Surface Oxidation Reaction Research Articles

Electrochemical Oxidation Mechanism of Pyrite in a Copper(II)-Citrate-Sodium Thiosulfate Composite System

Pyrite is an important gold carrier during gold leaching, but it is readily oxidized, which causes environmental problems such as acidic mine drainage. Thus, it is necessary to study the oxidation mechanism of pyrite in a gold-leaching electrolyte. The surface oxidation reaction of pyrite is a multi-electron transfer electrochemical oxidation process. Based on this, electrochemical technology was used to explore the electrochemical oxidation mechanism of pyrite in a Cu2+-Cit3−-S2O3 2− system. The surface oxidation products of the pyrite were characterized by Raman spectroscopy and X-ray photoelectron spectroscopy. The experiments showed that the thiosulfate concentration did not change the oxidation mechanism of pyrite at 0.30 V under the conditions of this experiment. Increasing the concentration and potential of thiosulfate accelerated the oxidation rate of pyrite. The electrochemical oxidation of pyrite in the Cu2+-Cit3−-S2O3 2− system occurred in two stages. At low potentials in a passivated state, the process was diffusion-controlled, and the surface oxidation rate was slow. When the potential exceeded 0.50 V, the passivation film on the surface was penetrated, allowing the oxidation reaction on the surface of pyrite to continue. The results of this experiment are useful for deepening the understanding of the oxidation mechanism of pyrite in electrolytes.

Effect of 2-butanone addition to ethylene fuel on soot formation in counterflow diffusion flames using newly proposed soot model

An improved consistent soot model is proposed and applied to evaluate the effect of 2-butanone addition (10 % to 50 % on a volume basis represented as case 1 to case 5) to ethylene fuel on soot formation using a counterflow burner configuration. The predictive capability of the suggested soot model is verified by assessing its performance against existing experimental data on soot formation (SF) configuration-type ethylene counterflow flames at diverse strain rates and various fuel additives. The proposed soot model comprises 55 inception reactions with temperature-dependent collision efficiency and 10 condensation reactions from 10 PAH species (from naphthalene to larger PAHs up to coronene), including modified HACA surface growth and oxidation reactions. 2-butanone is produced as a byproduct during the pyrolysis of biomass and the microbiological fermentation of agricultural waste. It holds various benefits as a prospective biofuel for spark ignition (SI) engines. Limited information exists regarding its sooting characteristics due to a lack of available soot measurements. The simulations are conducted for the soot formation (SF) type counterflow flames with a fixed fuel and oxidizer jet velocity. The proposed soot model can effectively replicate both the qualitative and quantitative aspects of the experimental trends and shows a better agreement than the existing models available in the literature. The soot volume fraction (SVF) and the particle number density (PND) decrease with increasing the 2-butanone concentration in the binary fuel mixture. The PAH concentration decreases with increasing 2-butanone addition in the fuel mixture. The peak SVF and the maximum temperature are reduced by ∼22.7 % and ∼3.6 %, with a 40 % increase in the 2-butanone portion in the fuel mixture from case 1 to case 5. Increasing the 2-butanone content in the fuel mixture decreases the inception rate, HACA rate, and condensation rate while it increases the oxidation rate.

Novel photocatalysis-assisted mechanical polishing of laser cladding cobalt-based alloy using TiO2 nanoparticles

This paper presents a novel photocatalysis-assisted mechanical polishing method for cobalt-based alloy cladding layers using TiO2 nanoparticles. By leveraging the active oxygen species generated by the photocatalyst under illuminated conditions, surface oxidation reactions on cobalt-based alloys are initiated, thereby enhancing material removal efficiency. The underlying principles of photocatalytic oxidation are elucidated, particularly the promotion of oxidation by •OH when it interacts with the metal surface, leading to the formation of a CoO oxide film on the cladding layer surface and a subsequent reduction in surface hardness. An experimental platform was established, and research findings identified an etching time of 60 min and a TiO2 concentration of 10 wt% as optimal process parameters. Comparative analysis with pure mechanical polishing and chemical mechanical polishing revealed that photocatalysis-assisted mechanical polishing yielded superior surface roughness of 60 nm and a material removal rate of 63.8 μm/min.

