Ru Regulated Electronic Structure of PdxCuy Nanosheets for Efficient Hydrogen Evolution Reaction in Wide pH Range.

The development of highly effective catalysts for hydrogen evolution reaction (HER) in a wide pH range is crucial for the sustainable utilization of green energy utilization, while the slow kinetic reaction rate severely hinders the progress of HER. Herein, the reaction kinetic issue is solved by adjusting the electronic structure of the Ru/PdxCuy catalysts. The champion catalyst displays a remarkable performance for HER with the ultralow overpotential (27, 28, and 97 mV) in 1.0 m KOH, 0.5 m H2SO4, and 1.0 m PBS at 10 mA cm-2 and high the mass activity (3036 A g-1), respectively, superior to those of commercial Pt/C benchmarks and most of reported electrocatalysts, mainly due to its low reaction activation energy. Density functional theory (DFT) calculations indicate that Ru doping contributes an electron-deficient 3d band, which promotes water adsorption. Additionally, this also leads to an upward shift of the d-band center of Pd and a downward shift of the d-band center of Cu, further optimizing the adsorption/dissociation of H2O and H*. Results from this work may provide an insight into the design and synthesis of high-performance pH-universal HER electrocatalysts.

Tetrahedral DNA-linked aptamer-antibody-based sandwich-type electrochemical sensor with Ag@Au core-shell nanoparticles as a signal amplifier for highly sensitive detection of α-fetoprotein.

The conventional electrochemical detection strategy for alpha-fetoprotein (AFP) is limited by the antigen-antibody (Ag-Ab) reactions and suffers from low sensitivity and poor reproducibility due to the inconsistency of Ab-modified electrodes. Herein, we designed and explored a sandwich-type electrochemical sensor for highly sensitive detection of AFP based on aptamer (Apt)-AFP-Ab interaction mode with silver@gold (Ag@Au) core-shell nanoparticles (NPs) as a signal amplifier. AuNPs were electrodeposited onto MXene (Ti3C2TX)-modified glassy carbon electrode (GCE) to get AuNPs/MXene/GCE and further used as the signal amplification substrate. The tetrahedral DNA-linked AFP aptamers were immobilized onto AuNPs/MXene/GCE surface via Au-S bonds and used as the sensing and recognition platform for AFP capturing. Ag@AuNPs with core-shell structures were synthesized, characterized, and bound with Ab as detection elements by catalyzing H2O2 reduction. In the presence of AFP, a stable Apt-AFP-Ab sandwich structure was formed owing to the high affinities of aptamer and Ab toward the target AFP. The catalytic current produced by H2O2 reduction increased linearly with the logarithm of AFP concentration from 5 × 10-4 ng/mL to 1 × 105 ng/mL, accompanied by a low detection limit (1.6 × 10-4 ng/mL). Moreover, the novel sandwich-type electrochemical sensor shows high sensitivity, outstanding selectivity, and promising performance in the analysis of actual samples, displaying a broad application prospect in bioanalysis.

Three-dimensional MoS2-graphene aerogel nanocomposites for electrochemical sensing of quercetin.

A facile and novel electrochemical sensing platform is reported for quercetin determination with MoS2 nanoflowers-3D graphene aerogel (3D MoS2-GA) nanocomposite as signal amplified material. The 3D MoS2-GA nanocomposite was synthesized through a two-step hydrothermal method, in which MoS2 nanoflowers were prepared in advance. Characterizations of 3D MoS2-GA were performed by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The 3D MoS2-GA-modified glassy carbon electrode (3D MoS2-GA/GCE) was used to investigate the electrochemical behaviors of quercetin with electrochemical parameters calculated, reaction mechanism discussed, and experimental conditions optimized. Notably, the redox peak current densities of quercetin on 3D MoS2-GA/GCE raised 5.14 and 6.40 times compared with those on a bare GCE. Furthermore, a novel electroanalytical approach was proposed for the sensitive determination of quercetin within the concentration range 0.01 ~ 5.0 µmol/L, accompanied by a low detection limit of 0.0026 µmol/L (at a working potential of 0.38 V vs. Ag/AgCl). The recovery for practical sample analysis ranges from 97.0 to 105%, and the relative standard deviation is less than 4.2%. This established method shows reliable performance in determination of quercetin in tablets and urine samples.

Confined Ni nanoparticles in N-doped carbon nanotubes for excellent pH-universal industrial-level electrocatalytic CO2 reduction and Zn-CO2 battery.

