Pd/Ni bimetallic modification of SrTiO3for enhancement of photocatalytic water splitting.

This paper investigates the impact of Pd/Ni modification on the photocatalytic hydrogen production performance of SrTiO3(STO). STO catalysts were synthesized using a hydrothermal method, and Pd/Ni modification was applied on the surface of STO through chemical deposition. Experimental results demonstrate that the hydrogen evolution rate of Pd/Ni-modified STO (Pd/Ni-STO) reaches 2232.14µmol g-1h-1. X-ray absorption fine structure spectroscopy analysis reveals substitutional doping of Ni with Ti and coordination of Pd with surface O. X-ray photoelectron spectroscopy analysis indicates the introduction of oxygen vacancies due to Pd/Ni doping. Density functional theory calculations suggest that Ni doping activates neighboring Ti atoms, leading to the formation of bimetallic catalytic sites composed of oxygen vacancies and Ti atoms, greatly enhancing the photocatalytic hydrogen evolution performance. This study not only provides an effective catalyst for photocatalytic applications but also offers insights into the underlying mechanism, which may stimulate the development of metal-doped catalytic materials and have implications for a range of other applications.

Ni-anchored g-C3N4for improved hydrogen evolution in photocatalysis.

In this study, we present a facile wet chemical method for synthesizing Ni-modified polymeric carbon nitride (g-C3N4) nanosheets. X-ray absorption fine structure spectroscopy reveals the formation of a unique Ni-N structure, resulting from Ni atoms anchoring in cavities of g-C3N4. The Ni anchoring on the surface N sites modifies the electronic structure of g-C3N4, demonstrating remarkable effectiveness even at low anchoring amounts. The as-prepared Ni/g-C3N4catalysts show robust performance for photocatalytic hydrogen evolution under visible light irradiation, attributed to the unique Ni-N interactions. Specifically, the photocatalytic H2production rate of the Ni/CN-45 catalyst reached 8482.14µmol·g-1·h-1with an apparent quantum efficiency of 0.75% under light irradiation at 427 nm. This rate surpasses most of the previously reported g-C3N4based photocatalysts and is nearly 8 times higher than that of the pure g-C3N4catalyst (1116.07µmol·g-1·h-1).

Methanol Oxidation at Platinum Coated Black Titania Nanotubes and Titanium Felt Electrodes.

Optimized Pt-based methanol oxidation reaction (MOR) anodes are essential for commercial direct methanol fuel cells (DMFCs) and methanol electrolyzers for hydrogen production. High surface area Ti supports are known to increase Pt catalytic activity and utilization. Pt has been deposited on black titania nanotubes (bTNTs), Ti felts and, for comparison, Ti foils by a galvanic deposition process, whereby Pt(IV) from a chloroplatinate solution is spontaneously reduced to metallic Pt (at 65 °C) onto chemically reduced (by CaH2) TNTs (resulting in bTNTs), chemically etched (HCl + NaF) Ti felts and grinded Ti foils. All Pt/Ti-based electrodes prepared by this method showed enhanced intrinsic catalytic activity towards MOR when compared to Pt and other Pt/Ti-based catalysts. The very high/high mass specific activity of Pt/bTNTs (ca 700 mA mgPt-1 at the voltammetric peak of 5 mV s-1 in 0.5 M MeOH) and of Pt/Ti-felt (ca 60 mA mgPt-1, accordingly) make these electrodes good candidates for MOR anodes and/or reactive Gas Diffusion Layer Electrodes (GDLEs) in DMFCs and/or methanol electrolysis cells.

Does the Application of ICTs Improve the Efficiency of Agricultural Carbon Reduction? Evidence from Broadband Adoption in Rural China.

Based on the Environmental Kuznets Curve (EKC) hypothesis, this paper examines whether rural broadband adoption affects agricultural carbon reduction efficiency (ACRE), using panel data from 30 Chinese provinces from 2011 to 2019. This paper achieves a measurement of ACRE by taking the carbon sink of agricultural as one of the desired outputs and using a Slacks-Based Measure (SBM) model and the global Malmquist-Luenberger (GML) index. The results show that: (1) Rural broadband adoption has a positive effect on ACRE. The relationship between the income of rural residents and ACRE was an inverted U-shaped, which confirms the EKC hypothesis. (2) Land transfer has a significant promoting effect on the relationship between rural broadband adoption and ACRE. When the land transfer rate is high, the positive effect of broadband adoption is obvious. (3) The positive effect of broadband adoption on ACRE was more obvious when farmers invested more in production equipment, that is to say, it has a significant positive moderating effect. As farmers in many developing countries suffer from increasingly frequent and severe extreme weather events, we believe that the results of this study also have implications for the implementation of agricultural carbon reduction and smart agricultural equipment roll-out in many countries.