Al3Sc thin films for advanced interconnect applications

AlxSc1-x thin films have been studied with compositions around Al3Sc (x = 0.75) for potential interconnect metallization applications. As-deposited 25 nm thick films were x-ray amorphous but crystallized at 190 °C, followed by recrystallization at 440 °C. After annealing at 500 °C, 24 nm thick stoichiometric Al3Sc showed a resistivity of 12.6 μΩcm, limited by a combination of grain boundary and point defect (disorder) scattering. Together with ab initio calculations that found a mean free path of the charge carriers of 7 nm for stoichiometric Al3Sc, these results indicate that Al3Sc bears promise for future interconnect metallization schemes. Challenges remain in minimizing the formation of secondary phases as well as in the control of the non-stoichiometric surface oxidation and interfacial reactions with underlying dielectrics.

(Invited) Design of Surface Oxidation and Nitridation Reactions on 4H-SiC for the Advanced SiC Gate Stack Formation Processes

Silicon carbide (SiC) MOSFETs are expected to replace Si bipolar transistors partially in applications such as automotive, railroad, and other high-voltage applications. But the resistance of the MOS inversion layer channel limits the performance of MOSFETs. It has been clarified that the effective carrier density in the inversion channel is significantly reduced by the carrier trapping by the high density of defect states distributed nearby SiO2/SiC interface. In this study, our understanding of oxidation and nitridation reactions of SiC for designing the gate stack formation processes to improve the MOS interface characteristics is presented.Choosing SiO2 as a gate dielectric for SiC is favorable from various aspects including its ability to form a thermodynamically stable interface with SiC, which is free of reactions at the process temperature. However, from a microscopic point of view, Si-O bond alone cannot cover the whole surface of SiC and the excess C atoms on the surface causes the formation of defect states. One of the possible approaches has been employing an appropriate thermal oxidation condition to enhance the excess carbon elimination by forming CO. For example, we have experimentally demonstrated a significant reduction of Dit by employing high-temperature thermal oxidation with a rapid heating furnace [1]. However, such approach seems to bring a serious drawback such as defect formation in the surface region of SiC, experimentally detected by a lattice distortion in the beneath of SiO2 after high-temperature oxidation [2]. One of the possible reasons for such deterioration would be an invasion of activated oxygen atoms into the surface region of SiC [3]. A possible approach to avoid such drawback of high-temperature oxidation process would be utilizing H2O vapor for the formation of SiO2/SiC interface at relatively lower temperature while avoiding the damages on SiC surface [4], since H2O oxidation was found to be advantageous to remove CO more efficiently than O2 oxidation even at low temperature.On the other hand, another approach to passivate SiC surface is the surface nitridation technique, which is the most common way in industry to fabricate SiC MOS interface typically achieved by high-temperature annealing in NO gas [5]. Nitridation can replace the topmost C sites with N without inducing significant distortion in the SiC surface structure, to suppress the C-related defect formation at the interface. The advantage of this reaction is that it proceeds self-limited manner and N atoms are introduced only on the topmost surface of SiC. Note that NO gas triggers the surface nitridation by removing the surface C atoms in the form of CO by oxidation. Actually, a very similar reaction occurs even when SiC is annealed in N2 [6] ambient with a slight addition of O2. We experimentally found that the surface N density saturated with different values when we employed various N2+O2 atmosphere with different O2 concentration. Therefore we setup a simple model to describe the saturation behavior, which is determined by the balance between the rate of N uptake (N+) and the rate of N desorption (N‒) mainly due to the oxidation reaction [7]. This model was found to represent the time-dependent change of surface N density well, by assuming that N+ remained constant during the reaction and N‒ was proportional to both the reaction rate of interface oxidation and the surface N density [8]. Based on this simplified model, it is possible to design a process to tune the N density. By choosing appropriate temperature and oxygen partial pressure we can increase N density at the surface to minimize the interface trap density. Further improvement of surface N density would be achieved by further controlling of the blance between N uptake and N desorption reactions.As we have discussed so far, the role of materials science to clarify the interface phenomena is significantly important to achieve a further improved SiC MOS interface characteristics for the next generation SiC power MOSFET process technology. [1] R. Kikuchi and K. Kita, Appl. Phys. Lett. 105, 032106 (2014).[2] A. D. Hatmanto and K. Kita, Appl. Phys. Express 11, 011201 (2018).[3] A. D. Hatmanto and K. Kita, Jpn. J. Appl. Phys. 59, SMMA02 (2020).[4] H. Hirai and K. Kita, Appl. Phys. Lett. Appl. Phys. Lett. 113, 172103 (2018).[5] J. Rozen et al., J. Appl. Phys. 105, 124506 (2009).[6] A.Chanthaphan et al., AIP Adv. 5, 097134 (2015).[7] T. Yang and K. Kita, Jpn. J. Appl. Phys. 61, SC1077 (2022).[8] T. Yang and K. Kita, SSDM 2023, Chiba.

