Fe-Doped SrCoOx FET Sensors for Extreme Alkaline pH Sensing.

The accurate measurement of pH in highly alkaline environments is critical for various industrial applications but remains a complex task. This paper discusses the development of novel Fe-doped SrCoOx-based FET sensors for the detection of extreme alkaline pH levels. Through a comprehensive investigation of the effects of Fe doping on the structure, electrical properties, and sensing performance of SrCoOx, we have identified the optimal doping level that significantly enhances the sensor's performance in highly alkaline conditions. With a Fe doping level of 5 mol %, the sensitivity of the sensor improves to 0.86 lg(Ω)/pH while maintaining the response rate. Further increasing the Fe doping to 10 mol % results in a sensor that demonstrates favorable response time, a suitable pH range, and a linear correlation between lg(R) and pH. The combination of X-ray photoelectron spectroscopy and X-ray diffraction analysis provides insight into the regulation mechanisms of Fe doping on the crystal structure, electronic structure, and oxygen vacancy concentration of SrCoOx. Our findings indicate that Fe doping leads to an increase in oxygen vacancy concentration and a decrease in the energy barrier for oxygen ion migration, which contributes to the improved sensing performance of the Fe-doped SrCoOx sensors. Additionally, the study highlights the influence of oxygen vacancy concentration on the electrical properties of SrCoOx. Precise control over the concentration of oxygen vacancies is crucial for optimizing the sensitivity and response speed of SrCoOx FET sensors under extreme alkalinity conditions.

Efficient and Stable pH-Universal Water Electrolysis Catalyzed by N-Doped Hollow Carbon Confined RuIrOx Nanocrystals.

A facile strategy is developed to fabricate 3 nm RuIrOx nanocrystals anchored onto N-doped hollow carbon for highly efficient and pH-universal overall water splitting and alkaline seawater electrolysis. The designed catalyst exhibits much lower overpotential and superior stability than most previously reported Ru- and Ir-based electrocatalysts for hydrogen/oxygen evolution reactions. It also manifests excellent overall water splitting activities and maintains ≈100% Faradic efficiency with a cell voltage of 1.53, 1.51, and 1.54 V at 10 mA cm-2 for 140, 255, and 200 h in acid, alkaline, and alkaline seawater electrolytes, respectively. The excellent electrocatalytic performance can be attributed to solid bonding between RuIrOx and the hollow carbon skeleton, and effective electronic coupling between Ru and Ir, thus inducing its remarkable electrocatalytic activities and long-lasting stability.

Electrocatalytic nitrate-to-ammonia conversion on CoO/CuO nanoarrays using Zn-nitrate batteries.

Zn-NO3- batteries can generate electricity while producing NH3 in an environmentally friendly manner, making them a very promising device. However, the conversion of NO3- to NH3 involves a proton-assisted 8-electron (8e-) transfer process with a high kinetic barrier, requiring high-performance catalysts to realize the potential applications of this technology. Herein, we propose a heterostructured CoO/CuO nanoarray electrocatalyst prepared on a copper foam (CoO/CuO-NA/CF) that can electrocatalytically and efficiently convert NO3- to NH3 at low potential and achieves a maximum NH3 yield of 296.9 µmol h-1 cm-2 and the Faraday efficiency (FE) of 92.9% at the -0.2 V vs. reversible hydrogen electrode (RHE). Impressively, Zn-NO3- battery based on the monolithic CoO/CuO-NA/CF electrode delivers a high NH3 yield of 60.3 µmol h-1 cm-2, FENH3 of 82.0%, and a power density of 4.3 mW cm-2. This study provides a paradigm for heterostructured catalyst preparation for the energy-efficient production of NH3 and simultaneously generating electrical energy.

High entropy alloy nanoparticles as efficient catalysts for alkaline overall seawater splitting and Zn-air batteries.

High entropy alloys (HEAs) are those metallic materials that consist of five or more elements. Compared with conventional alloys, they have much more catalytic active sites due to unique structural characteristics such as high entropy effect and lattice distortion, endowing them with promising applications in the region of hydrolysis catalysts. Herein, we successfully loaded high-entropy alloys onto carbon nanotubes (FeNiCoMnRu@CNT) by hydrothermal means. It exhibits excellent HER and OER properties in alkaline seawater. To accomplish two-electrode total water splitting when constructed into Zn air cells, it only needed 1.6 V, and the timing voltage curve showed a steady current density of 10 mA cm-2 during constant electrolysis for more than 30 h in alkaline seawater. The remarkably high HER and OER activity of FeNiCoMnRu@CNT HEAs NPS indicates the potentially broad application prospect of HEAs for Zn air battery.

Sulfur dopant-enhanced neutral hydrogen evolution performance in MoO3nanosheets.