Galvanic Restructuring of Exsolved Nanoparticles for Plasmonic and Electrocatalytic Energy Conversion.

There is a growing need to control and tune nanoparticles (NPs) to increase their stability and effectiveness, especially for photo- and electrochemical energy conversion applications. Exsolved particles are well anchored and can be re-shaped without changing their initial location and structural arrangement. However, this usually involves lengthy treatments and use of toxic gases. Here, the galvanic replacement/deposition method is used, which is simpler, safer, and leads to a wealth of new hybrid nanostructures with a higher degree of tailorability. The produced NiAu bimetallic nanostructures supported on SrTiO3 display exceptional activity in plasmon-assisted photoelectrochemical (PEC) water oxidation reactions. In situ scanning transmission electron microscopy is used to visualize the structural evolution of the plasmonic bimetallic structures, while theoretical simulations provide mechanistic insight and correlate the surface plasmon resonance effects with structural features and enhanced PEC performance. The versatility of this concept in shifting catalytic modes to the hydrogen evolution reaction is demonstrated by preparing hybrid NiPt bimetallic NPs of low Pt loadings on highly reduced SrTiO3 supports. This powerful methodology enables the design of supported bimetallic nanomaterials with tunable morphology and catalytic functionalities through minimal engineering.

Water Vapor Photoelectrolysis in a Solid-State Photoelectrochemical Cell with TiO2 Nanotubes Loaded with CdS and CdSe Nanoparticles.

In this study, polyol-made CdS and CdSe crystalline nanoparticles (NPs) are loaded by impregnation on TiO2 nanotube arrays (TNTAs) for solar-simulated light-driven photoelectrochemical (PEC) water vapor splitting. For the first time, we introduce a safe way to utilize toxic, yet efficient photocatalysts by integration in solid-state PEC (SSPEC) cells. The enabling features of SSPEC cells are the surface protonic conduction mechanism on TiO2 and the use of polymeric electrolytes, such as Nafion instead of liquid ones, for operation with gaseous reactants, like water vapor from ambient humidity. Herein, we studied the effects of both the operating conditions in gaseous ambient atmospheres and the surface modifications of TNTAs-based photoanodes with well-crystallized CdS and CdSe NPs. We showed 3.6 and 2.5 times increase in the photocurrent density of defective TNTAs modified with CdS and CdSe, respectively, compared to the pristine TNTAs. Electrochemical impedance spectroscopy and structural characterizations attributed the improved performance to the higher conductivity induced by intrinsic defects as well as to the enhanced electron/hole separation at the TiO2/CdS heterojunction under gaseous operating conditions. The SSPEC cells were evaluated by cycling between high relative humidity (RH) (80%) and low RH levels (40%), providing direct evidence of the effect of RH and, in turn, adsorbed water, on the cell performance. Online mass spectrometry indicated the corresponding difference in the H2 production rate. In addition, a complete restoration of the SSPEC cell performance from low to high RH levels was also achieved. The presented system can be employed in off-grid, water depleted, and air-polluted areas for the production of hydrogen from renewable energy and provides a solution for the safe use of toxic, yet efficient photocatalysts.

Galvanic Deposition of Pt Nanoparticles on Black TiO2 Nanotubes for Hydrogen Evolving Cathodes.

