Renaissance of Strong Metal-Support Interactions.

Strong metal-support interactions (SMSIs) have emerged as a significant and cutting-edge area of research in heterogeneous catalysis. They play crucial roles in modifying the chemisorption properties, interfacial structure, and electronic characteristics of supported metals, thereby exerting a profound influence on the catalytic properties. This Perspective aims to provide a comprehensive summary of the latest advancements and insights into SMSIs, with a focus on state-of-the-art in situ/operando characterization techniques. This overview also identifies innovative designs and applications of new types of SMSI systems in catalytic chemistry and highlights their pivotal role in enhancing catalytic performance, selectivity, and stability in specific cases. Particularly notable is the discovery of SMSI between active metals and metal carbides, which opens up a new era in the field of SMSI. Additionally, the strong interactions between atomically dispersed metals and supports are discussed, with an emphasis on the electronic effects of the support. The chemical nature of SMSI and its underlying catalytic mechanisms are also elaborated upon. It is evident that SMSI modification has become a powerful tool for enhancing catalytic performance in various catalytic applications.

Structure-dependence and metal-dependence on atomically dispersed Ir catalysts for efficient n-butane dehydrogenation.

Single-site pincer-ligated iridium complexes exhibit the ability for C-H activation in homogeneous catalysis. However, instability and difficulty in catalyst recycling are inherent disadvantages of the homogeneous catalyst, limiting its development. Here, we report an atomically dispersed Ir catalyst as the bridge between homogeneous and heterogeneous catalysis, which displays an outstanding catalytic performance for n-butane dehydrogenation, with a remarkable n-butane reaction rate (8.8 mol·gIr-1·h-1) and high butene selectivity (95.6%) at low temperature (450 °C). Significantly, we correlate the BDH activity with the Ir species from nanoscale to sub-nanoscale, to reveal the nature of structure-dependence of catalyst. Moreover, we compare Ir single atoms with Pt single atoms and Pd single atoms for in-depth understanding the nature of metal-dependence at the atomic level. From experimental and theoretical calculations results, the isolated Ir site is suitable for both reactant adsorption/activation and product desorption. Its remarkable dehydrogenation capacity and moderate adsorption behavior are the key to the outstanding catalytic activity and selectivity.

Nitrogen-Neighbored Single-Cobalt Sites Enable Heterogeneous Oxidase-Type Catalysis.

The development of biomimetic catalytic systems that can imitate or even surpass natural enzymes remains an ongoing challenge, especially for bioinspired syntheses that can access non-natural reactions. Here, we show how an all-inorganic biomimetic system bearing robust nitrogen-neighbored single-cobalt site/pyridinic-N site (Co-N4/Py-N) pairs can act cooperatively as an oxidase mimic, which renders an engaged coupling of oxygen (O2) reduction with synthetically beneficial chemical transformations. By developing this broadly applicable platform, the scalable synthesis of greater than 100 industrially and pharmaceutically appealing O-silylated compounds including silanols, borasiloxanes, and silyl ethers via the unprecedented aerobic oxidation of hydrosilane under ambient conditions is demonstrated. Moreover, this heterogeneous oxidase mimic also offers the potential for expanding the catalytic scope of enzymatic synthesis. We anticipate that the strategy demonstrated here will pave a new avenue for understanding the underlying nature of redox enzymes and open up a new class of material systems for artificial biomimetics.

Fully-exposed Pt-Fe cluster for efficient preferential oxidation of CO towards hydrogen purification.

