Adsorption Of Molecules Research Articles

Green Synthesis of Iron-Based Nanoparticles Using Pomegranate Leaf Extracts: Characterization, Biomolecules and Indole Removal

This study investigates the synthesis of iron-based nanoparticles (Fe NPs) using pomegranate leaf extracts and their application in removing indole, a persistent organic pollutant commonly found in wastewater. The physicochemical properties of the synthesized Fe NPs and the active biomolecules in the pomegranate leaf extracts were comprehensively characterized. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) analyses revealed that the Fe NPs exhibited quasi-spherical shapes, with sizes ranging from 75 to 105 nm. Energy-Dispersive X-ray Spectroscopy (EDS) confirmed a homogeneous distribution of elements, including C, O, Fe, and S, on the nanoparticle surfaces, with weight percentages of 43.59%, 42.95%, 12.58%, and 0.88%, respectively. Fourier-transform infrared spectroscopy (FTIR) identified key functional groups like −OH, −COOH, and −C=O, which are essential for the capping and stabilization of the nanoparticles. Biomolecules such as ellagic acid (C14H6O8) and gallic acid (C7H6O5) functioned as reducing agents, improving nanoparticle dispersion and preventing aggregation. The synthesized Fe NPs quickly achieved 45.5% removal of indole within just 20 min and maintained a stable removal efficiency of approximately 51.4% after 90 min. This performance was attributed to the synergetic interaction between the biomolecules and the nanoparticles, with the monolayer adsorption of indole molecules on the Fe NP surfaces likely setting an upper limit on the maximum achievable removal efficiency. It appears from this study that pomegranate leaf extracts can be effectively utilized to synthesize Fe NPs as a novel and eco-friendly approach, demonstrating promising potential for the rapid removal of indole from aqueous solutions.

Stabilization effect of nano-SiO2@iron-phosphorus on ferrallisols, calcareous soil and organic soil heavily polluted by heavy metals: A fast reaction curing stabilization process

The remediation of soil pollution by heavy metals (HMs) presents a significant challenge in environmental restoration. Stabilization remediation technology has proven effective in treating HMs contaminated soil. However, its development is constrained by drawbacks such as slow reaction kinetics and low adsorption capacity. This research synthesized a nano-SiO2@iron‑phosphorus (FPOH) material by SiO32− encapsulating the iron-phosphate precipitate obtained from Fe ion and phosphate. In addition, this research applied this material to ferrallisols, calcareous soils and organic soils with three different levels of high pollution by Cd, Pb, Cu and Zn. The experimental results indicate that all experimental soils stabilized rapidly within 1 day and met the requirements of remediation engineering standards (ChinaMEE HJ 1282-2023). Analysis of the possible mechanisms suggests that the FPOH material effectively fills voids with phosphate mineral formation, preventing the secondary release of HMs. During the stabilization process, FPOH involves the adsorption of free ions and small organic molecules in the soil, which does not affect its high reactivity. The development and utilization of FPOH offer valuable insights for soil stabilization remediation.

Experimental and molecular dynamics simulation of the synergistic mechanism of short-chain fluorocarbon surfactant and electrolyte on inhibiting coal dust pollution

This paper investigated the synergistic mechanism of short-chain fluorocarbon surfactant and electrolyte on inhibiting coal dust pollution via the experimental and molecular dynamics simulations Findings illustrated that the synergistic application of short-chain fluorocarbon and electrolyte achieves better dust suppression performance when compares with the individual application of FS-50 and FS-3100, the maximum suppression rates for FS-50 and FS-3100 after the addition of electrolytes are 94.48 % and 93.94 %, respectively. The addition of electrolyte reduces the diffusion coefficient of suppressants, and its effect on FS-3100 is much higher than on FS-50. The maximum particle size achieved by FS-50 reaches 304–344 μm, while only 238–269 μm and 269–306 μm are acquired by FS-3100. The smaller negative potential and the larger difference in EPE indicate that the addition of NaCl promotes the adsorption of H2O molecules by surfactants. Compared to FS-3100, FS-50 has a lower negative potential and a larger EPE difference, suggesting that FS-50 exhibits stronger reactivity and better ability of absorb ion hydrates and H2O molecules, and hence has superior agglomeration effect. The addition of NaCl also promotes the generation of more sodium hydrate ions and hydrated chloride ions, which enhances the ability of FS-3100 to absorb H2O. Compares with FS-50, due to special curved spatial configuration and the synergistic effect with electrolytes, FS-3100 could restrict the desorption of large numbers of H2O molecules more effectively, and therefore exhibiting better wettability.