Electrochemical Analysis and Quantification of Anodic Oxidation on Activated Carbon Cloth Electrodes through Cyclic Voltammetry

Capacitive Deionization (CDI) has applications ranging from water purification to biofuels processing. For CDI to be a viable scalable technology, electrode stability is critical. In extended experiments the activated carbon cloth (ACC), used for the electrode, has been previously observed to degrade as a result of surface oxidation reactions. Carbon cloth oxidation can reduce the surface area and alter the pore structure, in turn reducing the adsorption capacity. While the behavior of oxidation is known, a reliable method of quantifying the extent of degradation is lacking. To quantify it, cyclic voltammetry was explored to measure the capacitance of pristine and oxidized carbon cloth samples. A three-electrode electrochemical cell was used to quantify capacitance of activated carbon cloth in 1M NaCl solution. The specific capacitance of carbon cloth that underwent anodic oxidation was lower than cathodic and pristine carbon cloth. Further tests analyzed the change in the severity of the anodic degradation on whether the initial CDI separations were performed on organic or inorganic ions. Scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS) was utilized to verify and quantify surface oxidation. Cyclic voltammetry is demonstrated as a simple and reliable method for analyzing and quantifying anodic oxidation on activated carbon cloth electrodes in CDI stacks.

Optimizing electronic structure of CoSe2 nanorods via N-dopant modulation for superior electrocatalytic hydrogen evolution reaction

The hydrogen evolution reaction (HER) performance of transition metal selenides (TMSs) based electrocatalysts in alkaline media is severely affected by numerous issues, including structural instability due to surface oxidation reactions, high overpotentials, and sluggish water dissociation kinetics. Here, we present the simple and scalable synthesis of N-doped cobalt diselenide nanoflowers grown on conductive carbon cloth (N-CoSe2/CC). First, Co(OH)F/CC precursor with a well-defined pore structure through the solvothermal method followed by incorporation of Se ions on the Co mAtrix via a chemical vapor deposition method. Porous CoSe2 was further modified by a heteroatom (N) to enhance electrocatalytic activity, high performance might be attributed to the formation of plentiful active sites, synergistic effects, structural modulation, and improved electronic conductivity. The optimal N-CoSe2/CC catalyst exhibits a high electrochemically active surface area (ECSA) and possesses a low working potential of 73 mV (vs. RHE), which corresponds to 10 mA cm−2 current density, and a lower Tafel slope (75 mV dec−1) in an alkaline medium (1.0 M KOH) with longterm stability of 20 h. The outcomes of the experiment aided by DFT calculations demonstrate that doping of N can significantly alter the electronic states of the “Co” d-orbital, boosting HER performance. This study might open up new possibilities for designing anion-doped transition-metal dichalcogenide electrocatalysts for the potential applicability of HER.

ReaxFF molecular dynamics simulation and experimental validation about chemical reactions of water and alcohols on SiC surface

The high chemical inertness of silicon carbide (SiC) makes it difficult for surface chemical reactions to occur. Surface oxidation reactions are crucial for improving the processing efficiency and surface quality of SiC wafers. Extensive research has been conducted on conventional aqueous polishing slurries, while investigations on non-aqueous solvent-based polishing slurries have emerged as alternative options for enhancing SiC surface processing, as evidenced by recent scholarly reports. However, the surface chemical reaction mechanism of silicon carbide in either water or other hydroxyl groups containing solvents remains still unclear and is not well understood. In this work, ReaxFF molecular dynamics simulation was used to study the dynamic reaction processes between solvents and 6H SiC (001) surfaces. The oxidation of SiC surface in water and alcohol solvent is found to go through three stages: in the first stage, the solvent molecules move towards the SiC surface and react with the uncoordinated Si atoms and C atoms on the surface; in the second stage, the solvent molecules adsorbed on the surface of SiC reduces the Si–C bonding energy and promotes the breaking of Si–C bonds; in the third final stage, the migration of OH and H on the SiC surface induces the formation of Si–O–Si bonds, which promotes the continuous oxidation of the SiC surface. The order of simulated chemical reactivity between solvent and silicon carbide surface is consistent with experimental polishing removal rates. The reaction mechanism of solvent on silicon carbide surface was proposed by combining ReaxFF simulation results with polishing experiments, AFM, and XPS data analysis, shedding new insights on better understanding the mechanism of SiC chemical mechanical polishing.