A galvanic deposition method for the in-situ formation of Pt nanoparticles (NPs) on top and inner surfaces of high-aspect-ratio black TiO2 -nanotube electrodes (bTNTs) for true utilization of their total surface area has been developed. Density functional theory calculations indicated that the deposition of Pt NPs was favored on bTNTs with a preferred [004] orientation and a deposition mechanism occurring via oxygen vacancies, where electrons were localized. High-resolution transmission electron microscopy images revealed a graded deposition of Pt NPs with an average diameter of around 2.5 nm along the complete nanotube axis (length/pore diameter of 130 : 1). Hydrogen evolution reaction (HER) studies in acidic electrolytes showed comparable results to bulk Pt (per geometric area) and Pt/C commercial catalysts (per mg of Pt). The presented novel HER cathodes of minimal engineering and low noble metal loadings (µg cm-2 range) achieved low Tafel slopes (30-34 mV dec-1 ) and high stability in acidic conditions. This study provides important insights for the in-situ formation and deposition of NPs in high-aspect-ratio structures for energy applications.

The TiO2 topotactic transformation assisted trapping of an atomically dispersed Pt catalyst for low temperature CO oxidation.

Atomically dispersed Pt catalysts are synthesized on TiO2 with high activity and strong high temperature resistance by loading Pt in the process of converting the NH4TiOF3 precursor to TiO2 by a topotactic transformation process. The atomically dispersed Pt catalyst displayed high catalytic activity for the low temperature CO oxidation reaction.

In situ formation of defect-engineered N-doped TiO2 porous mesocrystals for enhanced photo-degradation and PEC performance.

N-Doped oxygen defective N/TiO2-x mesocrystal nanocubes were successfully prepared by a facile strategy in our system. Crystal topotactic transformation from NH4TiOF3 mesocrystals facilitated the formation of a porous structure of TiO2. Meanwhile, the introduction of N dopants and oxygen vacancies (OVs) was also achieved during this process. The as-prepared products exhibit much higher photoelectrochemical (PEC) and photocatalytic degradation performance under visible light illumination. It is suggested that the promising catalytic properties result from the synergistic effect of doping, OVs and the amazing porous mesocrystal structure of N/TiO2-x .

Defect-engineered TiO2 Hollow Spiny Nanocubes for Phenol Degradation under Visible Light Irradiation.

Herein, we mainly report a strategy for the facile synthesis of defect-engineered F-doped well-defined TiO2 hollow spiny nanocubes, constructed from NH4TiOF3 as precursor. The topological transformation of NH4TiOF3 mesocrystal is accompanied with fluorine anion releasing, which can be used as doping source to synthesize F-doped TiO2. Our result shows that the introduction of oxygen vacancies (Vo's) and F dopant can be further achieved by a moderate photoreduction process. The as prepared sample is beneficial to improve photocatalystic degradation and Photoelectrochemical (PEC) efficiency under visible light irradiation. And this improvement in photocatalytic and photoelectrocatalytic performance can be ascribed to the significant enhancement of visible light absorption and separation of excited charges resulted from the presence of oxygen vacancies, F- ions and hollow structure of TiO2.

[Study on chemical components of Aconitum flavum and their inflammatory and analgesic effects].

OBJECTIVE: To study the chemical compositions of active site of Aconitum flavum and their pharmacological effects on anti-inflammatory andantalgic. METHODS: Xylene-induced mice ear swollen and egg white-induce toe swollen test were used to assess the anti-inflammatory effect of Aconitum flavum. Acetic acid-induce mice writhing and hot-plate test were used to assess the antalgic effect of Aconitum flavum. Silica gel, ODS and Sephadex LH-20 techniques were employed for isolation and purification the constituents of Aconitum flavum. The chemical compounds were identified by 1H-NMR, 13C-NMR, DEPT, HMBC, HMQC and COSY. RESULTS: When compared with model group, there was significant difference in 30% alcohol active extract group (P < 0.05) in xylene-induce mice ear-swollen test. In the experiment of egg white-induce toe swollen test, 30% alcohol active extract group had great significant difference when compared with the model group (P < 0.01). In acetic acid writhing test, 30% alcohol active extract group had significant analgesic action when compared with model group. In hot plate test, when compared with model group, the analgesic effect of 30% alcohol active extract group (P < 0.05) at 30 and 45 minutes after administration was significanty increased. Fourteen compounds were isolated from the active extract,while seven compounds were identified as: sucrose (I), linarin (Ii), beta-sitosterol (III), beta-daucosterol (IV), beta-sitosterol-3, 5, 6-triol (VII), aconitine (V ) and hypaconitine (IV). CONCLUSION: 30% alcohol active extract of Aconitum flavum has anti-inflammatory and antalgic effects. Compounds I, II, IV, VI and VII are isolated for the first time.