Efficient Oxidation Research Articles

Cellulose conversion to 5-hydroxymethylfurfural via a simple and efficient phosphate-doped hafnium oxide catalyst

The efficient catalytic conversion of cellulose to 5-hydroxymethylfurfural (HMF) can provide a valuable reference for the high-value utilization of biomass. In this work, a series of simple phosphate-doped hafnium oxide catalysts (x-P-HfO2) were prepared, and their physicochemical properties were analyzed by ICP-OES, XRD, XPS, FTIR, SEM-EDX, N2 adsorption-desorption isotherms, NH3-TPD and Py-FTIR characterizes. Detailed evaluation of the reaction conditions demonstrated the ideal catalytic performance of the x-P-HfO2 catalysts, and the HMF yield from cellulose reached a satisfactory 61% in the water(NaCl)/tetrahydrofuran biphasic reaction system. Based on the captured intermediates and detected by-products, possible catalytic pathways are summarized. Meanwhile, the hydrothermal stability of the catalyst was also investigated, and the reason for its performance degradation after five cycles was determined to be the loss of useful Brønsted active sites. In addition, the effects of the phosphating and sulfating modification approaches on the catalyst activity were also compared, verifying that the introduction of phosphate is more conducive to the catalyst expressing high activity for the formation of HMF from cellulose.

Development of a tritium release system for ceramic tritium breeder pebbles irradiated by high intensity DT fusion neutron Generator at INEST

For ceramic breeder pebbles used in fusion energy, the tritium release data under fusion neutron irradiation is very important and valuable. In this study, a tritium release system for ceramic tritium breeder is introduced, which is matched with the High Intensity DT Fusion Neutron Generator (HINEG-CAS). The HINEG-CAS has been built and operated by the Institute of Nuclear Energy Safety Technology, Hefei Institutes of Physical Science, Chinese Academy of Sciences (INEST, HFIPS, CAS), achieving a fusion neutron yield of 1012n/s since 2016. Innovative design and fabrication of sample container enables minimization of the unexpected tritium loss. The dedicated tritium release system can monitor the tritium release behavior over time for both tritiated water and tritium gas, using the bubblers-based tritium trapping system with automatic replacement technology, coupled with highly efficient catalytic oxidants and liquid scintillation counter (LSC). We have performed a tritium release experiment with the Li2TiO3 pebbles as ceramic tritium breeder, and obtained the tritium releasing data at room temperature over time and clarified the tritium chemical form in recovery. It is concluded that this newly established system can serve as a good sharing platform for evaluating prime candidate breeder materials, as well as facilitating detailed design or optimization of tritium involved systems (such as the tritium extraction system).

Self-healing of active site in Co(OH)2/MXene electrocatalysts for hydrazine oxidation

The development of efficient hydrazine oxidation reaction (HzOR) catalysts is important for the construction of remarkable energy storage and conversion systems. However, after a period of electrochemical reaction, the active site of the catalyst will be irreversibly reduced or inactivated, and how to recover the active site is a major challenge. Here, we report 2D Co(OH)2/Ti3C2(OH)x MXene composites with rapid reconstruction and self-healing behaviors as efficient and stable electrocatalysts during HzOR process. Both experimental and theoretical results indicate that the introduction of Ti3C2(OH)x MXene can effectively reduce the dehydrogenation barrier of Co(OH)2, from 0.584 eV to 0.481 eV to form the real catalytic active center Co(OH)O. Subsequently, Co(OH)O/Ti3C2(OH)x MXene composites with metal-like conductivity not only present spontaneous adsorption capacity of N2H4, but also can modulated rate-determining step of dehydrogenation of *N2H4 to *N2H3 (0.54 eV) compared with Co(OH)O. Finally, the electrophilic oxygen of Co(OH)O/Ti3C2(OH)x can spontaneously obtain electrons and protons from N2H4, achieving the oxidation of N2H4 while reducing Co(OH)O to Co(OH)2, thus completing the self-healing of the efficient catalyst.