Study of Indium Phosphide Quantum Dots/Carbon Quantum Dots System for Enhanced Photocatalytic Hydrogen Production from Hydrogen Sulfide

Quantum dots (QDs) are promising semiconductor nanocrystals in photocatalysis due to their unique properties and in contrast to bulk semiconductors. Different from the traditional modification methods of indium phosphide (InP) QDs such as metal doping, shell design, and surface ligand modification, we firstly constructed the indium phosphide quantum dot and carbon quantum dot (InP QDs/CQDs) system and used it for the study of photocatalytic hydrogen production from hydrogen sulfide (H2S) in this work. The photocatalytic performance tests show that the average rate of photocatalytic decomposition of hydrogen sulfide to produce hydrogen of the InP QDs/CQDs system increases by 2.1 times in contrast to InP QDs alone. The steady-state and time-resolved photoluminescence spectra demonstrated that the introduction of CQDs can effectively improve the separation efficiency of photo-generated carriers. In addition, the surface electronegativity of the InP QDs/CQDs system is weaker than that of InP QDs, which may reduce the repulsion between the photocatalyst and reaction substrate, promoting the surface oxidation reaction in the photocatalytic process. This work indicates that the construction of the QDs hybrid system can improve their photocatalytic performance, providing a way to optimize QDs in photocatalysis.

Enhancing oxidation resistance of MoAlB based on its anisotropic oxidation mechanism: A theoretical calculation guided experimental investigation

MoAlB is considered the most promising material for oxidation resistance among the MAB phase family. However, the anisotropic oxidation mechanism at the atomic scale has not been fully investigated, which may limit its practical applications. In this work the anisotropic oxidation mechanism of MoAlB was first explored through systematic theoretical calculations, based on which an effective strategy to enhance its oxidation resistance was identified and successfully implemented in the experimental work. The theoretical calculation revealed that the anisotropic oxidation of MoAlB was primarily related to the difference in free energy of surface oxidation reactions due to the degrees of electron interaction localization of O-Al bonding. A series of candidates of various transition metal-doped MoAlB materials were then designed to improve the weaker surface of MoAlB for oxidation resistance enhancement. Among these candidates, Zr-doped MoAlB was selected to further evaluate the effects of doping on the anisotropic oxidation through the electronic structure and Ab initio molecular dynamics (AIMD). Finally, Zr-doped MoAlB was experimentally synthesized to validate the theoretical design. Non-isothermal oxidation kinetics analysis indicated that Zr doping can enhance the oxidation resistance of MoAlB by promoting the formation of a protective oxide scale and increasing the formation activation energy of volatile products, which finally reduced the thickness of the oxidation scale on the surface after isothermal oxidation of the bulk material. This work not only contributes to an in-depth understanding of the oxidation mechanisms in MoAlB but also presents a new approach to enhance its oxidation resistance and other Al containing ceramic materials beyond MAB phases.

Adsorption behavior of O2 on U-Nb surface: a first-principles study.

Oxygen is a chemically active gas. Metal uranium will be rapidly oxidized when exposed to oxygen directly, forming a complex and uncompacted oxide layer on the surface. The U-O2 reaction system is a very complex metal oxidation system. The surface oxidation reaction of uranium-niobium alloy is more complex, and it is also the main corrosion form of uranium-niobium alloy. Exploring the microscopic mechanism of surface oxidation corrosion of uranium-niobium alloy is of great significance for understanding the surface corrosion phenomenon in practical applications. The adsorption of O2 on U-Nb (5at.%) surface was investigated by first-principles calculation using a periodic slab model within the density functional theory (DFT). The effect of different levels of Nb doping on O adsorption was investigated, and the stability of O-U and O-Nb adsorption was studied in conjunction with the Bader charge distribution, differential charge density map, electron density of states, and surface work function. The results showed that physical adsorption happens when O2 is vertically adsorbed at the top site of Nb atom, whereas dissociative adsorption happened in all other configurations considered here. The interaction between adsorbed O2 and U-Nb surface was essentially the hybridization between the O/2p orbital electrons and the U/6d, U/5f, Nb/4p, Nb/5s, and Nb/4d orbital electrons to form a relatively stable ionic bond. When Nb was doped into the second layer of the surface, the most stable O2 adsorption configuration was top-site horizontal adsorption. The adsorption energy was - 22.38 eV, which was more negative than the adsorption energy of - 21.38 eV for the first doped layer horizontal adsorption at hollow-site. The interaction was essentially the hybridization between O/2p orbital electrons and U/6d and U/5f electrons and between O/2s orbital electrons and U/6p orbital electrons to form a relatively stable ionic bond. In this paper, the adsorption and dissociation of oxygen molecules on the surface of U-Nb system were systematically studied by first-principles calculations, in order to explore the surface oxidation corrosion mechanism of uranium-niobium alloy from the micro level. The VASP program uses PAW pseudopotential, which belongs to the density functional method, and uses DSP.