Hydrogen is increasingly being discussed as clean energy for the goal of net-zero carbon emissions, applied in the proton-exchange-membrane fuel cells (PEMFC). The preferential oxidation of CO (PROX) in hydrogen is a promising solution for hydrogen purification to avoid catalysts from being poisoned by the trace amount of CO in hydrogen-rich fuel gas. Here, we report the fabrication of a novel bimetallic Pt-Fe catalyst with ultralow metal loading, in which fully-exposed Pt clusters bonded with neighbor atomically dispersed Fe atoms on the defective graphene surface. The fully-exposed PtFe cluster catalyst could achieve complete elimination of CO through PROX reaction and almost 100% CO selectivity, while maintaining good stability for a long period. It has the mass-specific activity of 6.19 (molCO)*(gPt)-1*h-1 at room temperature, which surpasses those reported in literatures. The exhaustive experimental results and theoretical calculations reveal that the construction of fully-exposed bimetallic Pt-Fe cluster catalysts with maximized atomic efficiency and abundant interfacial sites could facilitate oxygen activation on unsaturated Fe species and CO adsorption on electron-rich Pt clusters to hence the probability of CO oxidation, leading to excellent reactivity in practical applications.

Low-Temperature Acetylene Semi-Hydrogenation over the Pd1-Cu1 Dual-Atom Catalyst.

The atomically dispersed metal catalyst or single-atom catalyst (SAC) with the utmost metal utilization efficiency shows excellent selectivity toward ethylene compared to the metal nanoparticles catalyst in the acetylene semi-hydrogenation reaction. However, these catalysts normally work at relatively high temperatures. Achieving low-temperature reactivity while preserving high selectivity remains a challenge. To improve the intrinsic reactivity of SACs, rationally tailoring the coordination environments of the first metal atom by coordinating it with a second neighboring metal atom affords an opportunity. Here, we report the fabrication of a dual-atom catalyst (DAC) that features a bonded Pd1-Cu1 atomic pair anchoring on nanodiamond graphene (ND@G). Compared to the single-atom Pd or Cu catalyst, it exhibits increased reactivity at a lower temperature, with 100% acetylene conversion and 92% ethylene selectivity at 110 °C. This work provides a strategy for designing DACs for low-temperature hydrogenation by manipulating the coordination environment of catalytic sites at the atomic level.

Building up libraries and production line for single atom catalysts with precursor-atomization strategy.

Having the excellent catalytic performance, single atom catalysts (SACs) arouse extensive research interest. However, the application of SACs is hindered by the lack of versatile and scalable preparation approaches. Here, we show a precursor-atomization strategy to produce SACs, involving the spray of droplets of solutions containing metal precursors onto support surface through ultrasonic atomization and the subsequent calcination. This approach is versatile to successful synthesis of a series of catalysts, including 19 SACs with different metal sites and supports and 3 derivatives of SACs (single atom alloys, double atom catalysts and bi-metallic SACs). Furthermore, it can be scaled up by a homemade production line with productivity over 1 kg day-1, and the well-controlled catalyst uniformity is evidenced by the identical characterization results and catalytic properties in Suzuki-Miyaura cross-coupling. This strategy lays a foundation for further investigation and may accelerate the trend from basic research to industrial applications of SACs.

Fully-Exposed Pd Cluster Catalyst: An Excellent Catalytic Antibacterial Nanomaterial.

Exploring antibacterial nanomaterials with excellent catalytic antibacterial properties has always been a hot research topic. However, the construction of nanomaterials with robust antibacterial activity at the atomic level remains a great challenge. Here a fully-exposed Pd cluster atomically-dispersed on nanodiamond-graphene (Pdn /ND@G) with excellent catalytic antibacterial properties is reported. The fully-exposed Pd cluster nanozyme provides atomically-dispersed Pd cluster sites that facilitate the activation of oxygen. Notably, the oxidase-like catalytic performance of the fully-exposed Pd cluster nanozyme is much higher than that of Pd single-atom oxidase mimic, Pd nanoparticles oxidase mimic and even the previously reported palladium-based oxidase mimics. Under the density functional theory (DFT) calculations, the Pd cluster sites can efficiently catalyze the decomposition of oxygen to generate reactive oxygen species, resulting in strong antibacterial properties. This research provides a valuable insight to the design of novel oxidase mimic and antibacterial nanomaterial.

CO-tolerant RuNi/TiO2 catalyst for the storage and purification of crude hydrogen.