Palladium-charcoal Catalyzed Direct Esterification of Aldehydes to Esters by NaIO4

Abstract:: An efficient direct oxidation method was developed to oxidize some aromatic and aliphatic aldehydes to esters by the dual utilization of NaIO4 and Pd-C. At ambient conditions, various aldehydes were employed in a clean esterification reaction to afford numerous esters in good to excellent yields. By this adopted method, some multifunctional aldehydes, high-energy-containing aromatic and unsaturated aldehydes, were advantageously oxidized to esters without noticeable difficulties. Moreover, no over-oxidation occurred to alcohols, and mostly by products were not formed during this oxidation process. Conventional and some modern methods lag behind owing to their easier operability and easy work-up process. This investigation has proven that the required oxidant (NaIO4) or catalyst (Pd-C) is useless to employ in excess, although some current methods utilize hugely expensive reagents for such conversions. Mundane reaction set-up, easy product recovery technique, nontoxic catalyst, and cheap and available starting materials are the noteworthy advantages of this method.

Controllable Boosting Activity on Co4N by Fe Substitution for Oxygen Evolution Reaction and Efficient 5-Hydroxymethylfurfural Oxidation

Controllable Boosting Activity on Co4N by Fe Substitution for Oxygen Evolution Reaction and Efficient 5-Hydroxymethylfurfural Oxidation

Light-induced phase transformation to two-dimensional amorphous spinel CoAlOx nanosheets as a tandem photothermal catalyst for efficient and durable toluene oxidation

Low temperature fabrication of spinel oxides and development of efficient and durable toluene photothermal catalysts remain challenging. Herein, two-dimensional amorphous spinel CoAlOx nanosheets (CoAl-LDH-L2) have been fabricated via a light-induced phase transformation strategy using intense photooxidation. Light-induced decomposition and phase transformation process have been used to elucidate the growth mechanism. The CoAl-LDH-L2 exhibits improved toluene adsorption and photothermal conversion, with the highest photothermal catalytic toluene conversion (∼100 % at 500 ppm) at 90 °C, outperforming most previously reported catalysts. Irradiation with mild external heating significantly increases the mineralization rate (∼90 %) and improves the long-term and cycling stability (∼5% losses within 39 h) relative to that under single-light-driven conditions. In-situ DRIFT spectroscopy was also performed for revealing the “tandem photothermal catalysis” mechanism for toluene conversion. This work offers a novel strategy for developing spinel oxides as low-temperature photothermal catalyst in a green and sustainable way.

The regulation mechanism of transition metal doping on Hg0 adsorption and oxidation on Ce/TiO2(001) surface: A DFT study

The mercury oxidation performance of Ce/TiO2 catalyst can be further enhanced by transition metal modifications. This study employed density functional theory (DFT) calculations to investigate the adsorption and oxidation mechanisms of Hg0 on Ce/TiO2(001) and its transition metal modified surfaces. According to the calculation results, Ru-, Mo-, Nb-, and Mn-doping increased the affinity of the Ce/TiO2(001) surface towards Hg0 and HCl, thereby facilitating the efficient capture and oxidation of Hg0. The increased adsorption energy (Eads) of the intermediate HgCl on the modified surfaces could promote its conversion to the final product HgCl2. The modification of transition metals impeded the desorption of the final products HgCl2 and HgO, but it did not serve as the rate-determining step. The oxidation of Hg0 by lattice oxygen and HCl followed the Mars-Maessen and Langmuir-Hinshelwood mechanisms, respectively. HCl exhibited higher mercury oxidation ability than lattice oxygen. The reactivity of lattice oxygen could be further improved by doping transition metals, their promotion order was Ru > Nb > Mo > Mn. In a HCl atmosphere, Mn modification could significantly reduce the energy barrier for HCl activation and HgCl2 formation, providing the optimal enhancement for the mercury oxidation ability of Ce/TiO2 catalyst. The screening method of transition metal modified components based on surface adsorption reaction and oxidation energy barrier was proposed in this study, which provided theoretical guidance for the development of CeTi based catalysts with high mercury oxidation activity.

Tuning electrochemical water activation over NiIr single-atom alloy aerogels for stable electrochemiluminescence

The anodic oxygen evolution reaction is a well-acknowledged side reaction in traditional aqueous electrochemiluminescence (ECL) systems due to the generation and surface aggregation of oxygen at the electrode, which detrimentally impacts the stability and efficiency of ECL emission. However, the effect of reactive oxygen species generated during water oxidation on ECL luminophores has been largely overlooked. Taking the typical luminol emitter as an example, herein, we employed NiIr single-atom alloy aerogels possessing efficient water oxidation activity as a prototype co-reaction accelerator to elucidate the relationship between ECL behavior and water oxidation reaction kinetics for the first time. By regulating the concentration of hydroxide ions in the electrolyte, the electrochemical oxidation processes of both luminol and water are finely tuned. When the concentration of hydroxide ions in electrolyte is low, the kinetics of water oxidation is attenuated, which limits the generation of oxygen, effectively mitigates the influence of oxygen accumulation on the ECL strength, and offers a novel perspective for harnessing side reactions in ECL systems. Finally, a sensitive and stable sensor for antioxidant detection was constructed and applied to the practical sample detection.

