Adsorption Of Molecules Research Articles

Theoretically design of 2D penta-BN2/penta-Graphene wdW heterostructure for NO gas sensing implications: a first-principles study

As air pollution becomes more and more serious, the detection of harmful gas of NO has become an urgent need in daily life. In this paper, the electronic and gas-sensing properties of penta-BN2/penta-Graphene heterojunction (P-BN2/P-G) are studied by density functional theory and non-equilibrium Green's function method. The analysis results indicate that the P-BN2/P-G heterojunction has metallic properties. The electronic structures in combination with the adsorption behavior shows that the P-BN2/P-G heterojunction can chemically adsorb NO gas molecules, and there is obvious charge transfer, indicating that it has high gas sensitivity to NO gas. In addition, the sensing performance of the gas sensor constructed by NO adsorption on upper, middle and lower layers of the P-BN2/P-G heterojunction is deeply studied. Transport calculations show that when NO is adsorbed on the upper and middle layers of the P-BN2/P-G heterojunction-based gas sensor, the current of the device decreases significantly. When adsorbed on the lower layer, the current shows a trend of first decreasing and then increasing. Under a bias of 0.1 V, the gas sensitivity can reach up to 49% when NO is adsorbed in the middle layer, which is substantially higher than that of the P-BN2 monolayer device. It can be seen that the gas sensitivity is significantly improved after forming the heterojunction. In addition, the bias transport spectrum and scattering state can reveal the change in device current caused by the adsorption of NO gas molecules, thereby clarifying its microscopic mechanism. Finally, all the findings indicate that penta-based materials can be used as a very promising gas-sensitive material for detecting NO.

Mechanistic effects of graphitization and oxygen functional groups on benzene competitive adsorption of porous carbon under high humidity conditions

Porous carbon is an ideal adsorbent for the elimination of volatile organic compounds (VOCs) attributed to their price, availability and excellent adsorption capacity. However, there are significant variation in the adsorption capacity and adsorption selectivity of different precursors for VOCs under humid conditions after modification because of the differences in their own structural properties. In this study, graphitized hydrophobic porous carbon with excellent specific surface area was successfully synthesized by selecting bamboo fiber, maize, coconut husk and coal as precursors and potassium hydroxide as an activator. Among them, the dynamic adsorption capacity of benzene in the sample with bamboo fiber as precursor was maintained at 74.7% under the high humidity condition (RH90%) compared with the dry state (RH0%). Grand Canonical Monte Carlo (GCMC) simulations and weak interaction force analyses showed that enhanced dispersion attraction between graphitized carbon surfaces and benzene molecules in comparison to disordered carbon surfaces. The existence of oxygen functional groups enhanced the interaction between porous carbon and water through hydrogen bonding leading to preferential adsorption of water molecules, which resulting in the decrease of their adsorption performance in wet condition. This research provided theoretical and experimental views of the effects of graphitization and oxygen functional groups on the competitive adsorption capture of benzene and water by porous carbon, which further provided a reliable approach to synthesizing porous carbon with high adsorption capture for benzene removal in high humidity environments.

Electrochemical Oxidation of Glyphosate Using Graphite Rod Electrodes: Impact of Acetic Acid Pretreatment on Degradation Efficiency

The uncontrolled use of herbicides such as glyphosate (GLY) (N-phosphonomethylglycine) in agricultural production has resulted in its presence in water bodies and in negative impacts on the environment and public health. On the frame of understanding the interaction between GLY and graphite rod surfaces, this contribution relies on the study of electrochemical responses of different GLY concentrations by cyclic voltammetry under both open and closed-circuit conditions. Furthermore, the effect of the electrodes’ electrochemical pretreatment with acetic acid on the double-layer capacitance and the subsequent surface functionalization of the graphite rod materials were evaluated. The increment in GLY concentration showed a decrease in the electrochemical oxidation response associated with the adsorption of the contaminant on the surface of the graphite rod electrode and the concomitant blockage of the active sites. Electrochemical pretreatment of the electrodes with acetic acid and GLY concentration play crucial roles in electric double-layer formation due to their ability to interact with both positive and negative electrical charges. By means of optical microscope observations and Fourier Transform Infrared Spectroscopy analysis, it was possible to detect the formation of oxygenated functional groups on the electrode surfaces after the electrochemical pretreatment. Through a 23 factorial design analysis in repetition, the factors significant in the degradation of GLY were identified. The high degradation of GLY with the pretreated electrodes can be attributed to the preferential adsorption of the zwitterionic molecule at the interface, which allowed great direct oxidation of the contaminant on the anode’s surface.