Viral inactivation using microwave-enhanced membrane filtration

Pathogenic viruses (e.g., Enteroviruses, Noroviruses, Rotaviruses, and Adenovirus) present in wastewater, even at low concentrations, can cause serious waterborne diseases. Improving water treatment to enhance viral removal is of paramount significance, especially given the COVID-19 pandemic. This study incorporated microwave-enabled catalysis into membrane filtration and evaluated viral removal using a model bacteriophage (MS2) as a surrogate. Microwave irradiation effectively penetrated the PTFE membrane module and enabled surface oxidation reactions on the membrane-coated catalysts (i.e., BiFeO3), which thus elicited strong germicidal effects via local heating and radical formation as reported previously. A log removal of 2.6 was achieved for MS2 within a contact time as low as 20 s using 125-W microwave irradiation with the initial MS2 concentration of 105 PFU∙mL-1. By contrast, almost no inactivation could be achieved without microwave irradiation. COMSOL simulation indicates that the catalyst surface could be heated up to 305 oC with 125-W microwave irradiation for 20 s and also analyzed microwave penetration into catalyst or water film layers. This research provides new insights to the antiviral mechanisms of this microwave-enabled catalytic membrane filtration.

Atomic reconstruction and oxygen adsorption behavior of the pyrite (100) surface: a DFT study.

The analysis of the surface chemical behavior of pyrite is highly crucial in the fields of environmental conservation, metal extraction, and flotation separation. In this paper, the mechanism of atomic reconstruction on the pyrite surface and the adsorption behavior of O2 on a reconstructed surface are calculated by density functional theory (DFT). Different reconstruction surfaces were constructed by deleting S and Fe atoms on the (100) surface of pyrite. In addition, the geometric configuration, formation energy, binding energy, cohesion energy, and surface electronic properties of the reconstruction surface were calculated. The adsorption energies and geometric configurations of O2 on different reconstructed surfaces were also determined. The results show that under Fe-poor conditions, the charge of Fe atoms increases, and S atoms form Sn on the reconstructed surface. The binding energy between the Sn and the substrate (ideal surface) is lower, which is similar to the Sn adsorption on the substrate surface with the Fe atom as the site. Sn has high cohesive energy and is resistant to being attacked by oxidants, which leads to structural collapse, and a low affinity for O2. Under S-poor conditions, the -[Fe-S]n- plane structure formed on the reconstructed surface. The -[Fe-S]n- structure stably bonds to the substrate by an Fe-S bond, and exhibits strong binding energy. However, the -[Fe-S]n- structure has low cohesive energy and exhibits thermodynamic instability. In contrast, O2 shows a strong affinity for the -[Fe-S]n- structure, indicating that the deficiency of the S atom promotes the surface oxidation reaction. The mechanism of atomic reconstruction on the surface of pyrite is of utmost importance for understanding its surface chemical behavior.