Spin Effect to Regulate the Electronic Structure of Ir─Fe Aerogels for Efficient Acidic Water Oxidation.

"Spin" has been recently reported as an important degree of electronic freedom to promote catalysis, yet how it influences electronic structure remains unexplored. This work reports the spin-induced orbital hybridization in Ir─Fe bimetallic aerogels, where the electronic structure of Ir sites is effectively regulated by tuning the spin property of Fe atoms. The spin-optimized electronic structure boosts oxygen evolution reaction (OER) electrocatalysis in acidic media, resulting in a largely improved catalytic performance with an overpotential of as low as 236mV at 10mAcm-2. Furthermore, the gelation kinetics for the aerogel synthesis is improved by an order of magnitude based on the introduction of a magnetic field. Density functional theory calculation reveals that the increased magnetic moment of Fe (3d orbital) changes the d-band structure (i.e., the d-band center and bandwidth) of Ir (5d orbital) via orbital hybridization, resulting in optimized binding of reaction intermediates. This strategy builds the bridge between the electron spin theory with the d-band theory and provides a new way for the design of high-performance electrocatalysts by using spin-induced orbital interaction.

3D-TNAs/N-TiO2 photoanode assisted heterogeneous electro-Fenton with a novel Fe-MOFs@CF cathode for efficient synergetic oxidation of organic contaminants

Photoelectro-catalysis (PEC) and heterogeneous electro-Fenton (HEF) reactions are two frontier research fields for real effluent treatments. In the present work, a synergetic system with integration of both PEC and HEF has been developed for pollutant removal. PEC process with lower external bias results in the efficient separation of photogenerated hole and electrons, which can also modulate the HEF catalytic performance at the counter electrode, and in other cases the active HEF reaction can in turn affect the intrinsic activity of PEC. In this system, three dimensional TiO2 nanotube arrays coupled with nitrogen doped TiO2 nanoparticles (3D-TNAs/N-TiO2) was prepared as photoanode for solar light-driven PEC process while NH2-MIL-101 loaded on carbon felt (Fe-MOFs@CF) have been used as the cathode for HEF reaction. The performances of the synergetic system showed much higher degradation efficiency, which were evaluated by degrading typical organic containments in water (with the best of~95% in 5min with 2*3 cm2 electrode area). The reaction rate in the coupling system were ∼7.25 and 1.18 times higher than single PEC or HEF with a wide pH applied range, well recycled and good stability for further application in water purification.

Preparation of MnO2@MPIA catalysts with a controlled oxygen vacancy for the efficient catalytic oxidation of formaldehyde at room temperature

Preparation of MnO2@MPIA catalysts with a controlled oxygen vacancy for the efficient catalytic oxidation of formaldehyde at room temperature

Morphology engineering of Co3O4 spinel for efficient oxidation of lean methane at low temperature

Nowadays, the development of high-performance non-noble metal catalysts is an important research direction for controlling methane emissions from liquefied natural gas (LNG)-powered vehicles and vessels, and Co3O4 spinel has attracted great attention. In this work, Co3O4 catalysts with different morphologies (flower, sheet, particle, and cube) were synthesized by hydrothermal method and their catalytic performance was evaluated. The results showed that the flower-like Co3O4 (Co3O4-F) catalyst exhibited the highest activity in the lean methane oxidation with the T90 (temperature at the methane conversion of 90%) of 365 °C. Compared to other catalysts, Co3O4-F contained an amount of Co3+ sites and the weakest Co3+-O bond, which facilitated the extraction of active lattice oxygen and the initial oxidation of methane to intermediate products (formate and -COO-) on the catalyst surface. Meanwhile, the abundant oxygen vacancies on the surface of the Co3O4 catalyst could efficient activate O2 to form active oxygen species, which promoted the oxidation of intermediate products to CO2 and H2O. The methane oxidation over the Co3O4-F was confirmed to conform with Mars-van Krevelen mechanism. This work provides a facile way to enhance the methane oxidation activity of Co3O4 catalysts by modulating the morphology.