Developing nonprecious-metal based catalysts with highly active and stable performance for hydrogen evolution reaction (HER) in neutral media is crucial points for realizing low-carbon economy because their practical use typically suffers from the slow kinetics. Herein, we developed S-doped MoO3nanosheets toward neutral HER, fabricated by a versatile solvothermal and subsequently sulfuration processes. The obtained catalyst exhibits a small overpotential of 106 mV to reach 10 mA cm-2in 1.0 M phosphate buffered saline, overwhelming most of recently reported catalysts. Meantime, it shows no notable deactivation after more than 60 h continuous electrolysis and 50 000 cycling tests. More importantly, the catalyst also can be applied in buffered seawater for electrocatalyzing HER, requiring 262 mV at 10 mA cm-2and maintaining over 60 h. These findings open a new route for designing MoO3-based catalysts for neutral hydrogen production.

Fe-doped MoS2nanosheets array for high-current-density seawater electrolysis.

Designing highly active and cost-effective electrocatalysts for seawater-splitting with large current densities is compelling for developing hydrogen energy. Great advancements in hydrogen evolution reaction (HER) have been achieved, but the progress on driving HER in seawater is still limited. Herein, Fe-doped MoS2nanoshseets array supported by 3D carbon fibers was explored to be an efficient HER electrocatalyst operating in seawater. Strikingly, it exhibited small overpotentials of 119 and 300 mV to reach the current densities of 10 and 250 mA cm-2in buffered seawater, respectively, both of them are comparable to the best-reported values under similar conditions. Meantime, the catalyst could keep the stable HER activity for 30 h without notable loss. Theoretical calculations revealed that Fe doping increases the S-edge activity. Our work provides a new avenue for designing MoS2-based HER electrocatalysts for industry application.

Bifunctional single-atomic Mn sites for energy-efficient hydrogen production.

The electrocatalytic hydrogen evolution reaction (HER) for H2 production is essential for future renewable and clean energy technology. Screening energy-saving, low-cost, and highly active catalysts efficiently, however, is still a grand challenge due to the sluggish kinetics of the oxygen evolution reaction (OER) in electrolyzing water. Herein, we present a single atomic Mn site anchored on a boron nitrogen co-doped carbon nanotube array (Mn-SA/BNC), which is perfectly combined with the hydrazine electrooxidation reaction (HzOR) boosted water electrolysis concept. The obtained catalyst achieves 51 mV overpotential at the current density of -10 mA cm-2 for the cathodic HER and 132 mV versus the reversible hydrogen electrode for HzOR, respectively. Besides, in a two-electrode overall hydrazine splitting (OHzS) system, the Mn-SA/BNC catalyst only needs a cell voltage of only 0.41 V to output 10 mA cm-1, with strong durability and nearly 100% faradaic efficiency for H2 production. This work highlights a low-cost and high-efficiency energy-saving H2 production pathway.

Multi-shelled hollow layered double hydroxides with enhanced performance for the oxygen evolution reaction.

Hollow materials with a sophisticated structure are promising for various applications with boosted performances and innovative properties. Herein, we report an in situ transformation strategy using multi-layered MOFs as templates to fabricate multi-shelled hollow NiZnCoFe layered double hydroxides (LDHs), which outperformed the double- and single-shelled hollow LDHs and commercial IrO2 in the oxygen evolution reaction.

Engineering Atomic Sites via Adjacent Dual-Metal Sub-Nanoclusters for Efficient Oxygen Reduction Reaction and Zn-Air Battery.

N-coordinated transition-metal materials are crucial alternatives to design cost-effective, efficient, and highly durable catalysts for electrocatalytic oxygen reduction reaction. Herein, the synthesis of uniformly distributed Cu-Zn clusters on porous N-doped carbon, which are accompanied by Cu/Zn-Nx single sites, is demonstrated. X-ray absorption fine structure tests reveal the co-existence of M-N (M = Cu or Zn) and M-M bonds in the catalyst. The catalyst shows excellent oxygen reduction reaction (ORR) performance in an alkaline medium with a positive half-wave potential of 0.884 V, a superior kinetic current density of 36.42 mA cm-2 at 0.85 V, and a Tafel slope of 45 mV dec-1 , all of which are among the best-reported results. Furthermore, when employed as an air cathode in Zn-Air battery, it reveals a high open-cycle potential of 1.444 V and a peak power density of 164.3 mW cm-2 . Comprehensive experiments and theoretical calculations approved that the high activity of the catalyst can be attributed to the collaboration of the Cu/Zn-N4 sites with CuZn moieties on N-doped carbons.

Stable and Efficient Single-Atom Zn Catalyst for CO2 Reduction to CH4.

The development of highly active and durable catalysts for electrochemical reduction of CO2 (ERC) to CH4 in aqueous media is an efficient and environmentally friendly solution to address global problems in energy and sustainability. In this work, an electrocatalyst consisting of single Zn atoms supported on microporous N-doped carbon was designed to enable multielectron transfer for catalyzing ERC to CH4 in 1 M KHCO3 solution. This catalyst exhibits a high Faradaic efficiency (FE) of 85%, a partial current density of -31.8 mA cm-2 at a potential of -1.8 V versus saturated calomel electrode, and remarkable stability, with neither an obvious current drop nor large FE fluctuation observed during 35 h of ERC, indicating a far superior performance than that of dominant Cu-based catalysts for ERC to CH4. Theoretical calculations reveal that single Zn atoms largely block CO generation and instead facilitate the production of CH4.