Surface active oxygen engineering of photoanodes to boost photoelectrochemical water and alcohol oxidation coupled with hydrogen production

Photoelectrochemical conversion of solar energy into fuels (or chemicals) is in urgent need of efficient photoanodes to drive its practical applications. Nevertheless, the development of high performance photoanode usually suffers from slow charge transfer and sluggish surface catalytic kinetics. Here, we report a surface active oxygen engineering strategy through the modification and activation of NiCo layered double hydroxide (NiCo-LDH), where the activated NiCo-LDH (NiCo-LDH-Act) captures the photogenerated holes and acts as cocatalyst for surface oxidation reactions. The as-developed BiVO4/NiCo-LDH-Act achieves more than 3-fold higher photocurrent density than that of pristine BiVO4. Experimental integrated with theoretical studies further testify the bifunctional of NiCo-LDH-Act for hole transport and catalytic reactions. Moreover, the adsorbed ·OH originated from active oxygen enables efficient oxidation of glycerol to attain 1,3-dihydroxyacetone (DHA) with a productivity of 20.5 μmol cm–2 h–1 at 1.4 V vs. RHE with simultaneously producing hydrogen at the cathode.

Bragg Coherent Diffraction Imaging Studies of Pt Nanograins Under Electrochemical Control Using Pipette Cells

Deeply penetrating X-rays are well suited to investigate the electrochemical systems and interfaces under in-situ / operando environments. In particular, a recently developed X-ray Bragg Coherent Diffractive Imaging (BCDI) is a powerful tool for 3D imaging of internal structures of nano-size particles, [1,2] and the internal compositions of alloy nanoparticles. [3-5] Further, the well-annealed alloy nanoparticles can be electrochemical treated to increase the surface strain and to enhance the certain electrocatalytic activities such as oxygen reduction reaction (ORR). [6] After introduction of the technique and examples, we will focus on how strain in a single Pt nano-grain evolves in response to applied potential. The strain responses then will be discussed within the context of surface oxidation and oxygen-evolution reaction (OER).For Pt nanograins of a film grown on a substrate, the strain response is tightly related to the place-exchange surface oxidation and electrochemical double layer to the applied potential range relevant to OER. During polarization, marked changes in surface strain arise from the Coulombic attraction between the electrode surface and electrolyte ions, while the strain in the bulk of the crystal remained unchanged. The concurrent surface redox reactions have a strong influence on the magnitude and nature of the strain dynamics under polarization.In careful BCDI analyses, we found that only the top 10 nm of Pt at the grain/electrolyte interface responded sensitively to applied potential, while a much more muted response was observed for the remainder of the bulk Pt grain. The potential-dependent strain responses were not present at grain boundaries locked to the neighbor grains and at the bottom interface in contact to the substrate, neither of which were exposed to electrolyte. Our measurements further suggested that even highly stable electrodes such as Pt are subject to irreversible structural changes during polarization, highlighting the importance of in-situ/operando techniques to draw faithful structure-activity relationships in electrochemistry. These observations were possible due to the high strain sensitivity of BCDI combined with the near-zero X-ray scattering background of the submicron scale nanopipette electrochemical cell.[1] Y. Liu et al., Nano Letters 17, 1595 (2017).[2] W. Cha, Y. Liu, H. You, G. B. Stephenson, and A. Ulvestad, Advanced Functional Materials 27, 1700331 (2017).[3] T. Kawaguchi et al., Physical Review Letters 123, 246001 (2019).[4] T. Kawaguchi, W. Cha, V. Latyshev, S. Vorobiov, V. Komanicky, and H. You, Journal of the Korean Physical Society 75, 528 (2019).[5] S. Choi et al., Nano Letters 20, 8541 (2020).[6] T. Kawaguchi, V. Komanicky, V. Latyshev, W. Cha, E. R. Maxey, R. Harder, T. Ichitsubo, and H. You, Nano Letters 21, 5945 (2021).

Nitrogen and Sulfur Codoped Porous Carbon Directly Derived from Potassium Citrate and Thiourea for High-Performance Supercapacitors.

By introducing a heteroatom into carbon material, an effective improvement in capacitance can be realized owing to surface oxidation and reduction reactions of pseudocapacitors. Herein, a simple one-pot carbonization activation method was proposed to convert potassium citrate into three-dimensional interconnected porous carbon (PC). Then, an effective double heteroatom doping method by thiourea was used to prepare nitrogen-sulfur-doped PC (N,S-PC). This porous structure facilitates the storage of a large number of ions and reduces their diffusion path. The synthesized N,S-PC nanomaterial has a capacitance of 674 F/g at 1 A/g in a 1 M H2SO4 electrolyte, can retain 94.41% of the initial capacitance after 10 000 cycles at 5 A/g, and has a long cycle life. More importantly, a symmetric supercapacitor assembled with this material can exhibit an energy density of up to 32.6 (W·h)/kg at a high-power density of 750 W/kg. This is due to the high performance of N,S-PC in supercapacitor electrode materials.