Solvent-free oxidation of benzylic C(sp3)–H bond over MA3Bi2Br9 perovskite photocatalyst by efficient singlet oxygen generation

Photocatalytic selective oxidation under solvent-free conditions plays a pivotal role in green chemistry, which can diminish pollutant production and minimize resource consumption in chemical reactions. In this process, the activation of molecular oxygen (O2) plays a crucial role. Here, we demonstrate the efficient oxidation of C(sp3)–H bond in pure toluene to produce oxygenated products of benzaldehyde (BAD) and benzyl alcohol (BA) using O2 as an oxidant over lead-free MA3Bi2Br9 perovskite. Systematic spectroscopic characterizations and controlled experiments validate that MA3Bi2Br9 enables the activation of O2 to superoxide radical (•O2−) and singlet oxygen (1O2) via charged electron transfer and excitonic energy transfer, respectively. Significantly, 1O2 emerges as an important active species. The optimal photocatalytic performance delivered by MA3Bi2Br9 reaches a BAD generation rate of 10756 µmol g−1h−1, with a BAD product selectivity of 81.5 %. The performance is greater than most classical photocatalysts, representing one of the best photocatalytic activities available in the literature. The lead-free feature of MA3Bi2Br9 perovskite coupled with its impressive catalytic performance makes it promising for practical applications.

Platinum meso-tetraphenylporphyrin (Pt(II)TPP) mediated the efficient oxidation of alkyl aromatics to ketones in the presence of tert-butyl hydroperoxide

Platinum meso-tetraphenylporphyrin (Pt(II)TPP) mediated the efficient oxidation of alkyl aromatics to ketones in the presence of tert-butyl hydroperoxide

Engineering Ultrathin Alloy Shell in Au@AuPd Core‐Shell Nanoparticles for Efficient Plasmon‐Driven Photocatalysis

AbstractBimetallic core‐shell nanoparticles (NPs) possessing a synergetic coupling of plasmonic and catalytic metals have emerged as promising prototypes for efficient plasmon‐driven photocatalysis. Here, Au@AuPd core‐shell NPs composed of Au core NP and ultrathin AuPd shell are introduced to acquire improved light utilization efficiency in photocatalytic selective oxidation. With systematical control of the composition of the ultrathin alloy shell, it reveals that the Au@AuPd core‐shell NPs with 10 at% Pd (in the single‐atom alloy regime) is an effective nanostructure capable of maximizing the quantum yield of plasmon‐induced light absorption and optimizing the surface electronic structure for catalytic reactions. This controlled system provides new insights into shell engineering for enhancing photocatalytic performance via the regulation of energy funneling processes in core‐shell nanocatalysts.

Non-Thermal Plasma Technology for Further Purification of Flue Gas in the Resource Utilization Process of Waste Mercury Catalyst: A Case Study in Xinjiang, China

This study aims to advance the recycling of mercury-containing waste and promote sustainable development within the polyvinyl chloride (PVC) industry. Our innovative system integrates pre-treatment technology (spraying potassium permanganate and demisting and dust removal) with efficient non-thermal plasma oxidation, resulting in excellent treatment efficiency, low cost, and simple operation. With a processing capacity of 3000 m3/h, the concentration of mercury emissions in flue gas can achieve the target of <0.01 mg/m3, boasting a removal efficiency exceeding 98%, which satisfies the standard “Emission standard of air pollutants for industrial kiln and furnace” (GB 9078-1996). Our results can provide technical support for the comprehensive purification of mercury-containing flue gas during the resource recovery process from mercury-containing waste. The application of our system can contribute to reducing mercury emissions in the PVC industry, lowering occupational exposure risks for workers, and promoting China’s better compliance with “the Minamata Convention on Mercury”.

Assessing the Chemical-Free Oxidation of Trace Organic Chemicals by VUV/UV as an Alternative to Conventional UV/H2O2.

