Nanoscience and Nanotechnology Commons^™

The Study Of Dynamical Electrochemical Impedance Spectroscopy For Oxygen Reduction Reaction On Pt/C Catalyst, Kun-Ming Shi, Jian-Wei Guo, Jia Wang

Journal of Electrochemistry

With joint techniques of rotating disc electrode(RDE) and electrochemical impedance spectroscopy(EIS), and further establishment on equivalent circuit model, this paper studied oxygen reduction reaction(ORR) on commercial Pt/C catalyst in acid medium. Our results found that the dynamical interface on Pt/C consists of two independent processes: 1) the PtO reduction from Pt surface, 2) the new PtO formation from ORR, thus providing key clues for catalyst stability and activity. This also implied that the dynamical interface facilitates reconstruction for porous electrode, and matches with mass transfer. One important issue is discovered that at high overpotential, the high reaction rate for ORR …

Fast Diffusion Of Silver In Tio2 Nanotube Arrays, Wanggang Zhang, Yiming Liu, Diaoyu Zhou, Hui Wang, Wei Liang, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

Using magnetron sputtering and heat treatment, Ag@TiO₂ nanotubes are prepared. The effects of heat-treatment temperature and heating time on the evolution of Ag nanofilms on the surface of TiO₂ nanotubes and microstructure of Ag nanofilms are investigated by X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. Ag atoms migrate mainly on the outmost surface of the TiO₂ nanotubes, and fast diffusion of Ag atoms is observed. The diffusivity for the diffusion of Ag atoms on the outmost surface of the TiO₂ nanotubes at 400 °C is 6.87 × 10⁻¹⁸ m²/s, …

Light-Activated Photocurrent Degradation And Self-Healing In Perovskite Solar Cells, Wanyi Nie, Jean-Christophe Blancon, Amanda J. Neukirch, Kannatassen Appavoo, Hsinhan Tsai, Manish Chhowalla, Muhammad A. Alam, Matthew Y. Sfeir, Claudine Katan, Jacky Even, Sergei Tretiak, Jared J. Crochet, Gautam Gupta, Aditya D. Mohite

Publications and Research

Solution-processed organometallic perovskite solar cells have emerged as one of the most promising thin-film photovoltaic technology. However, a key challenge is their lack of stability over prolonged solar irradiation. Few studies have investigated the effect of light soaking on hybrid perovskites and have attributed the degradation in the optoelectronic properties to photochemical or field-assisted ion migration. Here we show that the slow photocurrent degradation in thin-film photovoltaic devices is due to the formation of light-activated meta-stable deep-level trap states. However, the devices can self-heal completely by resting them in the dark for <1 min or the degradation can be completely prevented by operating the devices at 0°C. We investigate several physical mechanisms to explain the microscopic origin for the formation of these trap states, among which the creation of small polaronic states involving localized cooperative lattice strain and molecular orientations emerges as a credible microscopic mechanism requiring further detailed studies.

Direct Band Gap Gallium Antimonide Phosphide (Gasbxp1-X) For Solar Fuels., Harry Benjamin Russell

Electronic Theses and Dissertations

Photoelectrochemical water splitting has been identified as a promising route for achieving sustainable energy future. However, semiconductor materials with the appropriate optical, electrical and electrochemical properties have yet to be discovered. In search of an appropriate semiconductor to fill this gap, GaSbP, a semiconductor never tested for PEC performance is proposed here and investigated. Density functional theory (DFT+U) techniques were utilized to predict band gap and band edge energetics for GaSbP alloys with low amount of antimony. The overall objective of this dissertation is to understand the suitability of GaSb_xP_1-x alloys for photoelectrochemical water splitting application. Specifically, …

Preparation And Performance Of 3d Graphene Type Porous Carbon Employing Nano Fe(Oh)3 As Template For Oxygen Reduction Catalyst, Chong-Yun Sun, Zhong-Fang Li, Xue-Wei Lu, Xi-Zhan Zhong, Yu-Rong Liu

Journal of Electrochemistry

The 3D graphene type porous carbon was prepared using coal tar pitch as carbon source and nano Fe(OH)₃ as template. Optimal conditions for the catalytic oxygen reduction performance were determined as: the mass ratio of coal tar, nano Fe(OH)₃ and KOH is 6:8:4; the pyrolysis temperature is 800 ^oC. SEM images show that the products have uniformly porous structure. TEM images demonstrate that the products are porous with foam shapes. HRTEM images further indicate that the products have formed several-layers 3D graphene structure, which are also supported by XRD and Raman data, and the pore size mainly …

Syntheses Of Carbon Paper Supported High-Index Faceted Pt Nanoparticles And Their Performance In Direct Formic Acid Fuel Cells, Long Huang, Mei Zhan, Yu-Cheng Wang, Yan-Fen Lin, Shuo Liu, Ting Yuan, Hui Yang, Shi-Gang Sun