Efficient Removal of Brilliant Cresyl Blue from Solution Using Inula Racemosa: Experimental Insights, DFT Modeling, and Docking Simulation

AbstractThis study examined the efficacy of Inula Racemosa leaves in the adsorption of Brilliant Cresyl Blue (BCB) from aqueous solutions. The study uses both experimental and theoretical research, including Density Functional Theory (DFT), to gain a better understanding of how the adsorbent and Brilliant Cresyl Blue molecules interact with each other. We determined the point zero value of the charged powder of Inula Racemosa and characterized the functional groups using FTIR spectroscopy. The experimental results indicate a significant ability of our adsorbent to adsorb the cationic dye Brilliant Cresyl Blue, and we have identified optimal conditions for its effective removal. The results suggest that the most effective amount of our biosorbent was 0.1 g. The equilibrium period for biosorption was 10 min, and the biosorbent capacity for biosorption improved with increasing pH. The Pseudo‐second‐order model accurately predicts the retention of Brilliant Cresyl Blue using Inula Racemosa. The Freundlich model was found to be better suitable for analyzing the isotherm data, revealing a maximum adsorption capacity of 3.49 mg g−1, achieving an efficiency removal of 89.95 %. We compared Density Functional Theory (DFT) calculations with experimental observations to validate the theoretical predictions and improve our understanding of the adsorption mechanism. Docking simulations show how the molecules of Inula Racemosa and Brilliant Cresyl Blue interact with each other, including the interactions of hydrogen bonds and electrostatic forces.

Adsorption and evolution of N2 molecules over ZnO monolayer: a combined DFT and kinetic Monte-Carlo insight

AbstractA large surface area, wide band gap, and unique bonding property between Zn and O atoms make the hexagonal ZnO monolayer attractive as a gas sensor. In the present work, the adsorption and evolution of nitrogen (N2) molecules over a ZnO monolayer have been studied using two different theoretical methods: van der Waals density functional theory (vdW-DFT) and kinetic Monte-Carlo (kMC) simulation. The adsorption and diffusion (hopping over the surface) energy of a N2 gas molecule has been calculated considering the different sites over the ZnO substrate using the revPBE-vdW functional. Bader charge, electron localization function analysis, density of states and band structure plotting have been used to understand the adsorption mechanism. Lateral repulsive interaction between two N2 molecules limits the maximum packing number of gas molecules within one hexagonal ring. The output of the vdW-DFT calculation has been fed to the kMC code to predict the rate of adsorption, desorption, and diffusion, along with the overall surface coverage at different temperatures and pressures. Finally, the change in the N2 adsorption energy has been predicted with the increase of the ZnO layer number.

Structural Design of Hybrid Manganese(II) Halides for High Quantum Efficiency and Specific Response to Methanol.

