Changeable Active Sites by Pr Doping CuSA-TiO2 Photocatalyst for Excellent Hydrogen Production.

Photocatalytic water splitting for clean hydrogen production has been a very attractive research field for decades. However, the insightful understanding of the actual active sites and their impact on catalytic performance is still ambiguous. Herein, a Pr-doped TiO2-supported Cu single atom (SA) photocatalyst is successfully synthesized (noted as Cu/Pr-TiO2). It is found that Pr dopants passivate the formation of oxygen vacancies, promoting the density of photogenerated electrons on the CuSAs, and optimizing the electronic structure and H* adsorption behavior on the CuSA active sites. The photocatalytic hydrogen evolution rate of the obtained Cu/Pr-TiO2 catalyst reaches 32.88 mmol g-1 h-1, 2.3 times higher than the Cu/TiO2. Innovatively, the excellent catalytic activity and performance is attributed to the active sites change from O atoms to CuSAs after Pr doping is found. This work provides new insight for understanding the accurate roles of single atoms in photocatalytic water splitting.

n-Si/SiOx /CoOx -Mo Photoanode for Efficient Photoelectrochemical Water Oxidation.

Green hydrogen is considered to be the key for solving the emerging energy and environmental issues. The photoelectrochemical (PEC) process for the production of green hydrogen has been widely investigated because solar power is clean and renewable. However, mass production in this way is still far away from reality. Here, a Si photoanode is reported with CoOx as co-catalyst for efficient water oxidation. It is found that a high photovoltage of 350 mV can be achieved in 1.0 m K3 BO3 . Importantly, the photovoltage can be further increased to 650 mV and the fill factor of 0.62 is obtained in 1.0 m K3 BO3 by incorporating Mo into CoOx . The Mo-incorporated photoanode is also highly stable. It is shown that the incorporation of Mo can reduce the particle size of co-catalyst on the Si surface, improve the particle-distribution uniformity, and increase the density of particles, which can effectively enhance the light absorption and the electrochemical active surface area. Importantly, the Mo-incorporation results in high energy barrier in the heterojunction. All of these factors are attributed to improved the PEC performance. These findings may provide new strategies to maximize the solar-to-fuel efficiency by tuning the co-catalysts on the Si surface.

Transcriptomic analysis reveals hub genes and pathways in response to acetic acid stress in Kluyveromyces marxianus during high-temperature ethanol fermentation.

The thermotolerant yeast Kluyveromyces marxianus is known for its potential in high-temperature ethanol fermentation, yet it suffers from excess acetic acid production at elevated temperatures, which hinders ethanol production. To better understand how the yeast responds to acetic acid stress during high-temperature ethanol fermentation, this study investigated its transcriptomic changes under this condition. RNA sequencing (RNA-seq) was used to identify differentially expressed genes (DEGs) and enriched gene ontology (GO) terms and pathways under acetic acid stress. The results showed that 611 genes were differentially expressed, and GO and pathway enrichment analysis revealed that acetic acid stress promoted protein catabolism but repressed protein synthesis during high-temperature fermentation. Protein-protein interaction (PPI) networks were also constructed based on the interactions between proteins coded by the DEGs. Hub genes and key modules in the PPI networks were identified, providing insight into the mechanisms of this yeast's response to acetic acid stress. The findings suggest that the decrease in ethanol production is caused by the imbalance between protein catabolism and protein synthesis. Overall, this study provides valuable insights into the mechanisms of K. marxianus's response to acetic acid stress and highlights the importance of maintaining a proper balance between protein catabolism and protein synthesis for high-temperature ethanol fermentation.

Interface Engineering Induced Electron Redistribution at PtNs /NiTe-Ns Interfaces for Promoting pH-Universal and Chloride-Tolerant Hydrogen Evolution Reaction.