Journal of Electrochemistry

Direct formic acid fuel fuels (DFAFCs) are promising energy source for portable electronic devices. Palladium (Pd) is more active than platinum (Pt) for the formic acid electrooxidation. However, the stability of Pd is much poorer than that of Pt. Unfortunately, the ultra-low natural abundance of the Pt makes it extremely expensive and limits its application as a fuel cell catalyst. Boosting both the activity and stability of Pt nanoparticles to enhance their efficiency is urgent. As previous works illustrated, nanoparticles enclosed with high-index facets usually bare a higher activity toward fuel cell related reactions than those nanoparticles with low-index facet. …

Immobilization Of Cellulase For Large Scale Reactors To Reduce Cellulosic Ethanol Cost, Dezhi Zhang

Doctoral Dissertations

Cellulosic ethanol is an alternative renewable energy source. Cellulase used in the production of cellulosic ethanol is very expensive. The difficulty in separating cellulase from the cellulose solution after the hydrolysis process limits the reusability of the cellulase, which highly precludes the scales of this application because of the high cost of the enzyme. Immobilization of cellulase provides a promising approach to allow the enzyme to be recycled, thus reducing the production cost. This research focused on immobilizing cellulase for reuse to reduce the cellulosic ethanol cost.

Four immobilization techniques were explored for the immobilization of cellulase on four different …

Manufacturing Polyacrylonitrile Nanowires And Nanofibers For Sensing And Energy Storage Applications, Juan Chen

Doctoral Dissertations

A novel flow guided assembly approach is presented to well align and accurately position nanowire arrays in pre-defined locations with high throughput and large scale manufacturing capability. In this approach, polyacrylonitrile (PAN)/N, N-dimethylformamide (DMF) solution is first filled in an array of microfluidic channels. Then a gas flow is introduced to blow out most solutions while pushing a little leftover against the channel wall to assemble into polymer nanowires. In this way, highly-ordered nanowires are conveniently aligned in the flow direction and patterned along both sides of the microchannels. In this study, we demonstrated this flow-guided assembly process by producing …

Thermal Transport Properties Of Dry Spun Carbon Nanotube Sheets, Heath E. Misak, James L. Rutledge, Eric D. Swenson, Shankar Mall

Faculty Publications

The thermal properties of carbon nanotube- (CNT-) sheet were explored and compared to copper in this study. The CNT-sheet was made from dry spinning CNTs into a nonwoven sheet. This nonwoven CNT-sheet has anisotropic properties in in-plane and out-of-plane directions. The in-plane direction has much higher thermal conductivity than the out-of-plane direction. The in-plane thermal conductivity was found by thermal flash analysis, and the out-of-plane thermal conductivity was found by a hot disk method. The thermal irradiative properties were examined and compared to thermal transport theory. The CNT-sheet was heated in the vacuum and the temperature was measured with an …

Protein-Targeted Corona Phase Molecular Recognition, Gili Bisker, Juyao Dong, Hoyoung D. Park, Nicole M. Iverson, Jiyoung Ahn, Justin T. Nelson, Markita P. Landry, Sebastian Kruss, Michael S. Strano

Department of Agricultural and Biological Systems Engineering: Faculty Publications

Corona phase molecular recognition (CoPhMoRe) uses a heteropolymer adsorbed onto and templated by a nanoparticle surface to recognize a specific target analyte. This method has not yet been extended to macromolecular analytes, including proteins. Herein we develop a variant of a CoPhMoRe screening procedure of single-walled carbon nanotubes (SWCNT) and use it against a panel of human blood proteins, revealing a specific corona phase that recognizes fibrinogen with high selectivity. In response to fibrinogen binding, SWCNT fluorescence decreases by >80% at saturation. Sequential binding of the three fibrinogen nodules is suggested by selective fluorescence quenching by isolated sub-domains and validated …

Iron Phosphide Nanostructures As An Efficient Bifunctional Catalysts For Water Splitting, Nikitaa Ashokan

Masters Theses

"The first part of this thesis work focuses on developing a bifunctional catalyst for electrochemical water splitting encompassing both oxygen and hydrogen evolution. A highly efficient catalyst is necessary to improve kinetics of the sluggish four electron process for oxygen evolution reaction (OER) and two-electron process for hydrogen evolution reaction (HER). Recently, transition metal phosphides have gained increasing interest in this field because of their good electrical conductivity properties as well as better catalytic activity. Many transition-metal phosphides are being considered for this application and iron phosphide (FeP) has proved to be a good HER catalyst. In this work, we …

Peptide-Functionalized Magnetic Nanoparticles For Cancer Therapy Applications, Anastasia K. Hauser

