showed lower arginine levels and lower expression of the phosphorylated mTOR and P70S6K, suggesting lower activity of the related pathway and mitigation of the pathological differences observed in PFOS-exposed mice. CONCLUSIONS: Our study demonstrated the critical role of the fecal microbiota in PFOS-induced liver injury in mice. We also identified several critical bacteria that could protect against liver injury induced by PFOS in male and female mice. Our present research provided novel insights into the mechanism of PFOS-induced liver injury in mice. https://doi.org/10.1289/EHP10281.

Enhanced ammonia synthesis activity of carbon-supported Mo catalyst by Mo carburization.

It is urgent to develop new efficient ammonia synthesis catalysts using non-precious metals. Herein, the Mo2C species is introduced into a carbon-supported Mo catalyst by in situ carburization of a carbon-supported Mo catalyst in H2. In combination with the presence of the Mo2C phase as well as the enhancement of the graphitization degree of carbon and the amount of the low-valent Mo species, the migration and the exchange of the adsorbed species with the gaseous species are accelerated. As a result, the catalyst with carbonization treatment shows higher ammonia synthesis activity than the sample without carbonization, and the ill effect of the poisoning of reagent gases also is alleviated.

Efficiently Integrated Desulfurization from Natural Gas over Zn-ZIF-Derived Hierarchical Lamellar Carbon Frameworks.

Selective removal of carbonyl sulfide (COS) and hydrogen sulfide (H2S) is the key step for natural gas desulfurization due to the highly toxic and corrosive features of these gaseous sulfides, and efficient and stable desulfurizers are urgently needed in the industry. Herein, we report a class of nitrogen-functionalized, hierarchically lamellar carbon frameworks (N-HLCF-xs), which are obtained from the structural transformation of Zn zeolitic imidazolate frameworks via controllable carbonization. The N-HLCF-xs possess the desirable characteristics of large Brunauer-Emmett-Teller surface areas (645-923 m2/g), combined primary three-dimensional microporosity and secondary two-dimensional lamellar microstructure, and high density of nitrogen base sites with enhanced pyridine ratio (17.52 wt %, 59.91%). The anchored nitrogen base sites in N-HLCF-xs show improved accessibility, which boosts their interaction with acidic COS and H2S. As expected, N-HLCF-xs can be employed as multifunctional and efficient desulfurizers for selective removal of COS and H2S from natural gas. COS was first transformed into H2S via catalytic hydrolysis, and the produced H2S was then captured and separated and catalyzed oxidation into elemental sulfur. The above continuous processes can be achieved with solo N-HLCF-xs, giving extremely high efficiencies and reusability. Their integrated desulfurization performance was better than many desulfurizers used in the area, such as activated carbon, ß zeolite, MIL-101(Fe), K2CO3/γ-Al2O3, and FeOx/TiO2.

Sustainable synthesis of ordered mesoporous materials without additional solvents.

Micelles with well-defined nanostructures were generally formed in the presence of a suitable solvent. We report herein the accelerated construction of micelles with ordered nanostructures without assistance of additional solvents. The micelles were employed for ultrafast fabrication of ordered mesoporous silicas (OMS) using tetramethyl orthosilicate (TMOS) as silica source. When γ-aminopropyl triethoxysilane precursor was introduced, we obtained amine group (-NH2) decorated ordered mesoporous silicas (OMS-NH2-x, where x stands for the molar ratio of γ-aminopropyl triethoxysilane to TMOS). The resulted materials are large in BET surface area and tunable in content of -NH2 site, which are highly efficient for catalytic elimination of gaseous carbonyl sulfide and hydrogen sulfide. Using this strategy, other functionalized groups such as thiol and benzene can be also introduced into OMS. Furthermore, the introducing of phenolic precursor into the system leads to multiphase co-assembly for the formation of ordered mesoporous silica-polymer nanocomposites. It is demonstrated that the solvent-free ultrafast assembly offers a sustainable route for preparation of ordered mesoporous functional materials.

Bimetallic Metal-Organic Frameworks MIL-53(xAl-yFe) as Efficient Catalysts for H2S Selective Oxidation.