Tunable sulfur vacancies in amorphous-crystalline AC-Bi2S3-x@C derived from CAU-17 for efficient capture of radioiodine: Comparison of sulfur vacancies in amorphous and crystalline structures

Solid-phase adsorption has been recognized as an effective method for the control of volatile radioactive iodine in spent fuel reprocessing plant off-gases. However, it is still a challenge to develop efficient and stable iodine capture adsorbents. In this work, sulfur-vacancy-rich amorphous-crystalline AC-Bi2S3-x@C was prepared by solvothermal vulcanization using CAU-17 as a precursor. Based on the synergistic effect of the amorphous structure and sulfur vacancy defects, AC-Bi2S3-x@C exhibited fast adsorption equilibrium time (15 min), distinguished iodine adsorption capacity (1763.9 mg g−1), high percentage of chemical adsorption (93.4 %) as well as favorable thermal and irradiation stability. Adsorption experiments and theoretical calculations verified that the amorphous structure not only enhance the charge transfer between sulfur vacancy defects and iodine molecules, but also offers rapid diffusion channels for iodine molecules to the interior of the adsorbent and sufficient internal binding sites to promote iodine molecule adsorption in its interior. The used adsorbent showed high iodine retention (92.3 %) and excellent chemical durability (normalized iodine leaching rate of 4.63 × 10-5 g m−2 d-1) in glass solidification. In general, this work presented a new concept in the design and synthesis of efficient radioactive iodine capture materials.

Investigating Molecular Adsorption on Graphene-Supported Platinum Subnanoclusters: Insights from DFT + D3 Calculations.

Platinum (Pt) subnanoclusters have become pivotal in nanocatalysis, yet their molecular adsorption mechanisms, particularly on supported versus unsupported systems, remain poorly understood. Our study employs detailed density functional theory (DFT) calculations with D3 corrections to investigate molecular adsorption on Pt subnanoclusters, focusing on CO, NO, N2, and O2 species. Gas-phase and graphene-supported scenarios are systematically characterized to elucidate adsorption mechanisms and catalytic potential. Gas-phase Pt n clusters are first analyzed to identify stable configurations and assess size-dependent reactivity. Transitioning to graphene-supported Pt n clusters, both periodic and nonperiodic models are employed to study interactions with graphene substrates. Strong adsorbate interactions predominantly occur at single top sites, revealing distinct adsorption geometries and stabilization effects for specific molecules on Pt6 clusters. Energy decomposition analysis highlights the paramount role of graphene substrates in enhancing stability and modulating cluster-adsorbate interactions. The interaction energy emerges as a critical criterion within the Sabatier principle, crucial for distinguishing between physisorption and chemisorption. Hybridization indices and charge density flow tendencies establish direct relationships with stabilization processes, underscoring graphene's influence in stabilizing highly reactive subnanoclusters. This comprehensive investigation provides critical insights into molecular adsorption mechanisms and the catalytic potential of graphene-supported Pt nanoclusters. Our findings contribute to a deeper understanding of nanocatalysis, emphasizing the essential role of substrates in optimizing catalytic performance for industrial applications.

Bowl-shaped PAHs as gas adsorbents: Hydrogen storage and binding of gaseous pollutants

Understanding the non-covalent interactions of various molecules with bowl-shaped carbon structures at a quantum-chemistry level is important for the design of new materials. In this work, adsorption of three important diatomic molecules (H2, CO, and HF) on a flat coronene molecule and bowl-shaped PAHs (corannulene, sumanene, and triazasumanene) was theoretically investigated. The considerable increase of the interaction energy (Eint) was found for all molecules inside the curved structures compared to coronene (the increase was up to 2 × ). It was shown that dispersion interactions play the main role in total attraction for H2 and CO molecules. For HF molecules, the importance of induction (Eind) and electrostatics (Eel) for adsorption was revealed. QTAIM and IGM analyses showed the existence of non-covalent interactions (H2, CO) and H-bonding (HF) between the adsorbate molecules and the adsorbents. The obtained results establish the potential use of the studied bowl-shaped carbon structures in gas adsorbent systems.