Semiconducting Polymers for Oxygen Evolution Reaction under Light Illumination.

Sunlight-driven water splitting to produce hydrogen fuel has stimulated intensive scientific interest, as this technology has the potential to revolutionize fossil fuel-based energy systems in modern society. The oxygen evolution reaction (OER) determines the performance of overall water splitting owing to its sluggish kinetics with multielectron transfer processing. Polymeric photocatalysts have recently been developed for the OER, and substantial progress has been realized in this emerging research field. In this Review, the focus is on the photocatalytic technologies and materials of polymeric photocatalysts for the OER. Two practical systems, namely, particle suspension systems and film-based photoelectrochemical systems, form two main sections. The concept is reviewed in terms of thermodynamics and kinetics, and polymeric photocatalysts are discussed based on three key characteristics, namely, light absorption, charge separation and transfer, and surface oxidation reactions. A satisfactory OER performance by polymeric photocatalysts will eventually offer a platform to achieve overall water splitting and other advanced applications in a cost-effective, sustainable, and renewable manner using solar energy.

Boosting photocatalytic hydrogen production by creating isotype heterojunctions and single-atom active sites in highly-crystallized carbon nitride

Carbon nitride-based photocatalysts hold an enormous potential in producing hydrogen. A strategy to simultaneously create isotype heterojunctions and active sites in highly-crystallized carbon nitride is anticipated to significantly boost the photocatalytic activity, but is yet to be realized. Herein, we find that cobalt salt added in the ionothermal synthesis can promote the phase transition of heptazine-based crystalline carbon nitride (CCN) to triazine-based poly(triazine imide) (PTI), rendering the creation of single-atom cobalt coordinated isotype CCN/PTI heterojunction. Co-CCN/PTI exhibits an appreciable apparent quantum yield of 20.88% at 425 nm for photocatalytic hydrogen production with a rate achieving 3538 μmol h−1 g−1 (λ > 420 nm), which is 4.8 times that of CCN and 27.6 times that of PTI. The high photocatalytic activity is attributed to the Type II isotype highly-crystallized CCN/PTI heterojunction for promoting charge carrier migration, and the single-atom Co sites for accelerating surface oxidation reaction.

Effects of Halide Composition on the Self-Recovery of Photodegraded Cesium Lead Halide Perovskite Nanocrystals: Implications for Photoluminescence Applications

Photodegraded CsPbBr3 perovskite nanocrystals (NCs) can exhibit complete self-recovery following storage in the dark. This behavior results from the readsorption of surface ligands that experienced photoinduced desorption under UV light excitation. In the present work, mixed-halide CsPb(Cl0.4Br0.6)3, CsPb(Cl0.2Br0.8)3, and CsPb(Br0.7I0.3)3 NCs were prepared via ion exchange to evaluate the influence of halide composition on the photodegradation and self-recovery of NCs. Partially substituting Cl– for Br– enhanced the photoactivation, which improved the photoluminescence properties by optimizing the adsorption state of the surface ligands during light excitation. In contrast, partially substituting I– for Br– reduced the stability of the cubic crystal structure, thus subjecting the NCs to irreversible degradation (likely including a partial phase transition) and preventing their self-recovery. Cycle tests confirmed the reversibility of the photodegradation/self-recovery of CsPbBr3 NCs; however, this behavior was disturbed by irreversible surface oxidation reactions when the sample was exposed to ambient air. Therefore, it was concluded that ambient air must be excluded to effectively take advantage of the self-recovery phenomenon for practical applications.

Research Progress of First Principles Studies on Oxidation Behaviors of Ti-Al Alloys and Alloying Influence

Ti-Al alloys have good prospects in the aerospace, automobile, and other fields because of their excellent mechanical properties. However, the lack of high temperature oxidation resistance limits their practical applications. Various ways have been used to study their oxidation behaviors. Besides numerous experimental studies focused on the oxidation resistance properties of Ti-Al alloys, theoretical research based on first principles calculations has been carried out on the oxidation mechanisms on the atomic and electronic scales. In recent years, these theoretical studies have provided strong support for understanding the oxidation mechanisms and designing anti-oxidation modification measures. This review will focus on the surface oxidation reactions, element diffusion behaviors and interface bonding properties. The influencing mechanisms of alloying elements on the oxidation properties will be discussed in detail.