Manganese(II) halides have been a new generation of optoelectronic materials due to their fascinating luminescent properties, however, lacking specific solvent-responsive analogues with high quantum efficiency. Herein, we prepared three single crystals, [Pr(MIm)2][MnBr4] ([Pr(MIm)2]2+ = 1,3-di(methylimidazolium)-propane, Compound 1), [Pr(EIm)2][MnBr4] ([Pr(EIm)2]2+ = 1,3-di(ethylimidazolium)-propane, Compound 2), and [Bu(MIm)2][MnBr4] ([Bu(MIm)2]2+ = 1,4-di(methylimidazolium)-butane, Compound 3), where different Bola-type cations were chosen as organic components to separate [MnBr4]2- tetrahedrons. All three compounds emitted bright green light with excellent quantum yields of 95.3, 80.0, and 96.2%, benefiting from the large Mn···Mn distance. More interestingly, Compound 3 showed a highly selective response to methanol in a series of tested organic solvents, with a rapid and reversible change in emission color from green to red. The single crystal of [Bu(MIm)2][MnBr4]·CH3OH with red emission proved that the luminescence switching was attributed to the adsorption of CH3OH molecules into the lattice space in the form of the O-H···Br hydrogen bonds. To our knowledge, for tetrahedrally coordinated Mn(II) species, the reversible emission color switching between green and red triggered by a solvent without the change of coordination number is achieved for the first time, providing promising applications for the specific detection of methanol.

Solvent‐Engineering‐Assisted Ligand Exchange Strategy for High‐Efficiency AgBiS2 Quantum Dot Solar Cells

AbstractAs the initial synthesized colloidal quantum dots (CQDs) are generally capped with insulating ligands, ligand exchange strategies are essential in the fabrication of CQD films for solar cells, which can regulate the surface chemical states of CQDs to make them more suitable for thin‐film optoelectronic devices. However, uncontrollable surface adsorption of water molecules during the ligand exchange process introduces new defect sites, thereby impairing the resultant device performance, which attracts more efforts devoted to it but remains a puzzle. Here, we develop a solvent‐engineering‐assisted ligand exchange strategy to revamp the surface adsorption, improve the exchange efficiency, and modulate the surface chemistry for the environmentally friendly lead‐free silver bismuth disulfide (AgBiS2) CQDs. The optimized AgBiS2 CQD solar cells deliver an outstanding champion power conversion efficiency (PCE) of up to 8.95 % and improved long‐term stability. Our strategy is less environment‐dependent and can produce solar cells with negligible performance variance for several batches across several months. Our work demonstrates the critical role of solvents for ligand exchange in the surface chemistry of CQDs and the realization of high‐performance photovoltaic devices in a highly reproducible manner.

In situ regulating the interfacial work function of Ag doped Ni(OH)2 via trace of Fe2+ for efficient water splitting

Traditional approaches for tuning the water electrolysis performance of catalysts through manipulating their work function (WF) have primarily focused on the design of pre-catalysts prior to electrochemical test. Herein, an in situ interfacial WF modulation concept has been developed to synthesize the Fe modified nickel-based hydroxide electrocatalyst with enhanced OER (named as 0.168-FeO-Ag-Ni(OH)2/NF) and HER (0.168-FeH-Ag-Ni(OH)2/NF) activity. The modulator is trace amounts of Fe2+ in 1 M KOH, while the support comprises silver-modified nickel hydroxide, in which the Ag possesses a valence catalysis effect on Ni or Fe sites. Under optimized Fe2+ content, the deposition of Fe facilitates the release of the WF of Ag-Ni(OH)2/NF and accelerates the electron transfer between the catalyst and reaction intermediates. Meanwhile, the charge transfer from Fe to Ni sites coupled with the blue shift of d-band promote the adsorption of water molecules and the desorption of hydrogen protons, thereby accelerating the hydrogen evolution reaction kinetics. Consequently, the OER and HER activity of 0.168-FeO-Ag-Ni(OH)2/NF and 0.168-FeH-Ag-Ni(OH)2/NF enhanced 4.31 and 2.48 times, respectively. Notably, compared with Ag-Ni(OH)2/NF(+)//Ag-Ni(OH)2/NF(−), at a high current density of 1000 mA cm−2, the potential for energy consumption reduction of 0.168-FeO-Ag-Ni(OH)2/NF(+)//0.168-FeH-Ag-Ni(OH)2/NF(−) couple is at least 6 %, which endows it a promising application prospect in the actual electrolytic water system in the future.