Exploring highly efficient hydrogen evolution reaction (HER) electrocatalysts for large-scale water electrolysis in the full potential of hydrogen (pH) range is highly desirable, but it remains a significant challenge. Herein, a simple pathway is proposed to synthesize a hybrid electrocatalyst by decorating small metallic platinum (Pt) nanosheets on a large nickel telluride nanosheet (termed as PtNs /NiTe-Ns). The as-prepared PtNs /NiTe-Ns catalyst only requires overpotentials of 72, 162, and 65 mV to reach a high current density of 200 mA cm-2 in alkaline, neutral and acidic conditions, respectively. Theoretical calculations reveal that the combination of metallic Pt and NiTe-Ns subtly modulates the electronic redistribution at their interface, improves the charge-transfer kinetics, and enhances the performance of Ni active sites. The synergy between the Pt site and activated Ni site near the interface in PtNs /NiTe-Ns promotes the sluggish water-dissociation kinetics and optimizes the subsequent oxyhydrogen/hydrogen intermediates (OH*/H*) adsorption, accelerating the HER process. Additionally, the superhydrophilicity and superaerophobicity of PtNs /NiTe-Ns facilitate the mass transfer process and ensure the rapid desorption of generated bubbles, significantly enhancing overall alkaline water/saline water/seawater electrolysis catalytic activity and stability.

The impacts of dopants on the small polaron mobility and conductivity in hematite - the role of disorder.

Hematite (α-Fe2O3) is a promising transition metal oxide for various energy conversion and storage applications due to its advantages of low cost, high abundance, and good chemical stability. However, its low carrier mobility and electrical conductivity have hindered the wide application of hematite-based devices. Fundamentally, this is mainly caused by the formation of small polarons, which show conduction through thermally activated hopping. Atomic doping is one of the most promising approaches for improving the electrical conductivity in hematite. However, its impact on the carrier mobility and electrical conductivity of hematite at the atomic level remains to be illusive. In this work, through a kinetic Monte-Carlo sampling approach for diffusion coefficients combined with carrier concentrations computed under charge neutrality conditions, we obtained the electrical conductivity of the doped hematite. We considered the contributions from individual Fe-O layers, given that the in-plane carrier transport dominates. We then studied how different dopants impact the carrier mobility in hematite using Sn, Ti, and Nb as prototypical examples. We found that the carrier mobility change is closely correlated with the local distortion of Fe-Fe pairs, i.e. the more stretched the Fe-Fe pairs are compared to the pristine systems, the lower the carrier mobility will be. Therefore, elements which limit the distortion of Fe-Fe pair distances from pristine are more desired for higher carrier mobility in hematite. The calculated local structure and pair distribution functions of the doped systems have remarkable agreement with the experimental EXAFS measurements on hematite nanowires, which further validates our first-principles predictions. Our work revealed how dopants impact the carrier mobility and electrical conductivity of hematite and provided practical guidelines to experimentalists on the choice of dopants for the optimal electrical conductivity of hematite and the performance of hematite-based devices.

Formaldehyde gas sensor with extremely high response employing cobalt-doped SnO2 ultrafine nanoparticles.

Formaldehyde is a common carcinogen in daily life and harmful to health. The detection of formaldehyde by a metal oxide semiconductor gas sensor is an important research direction. In this work, cobalt-doped SnO2 nanoparticles (Co-SnO2 NPs) with typical zero-dimensional structure were synthesized by a simple hydrothermal method. At the optimal temperature, the selectivity and response of 0.5% Co-doped SnO2 to formaldehyde are excellent (for 30 ppm formaldehyde, R a/R g = 163 437). Furthermore, the actual minimum detectable concentration of 0.5%Co-SnO2 NPs is as low as 40 ppb, which exceeds the requirements for formaldehyde detection in the World Health Organization (WHO) guidelines. The significant improvement of 0.5%Co-SnO2 NPs gas performance can be attributed to the following aspects: firstly, cobalt doping effectively improves the resistance of SnO2 NPs in the air; moreover, doping creates more defects and oxygen vacancies, which is conducive to the adsorption and desorption of gases. In addition, the crystal size of SnO2 NPs is vastly small and has unique physical and chemical properties of zero-dimensional materials. At the same time, compared with other gases tested, formaldehyde has a strong reducibility, so that it can be selectively detected at a lower temperature.