Fabrication of a novel sensor based on ionic porous polymer microspheres for humidity monitoring

A novel humidity sensor based on ionic porous polymer (IPP) microspheres was prepared in this work. The chemical structure and morphology of IPP microspheres were carefully characterized. The intrinsic hydrophilic ionic units of IPP, –N+R– and Br–, could enhance the adsorption of water molecules and ionic conductivity. The aromatic groups in IPP can adjust its hydrophobicity and ensure stability. Meanwhile, the structure of microspheres provides a favorable space of channels for water molecules transport, which improves the response speed of sensing film further. The impedance of the sensor based on IPP microspheres changed more than three orders of magnitude in the relative humidity (RH) range of 11–95 % RH with a good linearity (R2=0.996) and a fast response speed (6 s/ 27 s). Finally, the mechanism was systematically studied by complex impedance spectrum and theoretical calculation. This study shows a new type of sensor based on ionic porous polymer microspheres, which will pave the way for IPP applications in humidity sensing.

A study on the corrosion inhibition impact of newly synthesized quinazoline derivatives on mild steel in 1.0 M HCl: Experimental, surface morphological (SEM-EDS and FTIR) and computational analysis

Two new quinazoline derivatives were investigated in this research, namely 12-(4-methoxyphenyl) and 3,3-dimethyl-12-(4-nitrophenyl)-3,4,5,12-tetrahydrobenzo[4,5]imidazo[2, 1-b]quinazolin-1(2 H)-one (Q-NO2). In 1 M hydrochloric acid (HCl), −3,3-dimethyl-3,4,5,12-tetrahydrobenzo[4,5]imidazo[2,1-b]quinazolin-1(2 H)-one (Q-OMe) proved to be an extremely effective corrosion inhibitor for mild steel. The maximum inhibition efficiencies of 94.7 % for Q-NO2 and 96.7 % for Q-OMe were achieved when the performance of the inhibitors was evaluated using potentiodynamic polarization (PDP), electrochemical frequency modulation (EFM) and electrochemical impedance spectroscopy (EIS). According to these findings, the Q-NO2 and Q-OMe molecules have a remarkable ability to generate a dense, resistant protective film on the mild steel surface. This protective film acted as a barrier, effectively blocking the penetration of corrosive ions and their interaction with the mild steel substrate. The adsorption characteristics of these inhibitors on the mild steel surface conform to the Langmuir adsorption isotherm. PDP experiments show that Q-NO2 and Q-OMe act as mixed-type inhibitors for mild steel in 1.0 M HCl. Surface characterization by energy dispersive X-ray spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM) determined that a protective layer had formed on the steel surface, preventing corrosion. The experimental results were corroborated by theoretical insights from density functional theory (DFT), which further clarified the molecular adsorption processes. This work highlights the potential of Q-NO2 and Q-OMe as effective inhibitors to protect mild steel in acidic situation.

Investigations of Crucial Factors for the Non-Covalent Functionalization of Black Phosphorus (BP) using Perylene Diimide Derivatives for the Passivation of BP Nanosheets.

The non-covalent functionalization of black phosphorus (BP) was studied with a scope of ten tailor-made perylene diimides (PDIs). A combination of UV/Vis-, fluorescence-, as well as Raman spectroscopy and atomic force microscopy was used to investigate the structural factors, which contribute to a pronounced PDI-BP interaction and thus support the protection of BP nanosheets against oxidative degradation. We were able to show, that water-soluble, amphiphilic PDIs with highly charged head groups can be used for the non-covalent functionalization of BP in aqueous media. Here, based on the hydrophobic effect, an efficient adsorption of the respective PDI molecules takes place and leads to the formation of a passivating film, yielding a considerable stabilization of the BP flakes under ambient conditions exceeding 30 days.