Abundant interfacial and intrinsic oxygen vacancies enabling small nickel/ceria nanocrystal efficient CO2 methanation

Smaller nano-sizes typically result in supported catalysts with abundant interfacial and intrinsic oxygen vacancies for better adsorption and activation of small molecules, including CO2, leading to improved efficiency of CO2 methanation. Here, Ni/CeO2-S with the smaller nano-size of around 4.2 nm is used to catalyze CO2 methanation, which exhibits significantly enhanced activity compared to larger nano-sized Ni/CeO2-L catalyst, even surpassing the most majority of previously reported catalysts using CeO2 as the support or Ni as the active metal. The coexistence of interfacial defects and intrinsic oxygen vacancies allows for enhanced adsorption and activation of CO2 molecules as well as H spillover, resulting in such improved CO2 methanation. In-situ DRIFTS demonstrate a nearly sole Formate pathway on Ni/CeO2-S for efficient CO2 hydrogenation. This research provides valuable insights into the reaction mechanism over a small nanosize supported catalyst.

Single walled carbon nanotubes/ZnO nanowires heterostructure array for NO2 gas sensing at low ppm levels

A layer-by-layer ZnO nanowire (NW)-Single Walled Carbon Nanotube (CNT) hybrid gas sensor has been proposed for effective detection of NO2 gas under a low exposure limit of 5 ppm. The fabricated hybrid sensor displayed good sensor response (S %), good selectivity and fast response time towards the target gas. S % value of 36.4 % under 5 ppm NO2 level at 250 °C and good selectivity response towards different interfering gases like SO2, CO and H2 have been observed. Meanwhile, fast response time values of 44.08 s (response) and 62.11 s (recovery) were observed at 300 °C under 5 ppm NO2 level. The sensor baseline resistance of the hybrid heterostructure (HS) was also found to be lower when compared to that of a bare ZnO NW sensor. In addition, the presence of Single Walled CNT in the HS was also shown to reduce the operational temperature of the sensor. Temperature played a significant role by controlling the adsorption and desorption kinetics of gas molecules on the surface. Moreover, the formation of p-n interface between Single Walled CNT (p-type) and ZnO NW (n-type) might have modulated the potential charge barrier on interacting with the adsorbed gases which inturn might have impacted the response of the hybrid sensor. In addition, the large surface areas offered by both NWs and nanotubes might have improved the gas adsorption capability thereby enhancing the overall hybrid sensor’s response.

A Bacterial Capturing, Neural Network-Like Carbon Nanotubes/Prussian Blue/Puerarin Nanocomposite for Microwave Treatment of Staphylococcus Aureus-Infected Osteomyelitis.

Staphylococcus aureus (S. aureus)-infected osteomyelitis is a deep tissue infection that cannot be effectively treated with antibiotics. Microwave (MW) thermal therapy (MTT) and MW dynamic therapy (MDT) based on MW-responsive materials are promising for the therapy of bacteria-infected osteomyelitis occurring in deep tissues that cannot be effectively treated with antibiotics. In this work, the MW-responsive system of carbon nanotubes (CNTs)/Prussian blue (PB)/puerarin (Pue) with stable network-like structures is constructed. The PB is grown in situ on the CNTs, and its introduction not only reduces the aggregation of the network-like structures of the CNTs, but the large specific surface area and mesoporous structure can also provide many active sites for the adsorption of oxygen and polar molecules. Pue is a natural anti-inflammatory material that reduces inflammation at the infection site. The composite of the CNTs and PB avoids the skin effect and thus can improve dielectric and reflection losses. The MW thermal response of CNTs/PB/Pue is mainly due to the occurrence of reflection loss, dielectric loss, multiple reflections and scattering, interface polarization, and dipole polarization. In addition, under MW irradiation, the CNTs/PB/Pue can produce reactive oxygen species (ROS), such as singlet oxygen (1O2), hydroxyl radical (·OH).

Molecular Reconfiguration of Disordered Tellurium Oxide Transistors with Biomimetic Spectral Selectivity.