Catalytic oxidation of H2S is a crucial green pathway that can fully convert H2S into value-added elemental S for commercial use. However, achieving high catalytic stability and S selectivity by traditional-metal-based catalysts still remain a major challenge. Herein, a facile one-step solvothermal strategy is designed for the fabrication of bimetallic MIL-53(xAl-yFe) catalysts. The as-synthesized MIL-53(1Al-5Fe) possesses ample coordinatively unsaturated metal sites, which served as efficient catalytic sites for the selective oxidation of H2S. As a result, the representative MIL-53(1Al-5Fe) achieves a S yield of nearly 100% at 100-160 °C with almost no obvious decrease of catalytic stability in the run of 30 h. Under the defined reaction conditions, the bimetallic metal-organic frameworks are obviously superior to MIL-53(Al) (49.3%) and MIL-53(Fe) (70.5%) in S yield. This study suggests that the introduction of elemental Al into MIL-53(xAl-yFe) could effectively modulate the electronic properties and spatial configuration of the catalysts, further conducing the adsorption and activation of H2S and thus accelerating the dissociation of H2S into a key intermediate S* and improving their catalytic performance.

Highly Poison-Resistant Single-Atom Co-N4 Active Sites with Superior Operational Stability over 460 h for H2 S Catalytic Oxidation.

Efficient catalytic elimination of hydrogen sulfide (H2 S) with high activity and durability in nature gas and blast-furnace gas is very critical for both fundamental catalytic research and applied environmental chemistry. Herein, atomically dispersed Co atom catalysts with Co-N4 sites that can transform H2 S into S with conversion rate of ≈100% are designed and prepared. The representative 4Co-N/NC achieves a sulfur yield of nearly 100% and TOF(Co) of 869 h-1 at 180 °C. Importantly, remarkable long-term durability is achieved as well, with no obvious loss of catalytic activity in the run of 460 h, outperforming most of the reported catalysts. The short bond length and strong cooperation of Co-N are beneficial to improve the structural stability of the Co-N4 centers, and significantly enhanced resistance of water and sulfation over single-atom Co-catalyst. The present mechanism involves the stepwise hydrogen transfer process via the adsorbed *HOO and *HS intermediates.

Integration of omics analysis and atmospheric pressure MALDI mass spectrometry imaging reveals the cadmium toxicity on female ICR mouse.

Acute cadmium toxicity induces multi-system organ failure. Mass spectrometry (MS)-based omics analyses and atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry imaging (AP-MALDI MSI) are powerful tools for characterizing the biomarkers. Many studies on cadmium toxicity by metabolomics have been investigated, whereas the applications of lipidomics and MSI studies are still inadequate. In this study, the systematic metabolomics study on female ICR mice tissues including liver, kidney, heart, stomach, brain as well as spleen under cadmium exposure was firstly conducted and lipidomic characterizations on female ICR mice liver, kidney and heart were further constructed step by step. To deeply understand its toxicological mechanisms, several representative lipids on the mouse liver were visualized by AP-MALDI MSI. The results demonstrated that exposure to cadmium caused significant metabolic alterations in the liver, kidney and heart among all the tissues. Additionally, the toxicological mechanisms of cadmium in the mouse models are closely associated with the inflammation response, energy expenditure, oxidative stress, DNA and mitochondria damage, and lipid homeostasis. These insights could enhance knowledge in acute cadmium toxicity of public health and guide risk assessment in the future.

Comprehensive multi-omics approaches reveal the hepatotoxic mechanism of perfluorohexanoic acid (PFHxA) in mice.

Perfluorohexanoic acid (PFHxA), one of the short-chain perfluoroalkyl acids (PFAAs), is considered as a substitute of perfluorooctane sulfonate (PFOS). This emerging organic pollutant is persistent and highly bioavailable to humans, raising concerns about its potential health risks. There are currently few researches on the toxicity of PFHxA. Liver has been suggested to be the main target of PFHxA toxicity, and the mechanism remains unclear. Herein, we investigated the transcriptomic, proteomic, and metabolomic landscape in PFHxA-exposed mice. Using these approaches, we identified several valuable biological processes involved in the process of liver injury, comprising fatty acid biosynthesis and degradation pathways, which might be induced by peroxisome proliferator-activated receptor (PPAR) signaling pathway. These processes further promoted oxidative stress and induced liver injury. Meanwhile, abnormalities in purine metabolism and glutathione metabolism were observed during the liver injury induced by PFHxA, indicating the production of oxidative stress. Finally, our present multi-omics studies provided new insights into the mechanisms involved in PFHxA-induced liver injury.

Highly efficient ammonia synthesis at low temperature over a Ru-Co catalyst with dual atomically dispersed active centers.