Tweaking the structural, micro–structural, optical and dielectric properties of anatase titanium dioxide via doping of nitrogen ions

The pure nanostructured anatase titanium dioxide (TiO2) and subsequent nitrogen–doped derivatives (TiO2–xNx; where, x = 0.005, 0.01, 0.05) were synthesized by sol–gel auto–combustion technique. XRD analysis confirms the formation of pure anatase phase of TiO2 up to doping of 1 mol% (x = 0.01) of nitrogen having tetragonal structure with space group of I41/amd whereas an additional monoclinic phase of TiO2–B was observed at 5 mol% of nitrogen doping in TiO2. This sample has smallest crystallite size of ∼4.7 ± 0.2 nm corresponding to TiO2–B phase and ∼12.0 ± 0.1 nm corresponding to anatase phase. XRD also reveals that the crystallite size of all other samples having pure anatase phase ranges between ∼8.7 ± 0.1 nm & 13.9 ± 0.1 nm. The crystalline phase revealed from XRD of all samples was further supported by the Raman analysis. The direct optical band gap of pure TiO2 (∼3.4 eV) was reduced non–monotonically after nitrogen doping in the ranges from ∼2.8 eV (TiO1.95N0.05) to ∼2.0 eV (TiO1.99N0.01). FTIR spectra confirm the metal oxide bond formation, surface adsorption of water molecules and presence of residual hydroxyl group in all crystalline samples. HRTEM analysis validates the coexistence of secondary phase of TiO2–B along with anatase phase of TiO2 in studied highest doped sample (TiO1.95N0.05) including its broader particle size distribution as compared to pure TiO2. The electrical studies reveal that the highest values of dielectric constant and ac conductivity can be realized for pure TiO2 and at 1 mol% (x = 0.01) of nitrogen doping, among all the studied nitrogen doped samples.

Unveiling the Role of Boron on Nickel‐Based Catalyst for Efficient Urea Oxidation Assisted Hydrogen Production

AbstractUrea oxidation reaction (UOR) is an ideal alternative to oxygen evolution reaction (OER) for efficient hydrogen production but is immensely plagued by slow kinetics. Herein, a multilayer hole amorphous boron‐nickel catalyst (a‐NiBx) is fabricated through a simple chemical plating method, which displays intriguing catalytic activity toward UOR, demanding a low working potential of 1.4 V to reach 100 mA cm−2. The high performance is credited to the formation of metaborate (BO2−), which can promote the formation of high‐oxidation‐state NiOOH active phase and optimize the adsorption of urea molecules. This can be confirmed by the operando spectroscopy characteristics and density functional theory calculations. Consequently, the assembled electrolyzer utilizing NiBx as bifunctional catalysts exhibited splendid catalytic activity, requiring an evidently lower voltage of 1.66 V to reach a current density of 100 mA cm−2 and 1.57 V when using Pt/C as a cathode catalyst. Moreover, the assembled electrolyzer secured a robust stability of over 200 h, as well as a four times higher hydrogen production rate than traditional water electrolysis.

Phosphorus heteroatom doped BiOCl as efficient catalyst for photo-piezocatalytic degradation of organic pollutant and unveiling the mechanism: Experiment and DFT calculation

A novel phosphorus heteroatom doped bismuth oxychloride (P-BiOCl) catalyst was synthesized and the photo-piezocatalytic degradation of rhodamine B dye performances were explored under the ultrasound vibration and light illumination. The P-BiOCl exhibited excellent photo-piezocatalytic degradation activity, such as an ultra-high reaction kinetic rate constant of 0.3961 min−1, efficient degradation efficiency (94.7 % within 8 min) and excellent stability compared to solely piezocatalysis and photocatalysis. More impressively, these outstanding performances of P-BiOCl exceeded pure BiOCl and most other catalytic materials systems. The relevant experimental and density functional theory (DFT) calculation results were exhibited to clarify enhanced photo-piezocatalytic mechanism. The introduction of P heteroatom could reduce the bandgap of BiOCl, modulate electronic structure and charge redistribution, provide novel electron channel to promote electron transfer and restrain charge carriers recombination. Additionally, P-doped could also enhance the adsorption of oxygen and water molecules, promote intrinsic catalytic activity, leading to the increased production of active free radicals ·O2– and ·OH, thus significantly boosting the efficiency of organic pollutant degradation. This work provides a comprehensive understanding of heteroatom doping enhancing photo-piezocatalytic activity and presents a potential new strategy for designing highly efficient catalysts for wastewater treatment.