Hydrogen storage by means of catalytic hydrogenation of suitable organic substrates helps to elevate the volumetric density of hydrogen energy. In this regard, utilizing cheaper industrial crude hydrogen to fulfill the goal of hydrogen storage would show economic attraction. However, because CO impurities in crude hydrogen can easily deactivate metal active sites even in trace amounts such a process has not yet been realized. Here, we develop a robust RuNi/TiO2 catalyst that enables the efficient hydrogenation of toluene to methyl-cyclohexane under simulated crude hydrogen feeds with 1000-5000 ppm CO impurity at around 180 °C under atmospheric pressure. We show that the co-localization of Ru and Ni species during reduction facilitated the formation of tightly coupled metallic Ru-Ni clusters. During the catalytic hydrogenation process, due to the distinct bonding properties, Ru and Ni served as the active sites for CO methanation and toluene hydrogenation respectively. Our work provides fresh insight into the effective utilization and purification of crude hydrogen for the future hydrogen economy.

Selective Catalytic Oxidation of Methane to Methanol in Aqueous Medium over Copper Cations Promoted by Atomically Dispersed Rhodium on TiO2.

Direct conversion of methane into value-added chemicals, such as methanol under mild conditions, is a promising route for industrial applications. In this work, atomically dispersed Rh on TiO2 suspended in an aqueous solution was used for the oxidation of methane to methanol. Promoted by copper cations (as co-catalyst) in solution, the catalysts exhibited high activity and selectivity for the production of methanol using molecular oxygen with the presence of carbon monoxide at 150 °C with a reaction pressure of 31 bar. Millimole level yields of methanol were reached with the selectivity higher than 99 % using the Rh/TiO2 catalysts with the promotion of the copper cation. CO was the reductive agent to generate H2 from H2 O, which led to the formation of H2 O2 through the reaction of H2 and O2 . Atomically dispersed Rh activated the C-H bond in CH4 and catalyzed the oxidation using H2 O2 . Copper cations maintained the low-valence state of Rh. Moreover, copper acted as a scavenger for suppressing the overoxidation, thus leading to the high selectivity of methanol.

Dietary supplementation Eucommia ulmoides extract at high content served as a feed additive in the hens industry.

Since numerous natural components in Eucommia ulmoides belong to phytoestrogen, its effect on hens production deserve more attention. To investigate the potential of E. ulmoides extract used as a feed additive, laying performance, egg quality, yolk cholesterol, yolk fatty acids, yolk fatty, yolk volatile components, albumen amino acids, plasma biochemical parameters, intestinal histology, and gut microbiota of hens (n = 120) were determined between basal diet (A) and dietary supplementation low (B), middle (C), and high (D) level E. ulmoides extract for 11 wk. When compared to A group, 2 percentage points elevation in laying rate was observed of D group. Significant up-regulation of immunoglobulin indexes and down-regulation of lipid related indexes in D group were also found if comparison with A group, suggesting that supplementation E. ulmoides extract at a relative high content benefited in immunity enhancing and blood-fat depressing. Meanwhile, obvious variation in albumen amino acids and yolk volatile compounds were inspected as dietary supplementation E. ulmoides extract, especially in D group, implied that the flavor of egg would change under high-level E. ulmoides extract treatment. Besides, villus height and villus height to crypt depth ratio of duodenum, jejunum, and ileum in D group were also significantly higher than that of in A group, indicating high-level E. ulmoides extract contributed to nutrient adsorption via intestinal histology changing. Moreover, the richness, diversity, and composition of gut microbiota in D group also significantly altered with a comparison of A group. These variation caused gut microbiota in D group major enriched in the KEGG pathway of insulin signing pathway, systemic lupus erythematosus, and bacterial invasion of epithelial cells, which were conducive to egg production elevation via facilitating nutrient adsorption, inflammation relieving, blood lipid amelioration, and insulin resistance alleviation. These results indicated that dietary supplementation E. ulmoides extract at high content could serve as a feed additive in the hens industry.

Atomically dispersed Ir/α-MoC catalyst with high metal loading and thermal stability for water-promoted hydrogenation reaction.