Low-pressure mercury lamps with high-purity quartz can emit both vacuum-UV (VUV, 185 nm) and UV (254 nm) and are commercially available and promising for eliminating recalcitrant organic pollutants. The feasibility of VUV/UV as a chemical-free oxidation process was verified and quantitatively assessed by the concept of H2O2 equivalence (EQH2O2), at which UV/H2O2 showed the same performance as VUV/UV for the degradation of trace organic contaminants (TOrCs). Although VUV showed superior H2O activation and oxidation performance, its performance highly varied as a function of light path length (Lp) in water, while that of UV/H2O2 proportionally decreased with decreasing H2O2 dose regardless of Lp. On increasing Lp from 1.0 to 3.0 cm, the EQH2O2 of VUV/UV decreased from 0.81 to 0.22 mM H2O2. Chloride and nitrate hardly influenced UV/H2O2, but they dramatically inhibited VUV/UV. The competitive absorbance of VUV by chloride and nitrate was verified as the main reason. The inhibitory effect was partially compensated by •OH formation from the propagation reactions of chloride or nitrate VUV photolysis, which was verified by kinetic modeling in Kintecus. In water with an Lp of 2.0 cm, the EQH2O2 of VUV/UV decreased from 0.43 to 0.17 mM (60.8% decrease) on increasing the chloride concentration from 0 to 15 mM and to 0.20 mM (53.5% decrease) at 4 mM nitrate. The results of this study provide a comprehensive understanding of VUV/UV oxidation in comparison to UV/H2O2, which underscores the suitability and efficiency of chemical-free oxidation with VUV/UV.

Anthraquinone-based polymer modified BiVO4 photoanode with strong electron-withdrawing functional groups for boasting photoelectrochemical water oxidation

The photoelectrochemical (PEC) performance ofBiVO4 is limited by sluggish water oxidation kinetics and severe carrier recombination. Herein, a novel high-performance BiVO4/NiFe-NOAQ photoanode is prepared by a simple one-step hydrothermal method, using BiVO4 and 1-Nitroanthraquinone (NOAQ) as raw materials. The BiVO4/NiFe-NOAQ photoanode has an excellent photocurrent density of 5.675 mA cm−2 at 1.23 VRHE, which is 3.35 times higher than that of the pure BiVO4 (1.693 mA cm−2) photoanode. The BiVO4/NiFe-NOAQ shows a significant improvement in charge separation efficiency (86.12 %) and charge injection efficiency (87.86 %). The improvement is ascribable to the NiFe-NOAQ form a type II heterojunction with BiVO4 to inhibit carrier recombination. More importantly, the kinetic isotope experiment suggests that the proton-coupled electron transfer (PCET) process can enhance the charge transfer of BiVO4/NiFe-NOAQ. The contact angle measurements show that modifying functional groups enhanced the hydrophilicity of BiVO4/NiFe-NOAQ, which can further accelerate the PCET process. The XPS and PL results as well as the tauc plot indicate that the strong electron-withdrawing ability of –NO2 which can promote the extension of π conjugation, results in more π electron delocalization and produces more efficient active sites, thus achieving efficient photoelectrochemical water oxidation.

Active Sites Engineered Bimetallic Iron–Vanadium Oxide (FeVOx) Thin Film Electrocatalyst for Efficient and Sustainable Water Oxidation

Active Sites Engineered Bimetallic Iron–Vanadium Oxide (FeVO_<i>x</i>) Thin Film Electrocatalyst for Efficient and Sustainable Water Oxidation

Mechanistic Understanding of Oxygen Activation on Bulk Au(111) Surface Using Tip-Enhanced Raman Spectroscopy.

Gaining mechanistic understanding of oxygen activation on metal surfaces is a topical area of research in surface science. However, direct investigation of on-surface oxidation processes at the nanoscale and the empirical validation of oxygen activation pathways remain challenging for the conventional analytical tools. In this study, we applied tip-enhanced Raman spectroscopy (TERS) to gain mechanistic insights into oxygen activation on bulk Au(111) surface. Specifically, oxidation of 4-aminothiophenol (4-ATP) to 4-nitrothiophenol (4-NTP) on Au(111) surface was investigated using hyperspectral TERS imaging. Nanoscale TERS images revealed a markedly higher oxidation efficiency in disordered 4-ATP adlayers compared to the ordered adlayers signifying that the oxidation of 4-ATP molecules proceeds via interaction with the on-surface oxidative species. These results were further validated via direct oxidation of the 4-ATP adlayers with H2O2 solution. Finally, TERS measurements of oxidized 4-ATP adlayers in the presence of H2O18 provided the first empirical evidence for the generation of oxidative species on bulk Au(111) surface via water-mediated activation of molecular oxygen. This study expands our mechanistic understanding of oxidation chemistry on bulk Au surface by elucidating the oxygen activation pathway.