Oxygen vacancy-enriched WO3 hierarchical tubes inherited from pine needle for the enhanced detection to ppb-level hydrazine at near room temperature

It is of great importance to develop low-temperature gas sensors for monitoring hydrazine (N2H4) with high toxicity and easy explosion. However, how to highly sense its ppb-level concentration remains challenging. For this purpose, biomorphic WO3 structure replicated by small-size nanoparticles was simply prepared though air calcinations of tungsten salt-immersed pine needle (PN) template. The mesoporous WO3-PN tubes with pore volume of 0.096 cc·g−1 had relatively large specific surface area (38 m2·g−1) for exposing more active sites, as well as rich oxygen vacancies (g = 2.005) and small band gap for promoting electron migration. With the assistance of W6+ Lewis acid catalytic sites, such unique multilevel structure facilitated the rapid transport and adsorption of basic N2H4 molecules, as well as their chemical reactions with high content of oxygen species (37.4 %) in sensing layer, thus first achieving the highly sensitive detection of ppb-level N2H4 gas at near room temperature. At 50 °C, WO3-PN sensor exhibited ultra-high response (S = 307), fast response time (Tres = 16 s) for 1 ppm N2H4, and low actual detection concentration (5 ppb). These key indicators were remarkably superior to reported semiconductor gas sensors. In addition, the enhanced low-temperature sensing mechanism of WO3-PN sensor was explored by means of analytical tests and DFT calculations.

Nitrogen-rich sulfur-containing heterocyclic adsorbents for effective selective adsorption of Au(III)/Pd(II)/Pt(IV)

Recovering precious metals from secondary resources has elicited considerable attention, and exploring an efficient adsorbent is a challenge. In this work, we have specifically tailored three highly effective adsorbents (THDA@PEI, DCTA@PEI and DCTD@PEI) by crosslinking PEI with sulfur-containing heterocyclic cross-linking agents (2,5-thiophenedicarboxaldehyde, 2,4-dichlorothiazole and 3,4-dichloro-1,2,5-thiadiazole) for recovery of Au(III), Pd(II), and Pt(IV). These agents are distinguished by a range of nitrogen atom counts that extend from zero to two, offering a foundation for exploring the correlation between their molecular structure and adsorption performance. THDA@PEI, DCTA@PEI, and DCTD@PEI exhibit remarkable adsorption capacities for Au(III), Pd(II), and Pt(IV), with values reaching up to 2169, 2240, and 2536 mg/g for Au(III), 771, 886, and 846 mg/g for Pd(II), and 832, 1021, and 887 mg/g for Pt(IV), respectively. Among the three materials, DCTD@PEI stands out with a broader pH applicability range for both gold (pH 2 to 9) and platinum (pH 1 to 11) adsorption and exhibits a more rapid adsorption rate for Au and Pd. The adsorption processes of the three adsorbents on precious metals are spontaneous and entropy-increasing processes. Increasing the adsorption temperature could improve the adsorption performance of the three adsorbents, except for Pd adsorption by DCTD@PEI. All of the three adsorbents exhibit good selectivity and reusability for Au, Pd, and Pt, with DCTA@PEI being the most outstanding. It is observed that an increase in nitrogen content in the adsorbents correlates positively with the improvement of key performance indicators, including a wider pH range, higher adsorption capacity, faster kinetics, better selectivity, and enhanced reusability, while the substituent positions of crosslinking agents also have a strong impact on the adsorption performance, especially for Pd and Pt.