The desire for a carbon-free society and the continuously increasing demand for clean energy make it valuable to exploit green ammonia (NH3) synthesis that proceeds via the electrolysis driven Haber-Bosch (eHB) process. The key for successful operation is to develop advanced catalysts that can operate under mild conditions with efficacy. The main bottleneck of NH3 synthesis under mild conditions is the known scaling relation in which the feasibility of N2 dissociative adsorption of a catalyst is inversely related to that of the desorption of surface N-containing intermediate species, which leads to the dilemma that NH3 synthesis could not be catalyzed effectively under mild conditions. The present work offers a new strategy via introducing atomically dispersed Ru onto a single Co atom coordinated with pyrrolic N, which forms RuCo dual single-atom active sites. In this system the d-band centers of Ru and Co were both regulated to decouple the scaling relation. Detailed experimental and theoretical investigations demonstrate that the d-bands of Ru and Co both become narrow, and there is a significant overlapping of t2g and eg orbitals as well as the formation of a nearly uniform Co 3d ligand field, making the electronic structure of the Co atom resemble that of a "free-atom". The "free-Co-atom" acts as a bridge to facilitate electron transfer from pyrrolic N to surface Ru single atoms, which enables the Ru atom to donate electrons to the antibonding π* orbitals of N2, thus resulting in promoted N2 adsorption and activation. Meanwhile, H2 adsorbs dissociatively on the Co center to form a hydride, which can transfer to the Ru site to cause the hydrogenation of the activated N2 to generate N2H x (x = 1-4) intermediates. The narrow d-band centers of this RuCo catalyst facilitate desorption of surface *NH3 intermediates even at 50 °C. The cooperativity of the RuCo system decouples the sites for the activation of N2 from those for the desorption of *NH3 and *N2H x intermediates, giving rise to a favorable pathway for efficient NH3 synthesis under mild conditions.

Engineering of crystal phase over porous MnO2 with 3D morphology for highly efficient elimination of H2S.

In the present work, we report a facile oxalate-derived hydrothermal method to fabricate α-, ß- and δ-MnO2 catalysts with hierarchically porous structure and study the phase-dependent behavior for selective oxidation of H2S over MnO2 catalysts. It was disclosed that the oxygen vacancy, reducibility and acid property of MnO2 are essentially determined by the crystalline phase. Systematic experiments demonstrate that δ-MnO2 is superior in active oxygen species, activation energy and H2S adsorption capacity among the prepared catalysts. As a consequence, δ-MnO2 nanosphere with a hierarchically porous structure shows high activity and stability with almost 100% H2S conversion and sulfur selectivity at 210 °C, better than majority of reported Mn-based materials. Meanwhile, hierarchically porous structure of δ-MnO2 nanosphere alleviates the generation of by-product SO2 and sulfate, promoting the adoptability of Mn-based catalysts in industrial applications.

Construction of a Pd(PdO)/Co3O4@SiO2 core-shell structure for efficient low-temperature methane combustion.

Catalytic combustion is a promising way to remove trace amounts of CH4 to alleviate serious environmental concerns. However, the reactivity of a catalyst at low temperature is usually limited because of the difficulty to activate the C-H bond of methane. Herein, we design a Pd(PdO)/Co3O4@SiO2 bimetallic oxide core-shell catalyst which shows much higher activity in the methane combustion reaction compared with Pd(PdO)/SiO2 and Co3O4@SiO2 catalysts without a core-shell structure. The T50% and T90% of Pd(PdO)/Co3O4@SiO2 are 357 °C and 445 °C, respectively, which decrease by 67 °C and 55 °C in comparison with those of Pd(PdO)/SiO2. Extensive characterization demonstrates that the bimetallic oxide core-shell structure can effectively enhance the metal interaction between Pd and Co, which can weaken the strength of the Co-O bond in Pd(PdO)/Co3O4@SiO2. The weakening of the Co-O bond could promote the release of more lattice oxygen species to participate in the C-H breaking, resulting in superior catalytic performance in methane combustion at low temperature.

Structural analysis of glycosaminoglycans from Oviductus ranae.

Oviductus ranae (O.ran.) has been widely used as a tonic and a traditional animal-based Chinese medicine. O.ran. extracts have been reported to have numerous biological activities, including activities that are often associated with mammalian glycosaminoglycans such as anti-inflammatory, antiosteoperotic, and anti-asthmatic. Glycosaminoglycans are complex linear polysaccharides ubiquitous in mammals that possess a wide range of biological activities. However, their presence and possible structural characteristics within O.ran. were previously unknown. In this study, glycosaminoglycans were isolated from O.ran. and their disaccharide compositions were analyzed by liquid chromatography-ion trap/time-of-flight mass spectrometry (LC-MS-ITTOF). Heparan sulfate (HS)/heparin (HP), chondroitin sulfate (CS)/dermatan sulfate (DS) and hyaluronic acid (HA) were detected in O.ran. with varied disaccharide compositions. HS species contain highly acetylated disaccharides, and have various structures in their constituent chains. CS/DS chains also possess a heterogeneous structure with different sulfation patterns and densities. This novel structural information could help clarify the possible involvement of these polysaccharides in the biological activities of O.ran..