Synthesis of atomically dispersed catalysts with high metal loading and thermal stability is challenging but particularly valuable for industrial application in heterogeneous catalysis. Here, we report a facile synthesis of a thermally stable atomically dispersed Ir/α-MoC catalyst with metal loading as high as 4 wt%, an unusually high value for carbide supported metal catalysts. The strong interaction between Ir and the α-MoC substrate enables high dispersion of Ir on the α-MoC surface, and modulates the electronic structure of the supported Ir species. Using quinoline hydrogenation as a model reaction, we demonstrate that this atomically dispersed Ir/α-MoC catalyst exhibits remarkable reactivity, selectivity and stability, for which the presence of high-density isolated Ir atoms is the key to achieving high metal-normalized activity and mass-specific activity. We also show that the water-promoted quinoline hydrogenation mechanism is preferred over the Ir/α-MoC, and contributes to high selectivity towards 1,2,3,4-tetrahydroquinoline. The present work demonstrates a new strategy in constructing a high-loading atomically dispersed catalyst for the hydrogenation reaction.

Crystal-phase engineering of PdCu nanoalloys facilitates selective hydrodeoxygenation at room temperature.

Selective hydrodeoxygenation of biomass-derived aromatic alcohols to value-added chemical or fuel is of great importance for sustainable biomass upgrading, and hydrodeoxygenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) is one of the most attractive reactions. Achieving the conversion of HMF to DMF using H2 at ambient temperature is challenging. In this work, we used PdCu nanoalloys to catalyze the selective hydrodeoxygenation reaction of HMF to DMF using H2 as the reducing agent. The reaction path and the product selectivity are governed by the crystallographic phase of the PdCu nanoalloys. It was discovered that body-centered cubic (BCC) PdCu nanoalloys supported on activated carbon (AC) exhibited outstanding performance with 93.6% yield of DMF at room temperature (PdCu/AC-BCC). A combination of experimental and density functional theory (DFT) studies showed that the tilted adsorption modes of furanic intermediates on PdCu-BCC nanoalloy surfaces accounted for the high selectivity of DMF; however, furan ring was activated on PdCu face-centered cubic (FCC) nanoalloy surfaces. Furthermore, PdCu/AC-BCC could also catalyze the hydrodeoxygenation of other aromatic alcohols at room temperature while maintaining the aromatic structures. This work opens the way for selective hydrodeoxygenation of the aromatic alcohols at room temperature with the aromatic ring intact.

Molecular epidemiological characteristics and antibiotic resistance of Clostridioides difficile in a tertiary hospital in Shaanxi Province / 中华微生物学和免疫学杂志

Objective:To investigate the molecular epidemiological characteristics and antibiotic resistance of Clostridioides difficile ( Cd) in hospitalized diarrhea patients in a tertiary hospital in Shaanxi Province. Methods:This study collected 425 stool samples of hospitalized diarrhea patients from October 2018 to December 2021 for isolation and identification of Cd. Toxin genes carried by the isolates were detected. Multilocus sequence typing (MLST) was performed to analyze the phylogenetic profile. Antibiotic susceptibility was analyzed by E-test. Results:Forty-nine strains of Cd were isolated from the 425 samples, including 37 strains of toxigenic Cd (75.5%, 37/49). The detection rate of Cd was 14.0% (25/179) in diarrhea patients aged ≥65 years old and 36.4% (4/11) in Nephrology Department. In the 37 toxigenic Cd strains, A -B + CDT -Cd, A + B + CDT -Cd and A + B + CDT +Cd accounted for 18.9% (7/37), 78.4% (29/37) and 2.7% (1/37), respectively. There were 24 ST types, among which ST2, ST3 and ST54 were the predominant types, each accounting for 12.2% (6/49). All strains were sensitive to metronidazole and vancomycin, with a high resistance rate of 93.9% (46/49) to ciprofloxacin and a low resistance rate of 12.2% (6/49) and 10.2% (5/49) to rifampicin and meropenem, respectively. Conclusions:The main type of toxigenic strains was A + B + CDT -. ST2, ST3 and ST54 were the predominant types and the distribution of ST types was scattered. All isolates were sensitive to metronidazole and vancomycin and most of them were resistant to ciprofloxacin.