Impact of Ag2O on the gas sensing properties of the star-shaped BaTiO3/ZnO heterostructures

In this work, star-shaped heterostructures of Ag2O/BaTiO3/ZnO were proposed as resistive-type gas sensors. Through combined analyzes of XRD, SEM, and EDS, the structure, surface morphology, and the elemental composition of the synthesized materials were confirmed. The star-shaped morphology of BaTiO3/ZnO was found to be intact even after loading with different quantities of Ag2O, as revealed by the SEM analysis. The impact of loading different amounts of Ag2O (ranging from 1 % to 3 %) on the sensors' ability to detect volatile organic compounds (VOCs) and carbon dioxide (CO2) was concretely gauged by their response, response/recovery times, selectivity, and long-term stability. For the detection of ethanol/acetone, CO2, and methanol, a 1:2 M ratio of BaTiO3/ZnO with 1 % and 2 % Ag2O, and a 1:3 M ratio of BaTiO3/ZnO with 1 % Ag2O were determined as the optimum content, respectively. From the gas sensing analysis, Ag2O/BaTiO3/ZnO sensors with different amounts of Ag2O additive gave different optimal temperatures for different target gases. Lower operating temperatures, i.e. 180 °C, and 260 °C for CO2 and VOCs, respectively, rapid responsivity with a response time of <1 s for VOCs, and fast recovery times (as low as 10, 13, and 6 s for ethanol, acetone, and methanol vapors, respectively) were observed. More importantly, the sensor exhibited good selectivity for several possible interferences. The underlying reasons for the acceleration of the gas molecules adsorption, hence the fast sensor response, are the high specific surface area established by the star-shaped morphology, and compatible energy band alignment at the p/n interface coupled with the catalytic effect induced by Ag2O.

Conjugated acid-base pairs in Keggin-type polyoxometalate-based metal-organic frameworks enhance proton conduction

To achieve high proton conductivities, it is pivotal to design and select appropriate functional organic ligands for constructing polyoxometalate-based metal–organic frameworks (POMOFs). In this work, the effects of functional groups upon the molecular electrostatic potentials and pKa of two organic ligands (4-abpt, theoretical pKa value of 25.13; Hdpt, theoretical pKa value of 9.24) are first investigated by theoretical calculations. And then, two new proton-conductive decorated POMOFs, {[Cu(4-abpt)2(H2O)][Cu(4-abpt)(H2O)][SiW12O40]}·6H2O (CUST-875) and {[Cu(Hdpt)(H2O)2] [Cu(Hdpt)][SiW12O40]}·2H2O (CUST-876), have been designed and obtained via hydrothermal method. Besides, their proton conduction performances and influencing factors also have been investigated in more details. It is found that more water molecules adsorption and the conjugated acid-base pairs played substantial roles in proton conduction. As a consequence, the three-dimensional framework CUST-875, composed of the higher theoretical pKa value organic ligand 4-abpt, exhibited a higher proton conductivity of 1.07 × 10−4 S cm−1 at 95 °C and 98 % relative humidity (RH), surpassing that of CUST-876 by three orders of magnitude. Additionally, CUST-875 possesses the ability to degrade H2O2, which readily generates during charging and discharging of battery and has adverse effects on the battery life. This work contributes new insights into the high efficiency preparation and structure–property relationships of new polyoxometalate (POM)-based crystalline proton conducting materials with relatively high intrinsic proton conductivities.

Incorporation of hydroxyl groups and π-rich electron domains into g-C3N4 framework for boosted sacrificial agent-free photocatalytic H2O2 production

Photocatalytic synthesis of hydrogen peroxide (H2O2) based graphitic carbon nitride (g-C3N4) materials has garnered significant attention due to its green and sustainable attributes. In this study, g-C3N4 nanosheets enriched with π‑rich electron domains and hydroxyl groups were synthesized through the pyrolysis of urea-tartaric acid mixed solution, and subsequently utilized for efficient photocatalytic production of H2O2. The incorporation of π-rich electron domains induced a downward shift in the conduction band edge, which can significantly diminish the Coulombic interactions of singlet Frenkel excitons, thereby facilitating efficient photo-generated charge separation and accelerated charge migration. Simultaneously, the modification with hydroxyl groups in g-C3N4 network enhances water molecule adsorption, reducing side reactions and thereby increasing the efficiency of selective H2O2 generation. The integration of π-rich electron domains with hydroxyl groups in g-C3N4, along with a comprehensive understanding of their underlying mechanisms, provides valuable insights for the rational design and synthesis of highly active energy conversion catalytic materials.