Development of Perovskite Oxide-Based Electrocatalysts for Oxygen Evolution Reaction.

Perovskite oxides are studied as electrocatalysts for oxygen evolution reactions (OER) because of their low cost, tunable structure, high stability, and good catalytic activity. However, there are two main challenges for most perovskite oxides to be efficient in OER, namely less active sites and low electrical conductivity, leading to limited catalytic performance. To overcome these intrinsic obstacles, various strategies are developed to enhance their catalytic activities in OER. In this review, the recent developments of these strategies is comprehensively summarized and systematically discussed, including composition engineering, crystal facet control, morphology modulation, defect engineering, and hybridization. Finally, perspectives on the design of perovskite oxide-based electrocatalysts for practical applications in OER are given.

Multi-Phase Heterostructure of CoNiP/Cox P for Enhanced Hydrogen Evolution Under Alkaline and Seawater Conditions by Promoting H2 O Dissociation.

Hydrogen evolution reaction (HER) is a key step for electrochemical energy conversion and storage. Developing well defined nanostructures as noble-metal-free electrocatalysts for HER is promising for the application of hydrogen technology. Herein, it is reported that 3D porous hierarchical CoNiP/Cox P multi-phase heterostructure on Ni foam via an electrodeposition method followed by phosphorization exhibits ultra-highly catalytic activity for HER. The optimized CoNiP/Cox P multi-phase heterostructure achieves an excellent HER performance with an ultralow overpotential of 36 mV at 10 mA cm-2 , superior to commercial Pt/C. Importantly, the multi-phase heterostructure shows exceptional stability as confirmed by the long-term potential cycles (30,000 cycles) and extended electrocatalysis (up to 500 h) in alkaline solution and natural seawater. Experimental characterizations and DFT calculations demonstrate that the strong electronic interaction at the heterointerface of CoNiP/CoP is achieved via the electron transfer from CoNiP to the heterointerface, which directly promotes the dissociation of water at heterointerface and desorption of hydrogen on CoNiP. These findings may provide deep understanding on the HER mechanism of heterostructure electrocatalysts and guidance on the design of earth-abundant, cost-effective electrocatalysts with superior HER activity for practical applications.

Hybrid cobalt-manganese oxides prepared by ordered steps with a ternary nanosheet structure and its high performance as a binder-free electrode for energy storage.

Binder-free electrodes for supercapacitors have attracted much attention as no additive is required in their preparation processes. Herein, a hybrid metal oxide composed of graphene oxide (Co3O4/MnO2/GO) was successfully prepared. Briefly, electrochemical deposition and sintering were applied to grow Co3O4 nanosheets on nickel foam. Subsequently, MnO2 nanosheets were deposited on Co3O4 nanosheets via the thermal decomposition of a KMnO4 aqueous solution. Finally, graphene oxide was added to improve the performance of the composite. Particularly, the as-obtained Co3O4/MnO2/GO sample grown on nickel foam possessed a ternary nanosheet structure, and when applied as a binder-free electrode in a supercapacitor, it exhibited an excellent electrochemical performance. Firstly, the electrode exhibited an ultrahigh capacitance value of 2928 F g-1 at 1 A g-1 in a three-electrode system. Besides, the electrode showed a promising rate performance of 853 F g-1 at a high current density of 20 A g-1. Moreover, the electrode displayed a relatively high energy density of 97.92 W h kg-1 at a power density of 125 W kg-1 and long cycle life of 93% retention after 5000 cycles at 10 A g-1 in a two-electrode system. Thus, all the electrochemical tests suggest that the Co3O4/MnO2/GO binder-free electrode is a potential candidate for energy storage.