Reconfigurable devices with field-effect transistor features and neuromorphic behaviors are promising for enhancing data processing capability and reducing power consumption in next-generation semiconductor platforms. However, commonly used 2D materials for reconfigurable devices require additional modulation terminals and suffer from complex and stringent operating rules to obtain specific functionalities. Here, a p-type disordered tellurium oxide is introduced that realizes dual-mode reconfigurability as a logic transistor and a neuromorphic device. Due to the disordered film surface, the enhanced adsorption of oxygen molecules and laser-induced desorption concurrently regulate the carrier concentration in the channel. The device exhibits high-performance p-type characteristics with a field-effect hole mobility of 10.02 cm2 V-1 s-1 and an Ion/Ioff ratio exceeding 106 in the transistor mode. As a neuromorphic device, the vision system exhibits biomimetic bee vision, explicitly responding to the blue-to-ultraviolet light. Finally, in-sensor denoising and invisible image recognition in static and dynamic scenarios are achieved.

Surface acoustic wave platform integrated with ultraviolet activated rGO-SnS2 nanocomposites to achieve ppb-level dimethyl methylphosphonate detection at room-temperature

Dimethyl methylphosphonate (DMMP) is commonly used as an alternative for demonstrating to detect sarin, which is one of the most toxic but odorless chemical nerve agents. Among various types of DMMP sensors, those utilizing surface acoustic wave (SAW) technology provide notable advantages such as wireless/passive monitoring, digital output, and a compact, portable design. However, key challenges for SAW-based DMMP sensors operated at room temperature lies in simultaneous enhancement of sensitivities and reduction of detection limits. In this study, we developed a binary material strategy by combining reduced graphene oxide (rGO) and tin disulfide (SnS2) with (100)-facets orientation as sensing layers of SAW device for DMMP detection utilized at room temperature. Ultraviolet (UV) light was applied to activate the sensitive film and reduce the sensor's response time. The developed SAW DMMP sensor demonstrated a superior sensitivity (−1298.82 Hz/ppm), a low detection limit of 50 ppb, and a hysteresis below 1.5%, along with fast response/recovery time (39.2 s/28.4 s), excellent selectivity, long-term stability and repeatability. The formation of shrub-like rGO-SnS2 heterojunctions with abundant surface defects and large specific surface areas, high-energy (100) crystalline surfaces of SnS2, and photogenerated carriers generated by UV irradiation were pinpointed as the crucial sensing mechanisms. These factors collectively enhanced adsorption and reaction dynamics of DMMP molecules.

Adsorption grand potential of OH on metal oxide surfaces.

Describing chemical processes at solid-liquid interfaces as a function of a fixed electron chemical potential presents a challenge for electronic structure calculations and is essential for understanding electrochemical phenomena. Grand Canonical Density Functional Theory (GCDFT) allows treating solid-liquid interfaces in such a way that studying the influence of a fixed electron potential arises naturally. In this work, GCDFT is used to compute the adsorption grand potential (AGP), a key parameter for understanding and predicting the behavior of adsorbates on surfaces. We focused on the adsorption of an OH molecule on three metallic surfaces commonly used in electrochemical processes, such as the oxygen evolution reaction (OER). Our study aims to offer insights into how AGP can be used to compare adsorption strengths under different fixed electron chemical potentials, which is crucial for designing efficient electrode materials. By determining the average number of electrons self-consistently under varying chemical potentials, we showed how one can distinguish between electron acquisition and depletion during the adsorption process, offering a deeper understanding of the adsorbate-surface interactions. The approach used in this work employs the Kohn-Sham-Mermin formulation of the Grand Canonical Density Functional Theory. The computations were performed using the periodic open-source density functional theory software, JDFTx, with the Garrity-Bennett-Rabe-Vanderbilt library of ultrasoft pseudopotentials. Calculations were made using truncated Coulomb potentials and the auxiliary Hamiltonian method with the PBE exchange-correlation functional, along with DFT-D2 long-range dispersion corrections. The implicit solvation model CANDLE was used to describe the electrolyte with a 1M concentration.