Design and regulation of defective electrocatalysts.

Electrocatalysts are the key components of electrochemical energy storage and conversion devices. High performance electrocatalysts can effectively reduce the energy barrier of the chemical reactions, thereby improving the conversion efficiency of energy devices. The electrocatalytic reaction mainly experiences adsorption and desorption of molecules (reactants, intermediates and products) on a catalyst surface, accompanied by charge transfer processes. Therefore, surface control of electrocatalysts plays a pivotal role in catalyst design and optimization. In recent years, many studies have revealed that the rational design and regulation of a defect structure can result in rearrangement of the atomic structure on the catalyst surface, thereby efficaciously promoting the electrocatalytic performance. However, the relationship between defects and catalytic properties still remains to be understood. In this review, the types of defects, synthesis methods and characterization techniques are comprehensively summarized, and then the intrinsic relationship between defects and electrocatalytic performance is discussed. Moreover, the application and development of defects are reviewed in detail. Finally, the challenges existing in defective electrocatalysts are summarized and prospected, and the future research direction is also suggested. We hope that this review will provide some principal guidance and reference for researchers engaged in defect and catalysis research, better help researchers understand the research status and development trends in the field of defects and catalysis, and expand the application of high-performance defective electrocatalysts to the field of electrocatalytic engineering.

Tunable Ferroionic Properties in CeO2/BaTiO3 Heterostructures.

Ferroionic materials combine ferroelectric properties and spontaneous polarization with ionic phenomena of fast charge recombination and electrodic functionalities. In this paper, we propose the concept of tunable polarization in CeO2-δ (ceria) thin (5 nm) films induced by built-in remnant polarization of a BaTiO3 (BTO) ferroelectric thin film interface, which is buried under the ceria layer. Upward and downward fixed polarizations at the BTO thin film (10 nm) are achieved by the lattice termination engineering of the SrO or TiO2 terminated Nb:SrTiO3 (NSTO or STN) substrate. We find that the ceria layer punctually replicates the polarization of the BTO interface via a dynamic reconfiguration of its intrinsic defects, i.e., oxygen vacancies and small polarons. Tunable oxidative or reducing properties (redox) also arise at the surface from the built-in polarization. Opposite polarities at the ceria termination tune the chemo-physical dynamics toward water molecule adsorbates. The inversion of the surface potential leads to a modulation of the water adsorption-desorption equilibrium and water ionization (splitting) redox overpotentials within ±400 mV at room temperature, depending on the ceria termination's charges. Such tunability opens up the perspectives of using ferroionics for wireless electrochemically enhanced catalysis.

Synthesis and enhanced H2S gas sensing performances of Co-doped NiO@g-C3N4 heterocomposites

Metal doping is an efficient approach to improve H2S gas sensing performances, but the metal-doped NiO is still faced poor recovery capability at low working temperature. Herein, Co-doped NiO@g-C3N4 heterocomposites were constructed firstly via a simple solid phase reaction. Texture characterizations indicate that Co-doped NiO@g-C3N4 heterocomposites with the architecture of hierarchical microspheres show high specific surface areas and rich surface oxygen vacancies. The gas-sensitive measurements exhibit that the response value of the heterocomposites with g-C3N4 content of 30 wt% (Co-NiO@g-C3N4-3) increases to 45 toward 20 ppm H2S gas at 172 °C, which is about 1.8 times of Co-NiO (23), as well as response/recovery times decreased to ca. 100/130 s. Besides, excellent repeatability, stability and selectivity of Co-NiO@g-C3N4-3 sensors are obtained. The improved H2S gas sensing performances of Co-NiO@g-C3N4 heterocomposites is mainly contributed to the formation of nano-heterojunctions, which promotes electron accumulation at nano-heterojunctions near Co-NiO, facilitates O2 molecules adsorption on the material surface and accelerates the resistance change of the sensors, resulting the enhanced gas sensing performances.