Platinum-Supported Cerium-Doped Indium Oxide for Highly Sensitive Triethylamine Gas Sensing with Good Antihumidity.

Triethylamine is extremely harmful to human health, and chronic inhalation can lead to respiratory and hematological diseases and eye lesions. Hence, it is essential to develop a triethylamine gas-sensing technology with high response, selectivity, and stability for use in healthcare and environmental monitoring. In this work, a simple and low-cost sensor based on the Pt- and Ce-modified In2O3 hollow structure to selectively detect triethylamine is developed. The experimental results reveal that the sensor based on 1% Pt/Ce12In exhibits excellent triethylamine-sensing performance, including its insusceptibility to water, reduced operating temperature, enhanced response, and superior long-term stability. This work suggests that the enhancement of sensing performance toward triethylamine can be attributed to the high relative contents of OV and OC, large specific surface area, catalytic effect, the electronic sensitization of Pt, and the reversible redox cycle properties of Ce. This sensor represents a unique and highly sensitive means to detect triethylamine, which shows great promise for potential applications in food safety inspection and environmental monitoring.

Nanoporous Carbon Derived from Green Material by an Ordered Activation Method and Its High Capacitance for Energy Storage.

Carbon materials have been widely used as electrode materials for supercapacitors, while the current carbon precursors are mainly derived from fossil fuels. Biomass-derived carbon materials have become new and effective materials for electrodes of supercapacitors due to their sustainability, low pollution potential, and abundant reserves. Herein, we present a new biomass carbon material derived from water hyacinth by a novel activation method (combination of KOH and HNO3 activation). According to the electrochemical measurements, the material presents an ultrahigh capacitance of 374 F g-1 (the current density is 1 A g-1). Furthermore, the material demonstrates excellent rate performance (105 F g-1 at a higher density of 20 A g-1) and ideal cycling stability (87.3% capacity retention after 5000 times charge-discharge at 2 A g-1). When used for a symmetrical supercapacitor device, the material also shows a relatively high capacity of 330 F g-1 at 1 A g-1 (a two-electrode system). All measurements suggest the material is an effective and noteworthy material for the electrodes of supercapacitors.

Enhanced performance of an acetone gas sensor based on Ag-LaFeO3 molecular imprinted polymers and carbon nanotubes composite.

High performance acetone gas sensors were fabricated with molecular imprinted polymers of Ag-LaFeO3 (ALFOMMIPs) and multi walled carbon nanotubes (CNTs) composite using the microwave assisted sol-gel method. The crystalline structure, functional groups, grain size and surface appearance of the synthesized materials were analyzed via different characterization techniques and the gas responses of the samples were examined. The detailed acetone gas sensing tests and analysis revealed that the CNTs and ALFOMIPs nanocomposite (CNT/ALFOMIP) sample possessed a higher response than that of the ALFOMIPs sample. Where 0.75 wt% CNTs were added into the ALFOMIPs (0.75% CNT/ALFOMIP nanocomposite) sensor, an excellent gas sensing performance was exhibited. The response of this sensor was up to 59 for 5 ppm acetone vapors and the response and recovery times were 58 and 33 s at low working temperature of 86 °C, respectively. In addition, it had the best selectivity only to acetone vapors due to the use of the molecular imprinting technique.

Carbon doping switching on the hydrogen adsorption activity of NiO for hydrogen evolution reaction.

Hydrogen evolution reaction (HER) is more sluggish in alkaline than in acidic media because of the additional energy required for water dissociation. Numerous catalysts, including NiO, that offer active sites for water dissociation have been extensively investigated. Yet, the overall HER performance of NiO is still limited by lacking favorable H adsorption sites. Here we show a strategy to activate NiO through carbon doping, which creates under-coordinated Ni sites favorable for H adsorption. DFT calculations reveal that carbon dopant decreases the energy barrier of Heyrovsky step from 1.17 eV to 0.81 eV, suggesting the carbon also serves as a hot-spot for the dissociation of water molecules in water-alkali HER. As a result, the carbon doped NiO catalyst achieves an ultralow overpotential of 27 mV at 10 mA cm-2, and a low Tafel slope of 36 mV dec-1, representing the best performance among the state-of-the-art NiO catalysts.