Tuning the selectivity of catalytic nitriles hydrogenation by structure regulation in atomically dispersed Pd catalysts.

The product selectivity in catalytic hydrogenation of nitriles is strongly correlated with the structure of the catalyst. In this work, two types of atomically dispersed Pd species stabilized on the defect-rich nanodiamond-graphene (ND@G) hybrid support: single Pd atoms (Pd1/ND@G) and fully exposed Pd clusters with average three Pd atoms (Pdn/ND@G), were fabricated. The two catalysts show distinct difference in the catalytic transfer hydrogenation of nitriles. The Pd1/ND@G catalyst preferentially generates secondary amines (Turnover frequency (TOF@333 K 709 h-1, selectivity >98%), while the Pdn/ND@G catalyst exhibits high selectivity towards primary amines (TOF@313 K 543 h-1, selectivity >98%) under mild reaction conditions. Detailed characterizations and density functional theory (DFT) calculations show that the structure of atomically dispersed Pd catalysts governs the dissociative adsorption pattern of H2 and also the hydrogenation pathway of the benzylideneimine (BI) intermediate, resulting in different product selectivity over Pd1/ND@G and Pdn/ND@G, respectively. The structure-performance relationship established over atomically dispersed Pd catalysts provides valuable insights for designing catalysts with tunable selectivity.

Regulating coordination number in atomically dispersed Pt species on defect-rich graphene for n-butane dehydrogenation reaction.

Metal nanoparticle (NP), cluster and isolated metal atom (or single atom, SA) exhibit different catalytic performance in heterogeneous catalysis originating from their distinct nanostructures. To maximize atom efficiency and boost activity for catalysis, the construction of structure-performance relationship provides an effective way at the atomic level. Here, we successfully fabricate fully exposed Pt3 clusters on the defective nanodiamond@graphene (ND@G) by the assistance of atomically dispersed Sn promoters, and correlated the n-butane direct dehydrogenation (DDH) activity with the average coordination number (CN) of Pt-Pt bond in Pt NP, Pt3 cluster and Pt SA for fundamentally understanding structure (especially the sub-nano structure) effects on n-butane DDH reaction at the atomic level. The as-prepared fully exposed Pt3 cluster catalyst shows higher conversion (35.4%) and remarkable alkene selectivity (99.0%) for n-butane direct DDH reaction at 450 °C, compared to typical Pt NP and Pt SA catalysts supported on ND@G. Density functional theory calculation (DFT) reveal that the fully exposed Pt3 clusters possess favorable dehydrogenation activation barrier of n-butane and reasonable desorption barrier of butene in the DDH reaction.

Fully Exposed Cluster Catalyst (FECC): Toward Rich Surface Sites and Full Atom Utilization Efficiency.

Increasing attention has been paid to single-atom catalysts (SACs) in heterogeneous catalysis because of their unique electronic properties, maximized atomic utilization efficiency, and potential to serve as a bridge between the heterogeneous and homogeneous catalysis. However, SACs can have limited advantages or even constrained applications for the reactions that require designated metallic states with multiple atoms or surface sites with metal-metal bonds. As a cross-dimensional extension to the concept of SACs, fully exposed cluster catalysts (FECCs) offer diverse surface sites formed by an ensemble of metal atoms, for the adsorption and transformation of reactants/intermediates. More importantly, FECCs have the advantage of maximized atom utilization efficiency. Thus, FECCs provide a novel platform to design effective and efficient catalysts for certain chemical processes. This outlook summarizes recent advances and proposes prospective research directions in the design of catalysts and characterizations of FECCs, together with potential challenges.

The correlation of long non-coding RNA NEAT1 and its targets microRNA (miR)-21, miR-124, and miR-125a with disease risk, severity, and inflammation of allergic rhinitis.