Assay for Characterizing Adsorption-Properties of Surfaces (APS).

Analytes, from sample preparation, until entering an analytical instrument, are prone to adsorb to surfaces, driven by the chemical properties of the surface and the liquids they are dissolved in. This problem can be addressed with internal standards when a single or few known analytes are quantified that are usually not available in omics. However, minimal to no loss of analytes is the aim. Here, we present a novel assay for qualifying and quantifying interactions responsible for adsorption of molecules to surfaces (APS) by using LC-MS/MS-based differential quantitative analysis. To reflect a broad range of chemical interactions with surfaces, a reference mixture of thousands of tryptic peptides, with known compositions was selected, representing a variety of different chemical characteristics. The assay was tested by investigating the adsorption properties of several different vials with different surface chemistries. A significant number of hydrophobic peptides adsorbed to conventional polypropylene vials. In contrast, only few peptides adsorbed to polypropylene vials, assigned as low-protein-binding. The highest number of peptides adsorbed to glass vials driven by electrostatic interactions. In summary, the new assay is suitable to characterize adsorption properties of different surfaces and to approximate the loss of analytes during sample preparation.

Label-Free Single-Molecule Electrical Sensor for Ultrasensitive and Selective Detection of Iodide Ions in Human Urine.

Herein, a label-free single-molecule electrical sensor was first proposed for the ultrasensitive and selective detection of iodide ions in human urine. Single-molecule conductance measurements in different halogen ion solutions via scanning tunneling microscopy break junction (STM-BJ) clearly revealed that I- ions strongly affect the stability and displacement distance (Δz) distribution of molecular junctions. Theoretical calculations prove that the specific adsorption of I- ions modifies the surface properties and weakens the molecular adsorption. Furthermore, the average conductance peak area versus the logarithm of the I- ion concentration has a very good linear relationship in the range of 5 × 10-6 to 5 × 10-10 M, with a correlation coefficient of 0.99. This quantitative analysis remains valid in the presence of interfering ions of SO42-, ClO4-, Br-, and Cl- as well as interfering molecules of ascorbic acid, uric acid, dopamine, and cysteine. A cross-comparison of the human urine detection results of this single-molecule electrical sensor with those of the clinical method of As3+-Ce4+ catalytic spectrophotometry revealed an average difference of 0.9%, which decreased the detection time of 2 h with the traditional method to approximately 15 min. This work proves the promising practical potential of the single-molecule electrical technique for relevant clinical analysis.

Chemoinformatics for corrosion science: Data-driven modeling of corrosion inhibition by organic molecules.

This paper reviews the application of machine learning to the inhibition of corrosion by organic molecules. The methodologies considered include quantitative structure-property relationships (QSPR) and related data-driven approaches. The characteristic features of their key components are considered as applied to corrosion inhibition, including datasets, response properties, molecular descriptors, machine learning methods, and structure-property models. It is shown that the most important factors determining their choice and application features are: (1) the small or very small size of datasets, (2) the mechanism of corrosion inhibition associated with the adsorption of inhibitor molecules on the metal surface, and (3) multifactorial conditioning and noisiness of response property. On this basis, the application of machine learning to the inhibition of corrosion of materials based on iron, aluminum, and magnesium is considered. The main trends in the development of QSPR and related data-driven modeling of corrosion inhibition are discussed, the shortcomings and common errors are considered, and the prospects for their further development are outlined.