Microwave-assisted synthesis of porous and hollow α-Fe2O3/LaFeO3 nanostructures for acetone gas sensing as well as photocatalytic degradation of methylene blue.

To address the urgent issues of hazardous gas detection and the prevention of environmental pollution, various functional materials for gas sensing and catalytic reduction have been studied. Specifically, the p-type perovskite LaFeO3 has been studied widely because of its promising physicochemical properties. However, there remains several problems to develop a controllable synthesis of LaFeO3-based p-n heterojunctions. In this work, α-Fe2O3 was further compounded with LaFeO3 to form a porous and hollow α-Fe2O3/LaFeO3 heterojunction to improve its gas-sensing performance and photocatalytic efficiency via a microwave-assisted hydrothermal method. While evaluated as sensors of acetone gas, the optimized sample exhibits excellent performance, including a high response (48.3), excellent selectivity, good reversibility, fast response, and recovery ability. Furthermore, it is an efficient catalyst for the degradation of methylene blue. This can be attributed to the enhancement effect of its larger specific surface area, fast diffusion, enhanced surface activities, and p-n heterojunction. Additionally, this work provides a rapid and rational synthesis strategy to produce metal oxides with both enhanced gas-sensing performance and improved photocatalytic properties.

Ultrasensitive xylene gas sensor based on flower-like SnO2/Co3O4 nanorods composites prepared by facile two-step synthesis method.

Xylene is a volatile organic compound which is harmful to the human health and requires precise detection. The detection of xylene by an oxide semiconductor gas sensor is an important research direction. In this work, Co3O4 decorated flower-like SnO2 nanorods (SnO2/Co3O4 NRs) were synthesized by a simple and effective two-step method. The SnO2/Co3O4 NRs show high xylene response (R g/R a = 47.8 for 100 ppm) and selectivity at the operating temperature of 280 °C, and exhibit high stability in continuous testing. The resulting SnO2/Co3O4 NRs nanocomposites show superior sensing performance towards xylene in comparison with pure SnO2 nanorods. The remarkable enhancement in the gas-sensing properties of SnO2/Co3O4 NRs are attributed to larger specific surface area and the formation of p-n heterojunction between Co3O4 and SnO2. These results demonstrate that particular nanostructures and synergistic effect of SnO2 and Co3O4 enable gas sensors to selectively detect xylene.

Ag Nanoparticles Sensitized In2O3 Nanograin for the Ultrasensitive HCHO Detection at Room Temperature.

Formaldehyde (HCHO) is the main source of indoor air pollutant. HCHO sensors are therefore of paramount importance for timely detection in daily life. However, existing sensors do not meet the stringent performance targets, while deactivation due to sensing detection at room temperature, for example, at extremely low concentration of formaldehyde (especially lower than 0.08 ppm), is a widely unsolved problem. Herein, we present the Ag nanoparticles (Ag NPs) sensitized dispersed In2O3 nanograin via a low-fabrication-cost hydrothermal strategy, where the Ag NPs reduces the apparent activation energy for HCHO transporting into and out of the In2O3 nanoparticles, while low concentrations detection at low working temperature is realized. The pristine In2O3 exhibits a sluggish response (Ra/Rg = 4.14 to 10 ppm) with incomplete recovery to HCHO gas. After Ag functionalization, the 5%Ag-In2O3 sensor shows a dramatically enhanced response (135) with a short response time (102 s) and recovery time (157 s) to 1 ppm HCHO gas at 30 °C, which benefits from the Ag NPs that electronically and chemically sensitize the crystal In2O3 nanograin, greatly enhancing the selectivity and sensitivity.