ABSTRACT: The present study aimed to investigate the correlation of long non-coding RNA nuclear-enriched abundant transcript 1 (lncRNA NEAT1) with microRNA (miR)-21, miR-124, and miR-125a, and their associations with disease risk, severity, and inflammatory cytokines of allergic rhinitis (AR).Totally 70 AR patients and 70 non-atopic obstructive snoring patients (as controls) were recruited. Inferior turbinate mucosa samples were collected from all participants for lncRNA NEAT1, its targets (miR-21, miR-124, and miR-125a), interleukin (IL)-4, IL-6, IL-10, and IL-17 detection via reverse transcription quantitative polymerase chain reaction. Disease severity of AR patients was assessed using individual nasal symptom score (INSS) and total nasal symptom score (TNSS).LncRNA NEAT1 was upregulated, while miR-21, miR-124, and miR-125a were downregulated in AR patients compared with controls. Additionally, lncRNA NEAT1, miR-21, and miR-125a displayed good values in differentiating AR patients from controls, while miR-124 could only slightly differentiate AR patients from controls. In AR patients, lncRNA NEAT1 was negatively associated with miR-21 and miR-125a, but not miR-124. However, in controls, no correlation of lncRNA NEAT1 with miR-21, miR-124, or miR-125a was observed. Furthermore, in AR patients, lncRNA NEAT1 was positively, while miR-21 and miR-125a was negatively associated with INSS (rhinorrhea, itching, congestion scores), TNSS and inflammatory cytokines; however, correlation of miR-124 with INSS, TNSS, and inflammatory cytokines was slight.LncRNA NEAT1 and its targets (miR-21 and miR-125a) present close correlations with disease risk, severity, and inflammation of AR, suggesting their potential as biomarkers for AR assessment.

A stable low-temperature H2-production catalyst by crowding Pt on α-MoC.

The water-gas shift (WGS) reaction is an industrially important source of pure hydrogen (H2) at the expense of carbon monoxide and water1,2. This reaction is of interest for fuel-cell applications, but requires WGS catalysts that are durable and highly active at low temperatures3. Here we demonstrate that the structure (Pt1-Ptn)/α-MoC, where isolated platinum atoms (Pt1) and subnanometre platinum clusters (Ptn) are stabilized on α-molybdenum carbide (α-MoC), catalyses the WGS reaction even at 313 kelvin, with a hydrogen-production pathway involving direct carbon monoxide dissociation identified. We find that it is critical to crowd the α-MoC surface with Pt1 and Ptn species, which prevents oxidation of the support that would cause catalyst deactivation, as seen with gold/α-MoC (ref. 4), and gives our system high stability and a high metal-normalized turnover number of 4,300,000 moles of hydrogen per mole of platinum. We anticipate that the strategy demonstrated here will be pivotal for the design of highly active and stable catalysts for effective activation of important molecules such as water and carbon monoxide for energy production.

Atomically Dispersed Ni/α-MoC Catalyst for Hydrogen Production from Methanol/Water.

Methanol-water reforming is a promising solution for H2 production/transportation in stationary and mobile hydrogen applications. Developing inexpensive catalysts with sufficiently high activity, selectivity, and stability remains challenging. In this paper, nickel-supported over face-centered cubic (fcc) phase α-MoC has been discovered to exhibit extraordinary hydrogen production activity in the aqueous-phase methanol reforming reaction. Under optimized condition, the hydrogen production rate of 2% Ni/α-MoC is about 6 times higher than that of conventional noble metal 2% Pt/Al2O3 catalyst. We demonstrate that Ni is atomically dispersed over α-MoC via carbon bridge bonds, forming a Ni1-Cx motif on the carbide surface. Such Ni1-Cx motifs can effectively stabilize the isolated Ni1 sites over the α-MoC substrate, rendering maximized active site density and high structural stability. In addition, the synergy between Ni1-Cx motif and α-MoC produces an active interfacial structure for water dissociation, methanol activation, and successive reforming processes with compatible activity.