Electrocatalytic reduction of CO2 (ECR) offers a promising approach to curbed carbon emissions and complete carbon cycles. However, the inevitable creation of carbonates and limited CO2 utilization efficiency in neutral or alkaline electrolytes result in low energy efficiency, carbon losses and its widespread commercial utilization. The advancement of CO2 reduction under acidic conditions offers a promising approach for their commercial utilization, but the inhibition of hydrogen evolution reaction and the corrosion of catalysts are still challenging. Herein, Ni nanoparticles (NPs) wrapped in N-doped carbon nanotubes (NixNC-a) are successfully prepared by a facile mixed-heating and freeze-drying method. Ni100NC-a achieves a high Faraday efficiency (FE) of near 100 % for CO under pH-universal conditions, coupled with a promising current density of CO (>100 mA cm-2). Especially in acidic conditions, Ni100NC-a exhibits an exceptional ECR performance with the high FECO of 97.4 % at -1.44 V and the turnover frequency (TOF) of 11 k h-1 at -1.74 V with a current density of 288.24 mA cm-2. This excellent performance is attributed to the synergistic effect of Ni NPs and N-doped carbon shells, which protects Ni NPs from etching, promotes CO2 adsorption and regulates local pH. Moreover, Ni100NC-a could drive the reversible Zn-CO2 battery with a high power-density of 4.68 mW cm-2 and a superior stability (98 h). This study presents a promising candidate for efficient pH-universal CO2 electroreduction and Zn-CO2 battery.

Highly proton-conductive and low swelling polymeric membranes achieved by hydrophilic covalent cross-linking.

Proton exchange membranes (PEMs) applied in fuel cell technology suffer from the trade-off between fast proton conduction and durable operation involving dimensional stability, mechanical strength, and oxidative resistance. To address this issue, a novel branched polybenzimidazole (brPBI) was synthesized, covalently cross-linked with (3-chloropropyl)triethoxysilane (CTS), and doped with a novel proton conductor FeATMP to prepare brPBI-CTS/FeATMP membranes. The branching degree of brPBI was optimized to achieve high molecular weight while the branching structure offered high free volume, abundant end-groups, and self-cross-linking moiety that enhanced proton conduction and dimensional/mechanical/oxidative stability. Covalent cross-linking with CTS enhanced the dimensional, mechanical, and oxidative stability while improving the water-assisted proton conduction owing to the hydrophilic nature of siloxane structure formed. At 180 ℃, the proton conductivity of the brPBI3-CTS/FeATMP composite membrane reached 0.136, 0.073, and 0.041 S cm-1 at 100 % RH, 50 % RH, and 0 % RH, respectively, while its swelling ratio after immersion in water at 90 ℃ for 24 h was 4.69 %. The performance of the membranes demonstrated that construction of hydrophilic structure by covalent cross-linking was a successful strategy to break the trade-off effect for PEMs.

Hemin/G-quadruplex and AuNPs-MoS2 based novel dual signal amplification strategy for ultrasensitively sandwich-type electrochemical thrombin aptasensor.

In this work, a novel sandwich-type electrochemical aptasensor based on the dual signal amplification strategy of hemin/G-quadruplex and AuNPs-MoS2 was designed and constructed, which realized the highly sensitive and specific detection of thrombin (TB). In this aptasensor, the 15-mer TB-binding aptamer (TBA-1) modified with thiol group was immobilized on the surface of AuNPs modified glassy carbon electrode (AuNPs/GCE) as capturing elements. Another thiol-modified 29-mer TB-binding aptamer (TBA-2) sequence containing G-quadruplex structure for hemin immobilization was designed. The formed hemin/G-quadruplex/TBA-2 sequence was further combined to the AuNPs decorated flower-like molybdenum disulfide (AuNPs-MoS2) composite surface via Au-S bonds, acting the role of reporter probe. In presence of the target TB, the sandwich-type electrochemical aptamer detection system could be formed properly. With the assistance of the dual signal amplification of AuNPs-MoS2 and hemin/G-quadruplex toward H2O2 reduction, the sandwich-type electrochemical aptasensor was successfully constructed for sensitive detection of TB. The results demonstrate that the fabricated aptasensor displays a wide linear range of 1.0 × 10-6 âˆ¼ 10.0 nM with a low detection limit of 0.34 fM. This proposed aptasensor shows potential application in the detection of TB content in real biological samples with high sensitivity, selectivity, and reliability.

Soil enzyme profile analysis for indicating decomposer micro-food web.