High Methanol Gas-Sensing Performance of Sm2O3/ZnO/SmFeO3 Microspheres Synthesized Via a Hydrothermal Method.

In this work, we synthesized Sm2O3/ZnO/SmFeO3 microspheres by a hydrothermal method combined with microwave assistance to serve as a methanol gas sensor. We investigated the effect on the microstructure at different hydrothermal times (12 h, 18 h, 24 h, and 30 h), and the BET and XPS results revealed that the specific surface area and adsorbed oxygen species were consistent with a microstructure that significantly influences the sensing performance. The gas properties of the Sm2O3-doped ZnO/SmFeO3 microspheres were also investigated. With a hydrothermal time of 24 h, the gas sensor exhibited excellent sensing performance for methanol gas. For 5 ppm of methanol gas at 195 °C, the response reached 119.8 with excellent repeatability and long-term stability in a 30-day test in a relatively high humidity atmosphere (55-75% RH). Even at 1 ppm of methanol gas, the response was also higher than 20. Thus, the Sm2O3-doped ZnO/SmFeO3 microspheres can be considered as prospective materials for methanol gas sensors.

Boosted Visible-Light Photodegradation of Methylene Blue by V and Co Co-Doped TiO2.

In this work, TiO2 photocatalysts, co-doped with transition metal ions vanadium (V) and cobalt (Co) ((V,Co)⁻TiO2), were synthesized by the sol⁻gel method. The synthesized photocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption and desorption measurement, UV-Vis absorption and photoluminescence spectrum (PL) spectra. The results show that V and Co co-doping has significant effects on sample average crystalline grain size, absorption spectrum, recombination efficiency of photo-induced electron-hole pairs (EHPs), and photocatalytic degradation efficiency of methylene blue (MB). (V,Co)⁻TiO2 photocatalyst exhibits an obvious red shift of the absorption edge to 475 nm. Photocatalytic degradation rate of (V,Co)⁻TiO2 sample for MB in 60 min is 92.12% under a Xe lamp with a cut-off filter (λ > 400 nm), which is significantly higher than 56.55% of P25 under the same conditions. The first principles calculation results show that V and Co ions doping introduces several impurity energy levels, which can modulate the location of the valence band and conduction band. An obvious lattice distortion is produced in the meantime, resulting in the decrease in photo-generated EHP recombination. Thus, (V,Co)⁻TiO2 photocatalyst performance is significantly improved.

Design of ultrasensitive Ag-LaFeO3 methanol gas sensor based on quasi molecular imprinting technology.

An ultrasensitive methanol gas sensing device based on the quasi-molecular imprinting technology (quasi-MIT) is studied in this work. We applied the sol-gel method (ALS denotes Ag-LaFeO3 prepared by the sol-gel method) and combustion synthesis (ALC denotes Ag-LaFeO3 prepared by combustion synthesis) to prepare Ag-LaFeO3 based sensors. The morphologies and structures of the Ag-LaFeO3 materials were examined via various detection techniques. The ALSM and ALCM sensor (ALSM and ALCM denotes the devices prepared by coating the ALS and ALC materials with methanol, respectively) fabricated using the sol-gel method and combustion synthesis combined with quasi-MIT exhibit good gas sensing properties to methanol, in contrast with the two devices (ALSW and ALCW denote the devices prepared for coating the ALS and ALC materials with water, respectively) without the use of quasi-MIT. The results show that quasi-MIT introduced the target gas in the fabrication process of the device, playing an important role in the design of the ultrasensitive methanol gas sensor. The sensing response and the optimum working temperature of ALSM and ALCM gas sensor are 52.29 and 155 °C and 34.89 and 155 °C, respectively, for 5 ppm methanol, and the highest response to other gases is 8. The ALSM and ALCM gas sensors reveal good selectivity and response for methanol.