Theses and Dissertations--Chemical and Materials Engineering

Lung cancer is one of the leading causes of cancer deaths in the United States. Radiation and chemotherapy are conventional treatments, but they result in serious side effects and the probability of tumor recurrence remains high. Therefore, there is an increasing need to enhance the efficacy of conventional treatments. Magnetic nanoparticles have been previously studied for a variety of applications such as magnetic resonance imaging contrast agents, anemia treatment, magnetic cell sorting and magnetically mediated hyperthermia (MMH). In this work, dextran coated iron oxide nanoparticles were developed and functionalized with peptides to target the nanoparticles to either the extracellular matrix …

Synthesis Of Titania Thin Films With Controlled Mesopore Orientation: Nanostructure For Energy Conversion And Storage, Suraj R. Nagpure

Theses and Dissertations--Chemical and Materials Engineering

This dissertation addresses the synthesis mechanism of mesoporous titania thin films with 2D Hexagonal Close Packed (HCP) cylindrical nanopores by an evaporation-induced self-assembly (EISA) method with Pluronic surfactants P123 and F127 as structure directing agents, and their applications in photovoltaics and lithium ion batteries. To provide orthogonal alignment of the pores, surface modification of substrates with crosslinked surfactant has been used to provide a chemically neutral surface. GISAXS studies show not only that aging at 4°C facilitates ordered mesostructure development, but also that aging at this temperature helps to provide orthogonal orientation of the cylindrical micelles which assemble into an …

Synthesis Of Porous Carbon Nanosheets And Its Application In Sodium-Ion Battery, Jing-Fei Zhang, Jing Lu, Xiao-Yu Yang, Yun-Di Huang, Lin Xu, Dong-Mei Sun, Ya-Wen Tang

Journal of Electrochemistry

Owning to sodium’s high abundance, relatively low cost, similar chemical properties to Li and very suitable redox potential of E₀(Na⁺/Na) = -2.71 V versus SHE which is only 0.3 V above that of lithium, rechargeable sodium ion battery hold much promise as potential alternatives to current lithium ion batteries for energy storage applications. Carbon material is regarded as the most promising anode candidate for sodium ion battery. Particularly, carbon nanosheet with porous structure and high conductivity is expected to have improved sodium ion storage properties. In this paper, we present a two-step pyrolysis-based method for facile …

Preparation And Characterization Of Carbon Supported Pd-Sb Composite Nanocatalysts For Formic Acid Electrooxidation, Long-Long Wang, Xiao-Lu Cao, Ya-Jun Wang, Jin-Hao Ping, Qiao-Xia Li

Journal of Electrochemistry

Palladium is considered as an efficient anode catalyst with high catalytic activity for electrooxidation of formic acid. To further improve the catalytic activity and stability, alloying or surface modification with Sb is an effective way. In this work, the well dispersed carbon supported Pd-Sb composite nanocatalysts (Pd-Sb/C) were synthesized by traditional impregnation reduction method with trisodium citrate as the complexing agent, sodium borohydride as the reducing agent. The morphologies of Pd-Sb/C and the effects of molar ratio of Pd to Sb on the electrocatalytic properties of Pd-Sb/C for HCOOH electrooxidation were studied. The XRD and XPS analyses on the as-prepared …

Effect Of Adsorption Potential On Co Oxidation At Au@Pt Nanoparticles Electrodes, A Surface Enhanced Raman Spectroscopic Study, Pu Zhang, Yi Wei, Yong-Li Zheng, Yan-Xia Chen, Zhong-Qun Tian

Journal of Electrochemistry

The adsorption/oxidation of CO on the 55 nm [email protected] nm Pt nanoparticles electrode in both potentiodynamic and potentiostatic modes were investigated by surface enhanced Raman spectroscopy in a thin layer electrochemical flow cell under controlled mass transport, with the aim of clarifying the origin CO oxidation at lower electrode potentials (in current pre-wave region of corresponding cyclic voltammograms). Our results demonstrated that the CO oxidation kinetics differed significantly from the three kinds of different CO adsorption history, with almost no CO oxidation current in the pre-peak potential region after 0.35 V_RHE CO adsorption with or without subsequent holding the …

Effect Of Carbon Nanotubes On Anodic Properties Of Ti/Ru-Ir-Sn Oxides, Feng Lian, Yong-Lei Xin, Bo-Jiang Ma, Li-Kun Xu

Journal of Electrochemistry

The Ru-Ir-Sn metal oxide anodes coated on titanium (Ti/Ru-Ir-Sn) were prepared by thermal decomposition. The effects of amounts of carbon naotubes (CNTs) on anodic properties were studied by TGA, SEM, EDS, cyclic voltammetry, EIS, polarization measurements and accelerated life test. The thermogravimetric analysis and EDS spectrum data showed that the high temperature oxidation decomposition of CNTs did not take place under the condition of the sintering temperature of 470 ℃, and the CNTS still existed in the anode coating in an element form. Compared with the contrast samples, the surface crack of the coating increased, but remained typical morphology. Adding …