Highly diverse exoenzymes mediate the energy flow from substrates to the multitrophic microbiota within the soil decomposer micro-food web. Here, we used a "soil enzyme profile analysis" approach to establish a series of enzyme profile indices; those indices were hypothesized to reflect micro-food web features. We systematically evaluated the shifts in enzyme profile indices in relation to the micro-food web features in the restoration of an abandoned cropland to a natural area. We found that enzymatic C:N stoichiometry and decomposability index were significantly associated with substrate availability. Furthermore, the higher Shannon diversity index in the exoenzyme profile, especially for the C-degrading hydrolase, corresponded to a greater microbiota community diversity. The increased complexity and stability of the exoenzyme network reflected similar changes with the micro-food web networks. In addition, the gross activity of the enzyme profile as a parameter for soil multifunctionality, effectively predicted the substrate content, microbiota community size, diversity, and network complexity. Ultimately, the proposed enzymic channel index was closely associated with the traditional decomposition channel indices derived from microorganisms and nematodes. Our results showed that soil enzyme profile analysis reflected very well the decomposer food web features. Our study has important implications for projecting future climate change or anthropogenic disturbance impacts on soil decomposer micro-food web features by using soil enzyme profile analysis.

Examining the Shift in the Decomposition Channel Structure of the Soil Decomposer Food Web: A Methods Comparison.

Selecting the appropriate indicators and measuring time point numbers is important for accurately examining the shift in soil gross decomposition channel structure. Through a selected case study on a natural forest vs. rainfed arable system over a two-month-long experiment, the utility of three commonly employed indicators (fungi to bacteria ratio (F:B), fungivore to bacterivore ratio (FF:BF), and glucosamine to muramic acid ratio (GlcN:MurN)) were compared to reflect the shift in soil gross decomposition channel structure. The requirement of measuring the time point numbers for the three indicators was also assessed, and we suggest a potential methodology. Our results revealed that the GlcN:MurN ratio was more reliable for assessing the shifts in gross decomposition channel structure for long-term land use changes, while it was less sensitive to short-term drought compared with the other two indicators. The F:B ratio was more applicable than the FF:BF ratio for reflecting both long- and short-term changes. Furthermore, the reliability of the GlcN:MurN ratio was the least dependent on measuring time point numbers. We suggest the use of multiple indicators and the adoption of multiple measuring time points for the overall methodology.

Large-scale defect-rich iron/nitrogen co-doped graphene-based materials as the excellent bifunctional electrocatalyst for liquid and flexible all-solid-state zinc-air batteries.

Defect-engineering in transition-metal-doped carbon-based catalyst plays an essential role for improving the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performance. Herein, we report a ball-milling induced defect assisted with ZnCl2 strategy for fabricating defect-rich iron/nitrogen co-doped graphene-based materials (Fe-N-G). The substantial mechanical shear forces and the constant corrosion to the carbon matrix by ZnCl2 lead to the creation of abundant defects in graphene-based materials, which facilitates doping for heteroatoms. The defect-rich Fe-N-G catalyst with abundant Fe-Nx active sites displays excellent ORR performance. For OER, the over potential for Fe-N-G outperforms that of RuO2 in 1 M KOH at 10 mA cm-2. The Density Functional Theory calculations unravel that the impressive OER performance is attributable to the introduction of abundant defects. Additionally, the liquid and all-solid-state zinc-air batteries equipped with the prepared material as the air cathode demonstrate high power density, high specific capacity, and long charge-discharge stability. This work offers a practical method for manufacturing high-performance electrocatalysts for environmental and energy-related fields.

Bacteriophages in water pollution control: Advantages and limitations.

Wastewater is a breeding ground for many pathogens, which may pose a threat to human health through various water transmission pathways. Therefore, a simple and effective method is urgently required to monitor and treat wastewater. As bacterial viruses, bacteriophages (phages) are the most widely distributed and abundant organisms in the biosphere. Owing to their capacity to specifically infect bacterial hosts, they have recently been used as novel tools in water pollution control. The purpose of this review is to summarize and evaluate the roles of phages in monitoring pathogens, tracking pollution sources, treating pathogenic bacteria, infecting bloom-forming cyanobacteria, and controlling bulking sludge and biofilm pollution in wastewater treatment systems. We also discuss the limitations of phage usage in water pollution control, including phage-mediated horizontal gene transfer, the evolution of bacterial resistance, and phage concentration decrease. This review provides an integrated outlook on the use of phages in water pollution control.