The Origin of Superhydrophobicity for Intrinsically Hydrophilic Metal Oxides: A Preferential O2 Adsorption Dominated by Oxygen Vacancies.

The superhydrophobicity of intrinsically hydrophilic materials is still not well understood. Now, intrinsically hydrophilic metal oxides with different topographic structures are taken as model materials to reveal the origin of their superhydrophobicity. These metal oxides show enhanced hydrophobicity or superhydrophobicity in O2 relative to that in air, but exhibit superhydrophilic behavior in N2 . The presence of rich oxygen vacancies greatly enhanced the adsorption of O2 with an adsorption energy larger than N2 and H2 O, resulting in a stable O2 adsorption rather than air-trapping within grooves of rough-textured surfaces, which endows these intrinsically hydrophilic oxides with superhydrophobicity. Our results highlight a further understanding of the origin of superhydrophobicity for intrinsically hydrophilic materials, and is of great significance for designing novel devices with desired wettability.

Efficient Electroreduction CO2 to CO over MnO2 Nanosheets.

As a critical alternative step for the synthesis of important chemical feedstocks and complex carbon-based fuels, the electrochemical transformation of CO2 into CO holds great significance for the chemical industry. Here, MnO2 nanosheets array supported nickel foam has been synthesized and adopted as a binder-free catalyst for electrochemical CO2 reduction reaction (CO2RR). The well-distributed nanosheets of MnO2 impart a much higher density of accessible active sites for CO2RR, enabling the selective CO2 reduction to CO with a large current density (14.1 mA cm-2), excellent Faradaic efficiency (71%) and high electrochemical stability (10 h). This work first demonstrates the great potential of Mn-based oxides for electrocatalytic transformation of CO2 to valuable products.

Porous Mn-Doped FeP/Co3 (PO4 )2 Nanosheets as Efficient Electrocatalysts for Overall Water Splitting in a Wide pH Range.

Development of highly active and stable electrocatalysts for overall water splitting is important for future renewable energy systems. In this study, porous Mn-doped FeP/Co3 (PO4 )2 (PMFCP) nanosheets on carbon cloth are utilized as a highly efficient 3 D self-supported binder-free integrated electrode for the oxygen evolution and hydrogen evolution reactions (OER and HER) over a wide pH range. Specifically, overpotentials of 27, 117, 85 mV are required for the PMFCP nanosheets to attain 10 mA cm-2 for HER in 0.5 m H2 SO4 , 1.0 m phosphatebuffered saline (PBS), and 1.0 m KOH, respectively. In addition to the excellent performance for HER electrocatalysis, PMFCP nanosheets were also efficient electrocatalysts for the OER. Thus, the PMFCP nanosheets can serve as anodes and cathodes for overall water splitting (OWS). The OWS working voltages to attain 10 mA cm-2 are found to be 1.75, 1.82, and 1.61 V in acid, neutral, and alkaline electrolytes, respectively. Chronopotentiometric tests show that the PMFCP electrode can maintain its excellent pH-universal OWS activity for more than 30 000 s. This work also provides new insights into developing high-performance electrocatalysts for water splitting over a wide pH range. The improvement in electrochemical performance by introduction of Mn dopant and nano-holes offers new opportunities in the development of effective electrodes for other energy-related applications.

A unique semiconductor-carbon-metal hybrid structure design as a counter electrode in dye-sensitized solar cells.

The catalytic activity of counter electrodes (CEs) severely restricts the photovoltaic conversion efficiency of dye-sensitized solar cells. However, electrons trapped by bulk defects greatly reduce the catalytic activity of the CE. In this study, we report a novel In2S3-C-Au hybrid structure designed by simply decorating Au particles on the surface of carbon-coated hierarchical In2S3 flower-like architectures, which could avoid the abovementioned problems. This effect can be attributed to the unique contribution of indium sulfide, carbon, and Au from the hybrid structure, as well as to their synergy. Electrochemical measurements revealed that the hybrid structure possessed high catalytic activity and electrochemical stability for the interconversion of the redox couple I3-/I-. Moreover, this superior performance can be incorporated into the dye-sensitized solar cells system. We used this hybrid structure as a counter electrode by casting it on an FTO substrate to form a film, which displayed better photovoltaic conversion efficiency (8.91%) than the commercial Pt counterpart (7.67%).

Improved H2S gas sensing properties of ZnO nanorods decorated by a several nm ZnS thin layer.

To avoid a spontaneous reaction between ZnO gas sensing materials and detected H2S gas, ZnO nanorods decorated with a several nm ZnS thin layer were designed. The ZnS-decorated layer was prepared by passivating oriented ZnO nanorods in a H2S atmosphere. The effect of the passivation processes on the H2S sensing properties was investigated. It was found that ZnO nanorods decorated with a 2 nm-thick ZnS layer possessed a repeatable and superior response to ppm-level H2S at room temperature. Moreover, a confinement effect was proposed to explain the improved sensing properties of the decorated ZnO nanorods.