Mitigation effect of a biodegradable surfactant N,N,N-trimethyl-2-(((hexadecyloxy)carbonyl)oxy)ethan-1-aminiumiodide for mild steel corrosion in 5% HCl: Experimental and theoretical insights

A cleavable cationic surfactant having carbonate linkage, N,N,N-trimethyl-2-(((hexadecyloxy)carbonyl)oxy)ethan-1-aminiumiodide referred to as THC was synthesised and characterized employing elemental analysis, FT-IR (Fourier Transform Infrared Spectroscopy), 1H NMR (Nuclear Magnetic Resonance) and 13C NMR. The extent of corrosion inhibition of THC was for the first time studied experimentally and theoretically on mild steel (MS) substrate in 5 % HCl solution at temperatures 303, 313, 323, 333, 343, 353 K. Experimental investigations include gravimetric analysis, potentiodynamic polarization (PDP) and electrochemical impedance analysis (EIS). THC provided maximum inhibition efficiency of 93.2 % at concentration of 1×10−4 M at 303 K which was further raised to 98.1 % at 353 K. PDP studies reveal that given surfactant is mixed type inhibitor. Surface studies such as contact angle measurement, AFM (Atomic Force Microscopy), SEM-EDX (Scanning Electron Microscope-Energy Dispersive X-ray Analysis), and XPS (X-ray Photoelectron Spectroscopy) were employed to justify the adsorption of inhibitor molecules on MS surface. Furthermore, biodegradability test on THC was done to support the environment friendly nature of the surfactant.

Triggering Asymmetric Layer Displacement Polarization and Redox Dual-Sites Activation by Inside-Out Anion Substitution for Efficient CO2 Photoreduction.

Sluggish bulk charge transfer and barren catalytic sites severely hinder the CO2 photoreduction process. Seeking strategies for accelerating charge dynamics and activating reduction and oxidation sites synchronously presents a huge challenge. Herein, an inside-out chlorine (Cl) ions substitution strategy on the layered polar Bi4O5Br2 is proposed for achieving layer structure-dependent polarization effect and redox dual-sites activation. Cl ions in the bulk phase shrink the halogen layer interspace by 8‰, triggering asymmetric [Bi4O5]2+ layer displacement polarization, prolonging the average photocharge lifetime to 201.8ps. Meanwhile, surface substituted Cl ions enhance the electron-donating capability of neighboring Bi atoms, activating the intrinsic Bi reduction sites, and increasing H2O molecule adsorption on nearby intrinsic O oxidation site (cal. by 0.105eV), also self-donating as an alien oxidation site. Besides, Cl upshifts the p-band center closer to the Fermi level, facilitating the reactant adsorption. Therefore, the energy barrier for CO2 activation and rate-limiting *COOH intermediate formation steps are significantly decreased. Without cocatalysts and sacrificial reagents, inside-out Cl-substituted Bi4O5Br2 delivers a remarkable CO2-to-CO photoreduction rate of 50.18µmol g-1 h-1, being one of the state-of-the-art catalysts. This finding offers insights into exploiting polarization at the molecular-level and enhances understanding of catalytic site activation.

Constructing 2D Porous ZnO Gas Sensors Based on Polyvinylpyrrolidone-Assisted Zn-MOF Nanosheets for NO2 Detection.

Two-dimensional (2D) ZnO nanomaterials are promising for gas sensing, because of their large surface area, abundant active sites, and rapid charge transfer. However, it is challenging to prepare 2D ZnO nanosheet gas sensors with high sensing performance, due to the tight interlayer stack and low adsorptive property of ZnO for NO2 molecules. Herein, we synthesized Zn-MOF nanosheets employing polyvinylpyrrolidone (PVP) as the structure-directing agent, further through pyrolysis of the Zn-MOF to obtain 2D ZnO nanosheet gas sensors. As anticipated, the 2D ZnO gas sensors exhibited high sensitivity and selectivity for NO2, and the optimal sample could achieve a response value of 162 at the working temperature of 160 °C, which is 10 times higher than that of pristine ZnO. Meanwhile, experimental and DFT results showed that PVP plays critical roles in the lateral lattice growth of 2D Zn-MOF nanosheets, while the existence of PVP makes the ZnO gas sensors with rich porous property and more oxygen vacancy after the pyrolysis process, which promoted the adsorption, activity, and surface reaction for NO2 molecules. It provides a new approach for the application of 2D ZnO nanosheets in the NO2 detection field.