Minimizing Sheet Resistance Of Organic Photovoltaic Cell Top Contact Electrode Layer: Silver Nanowire Concentration Vs. Conductive Polymer Doping Concentration, Caitlyn Cook

Materials Engineering

The top contact electrode layers of nine organic photovoltaic cells were prepared with two varying factors: three Silver nanowire (AgNW) densities deposited on a conductive polymer doped with three concentrations. Silver’s low sheet resistance of 20-Ω/sq is hypothesized to lower the sheet resistance of the anode layer and thus enhance the overall efficiency of the cell. Four-point probe measurements indicated that increasing AgNW density in the top contact electrode layer of an organic photovoltaic cell significantly reduces sheet resistance from 52.2k-Ω/sq to 18.0 Ω/sq. Although an increase in doping concentration of the conductive polymer reduced sheet resistance in low AgNW …

Computer Simulations Of Propulsion Of Self-Propelled Flexible Nanobody, Ye Luo

Masters Theses

Swimming bodies such as flagellum and fishes are found everywhere in liquid environment. The research of simulation of swimmers is one of the most important branches among the field of biophysics. This study focus on the direct computer simulation of self-propelled flexible nanobody in fluid field. Two new objectives is studied based on the previous research of Tai-hsien Wu and Dewei ai (2014)[1]. ln Wu's article, the front end of micro swimming body is fixed and the migration of swimmers is neglected. For a further study, one of new targets is to release the head in 3-D simulation fluid area. …

Measuring The Effectiveness Of Photoresponsive Nanocomposite Coatings On Aircraft Windshields To Mitigate Laser Intensity, Ryan S. Phillips, Hubert K. Bilan, Zachary X. Widel, Randal J. Demik, Samantha J. Brain, Matthew Moy, Charles Crowder, Stanley L. Harriman, James T. O'Malley Iii, Joseph E. Burlas, Steven F. Emmert, Jason J. Keleher

Journal of Aviation Technology and Engineering

In 2004, pilots reported 46 laser illumination events to the Federal Aviation Administration (FAA), with the number increasing to approximately 3,600 in 2011. Since that time, the number of reported laser incidents has ranged from 3,500 to 4,000. Previous studies indicate the potential for flight crewmember distraction from bright laser light being introduced to the cockpit. Compositional variations of the photoresponsive nanocomposite coatings were applied to an aircraft windscreen using a modified liquid dispersion/heating curing process. The attenuating effects of the deposited films on laser light intensity were evaluated using an optical power meter and the resultant laser intensity data …

Porous Co3O4 Hollow Nanospheres Cathode Catalyst For High-Capacity And Long-Cycle Li-Air Batteries, Tong Liu, Na Li, Qing-Chao Liu, Xin-Bo Zhang

Journal of Electrochemistry

In this paper, a high specific surface area of porous Co3O4 hollow nanospheres was successfully synthesized via hydrothermal carbonization at 140 °C, followed by calcination using cobalt nitrate hexahydrate (Co(NO3)2·6H2O), hexamethylenetetramine (HMT), sucrose, and sodium citrate (Na3C6H5O7). The porous Co3O4 hollow nanospheres consisted of nanoparticles with high specific surface area of mesoporous structure, and could provide active reaction sites for OER and ORR. When used as lithium-air battery cathode catalyst, the Co3O4/Super P (SP) electrode exhibited excellent cycle performance, resulting in high capacity and long life of lithium-air batteries.

Functional Clay Nanotubes And Composites, Yafei Zhao

Doctoral Dissertations

Tubular nanomaterials and their composites have been extensively studied in recent years in the fields of physics, chemistry, biology, and biomedicine. Carbon nanotube is the most commonly studied tubular nanomaterial; however, toxicity and high cost make it less attractive in industry and thus restricts its applications. Halloysite nanotubes, which are available in abundance in the United States as well as in other countries around the world, is a low-cost, unique and versatile aluminosilicate mineral with a chemical formula of Al4Si4O10(OH)8·nH2O. Basically, the halloysite tube diameter is around 50 nm and the length varies with different locations ranging from 0.4-1.5 μm. …

Biomimetic Oral Mucin From Polymer Micelle Networks, Sundar Prasanth Authimoolam

Theses and Dissertations--Chemical and Materials Engineering

Mucin networks are formed by the complexation of bottlebrush-like mucin glycoprotein with other small molecule glycoproteins. These glycoproteins create nanoscale strands that then arrange into a nanoporous mesh. These networks play an important role in ensuring surface hydration, lubricity and barrier protection. In order to understand the functional behavior in mucin networks, it is important to decouple their chemical and physical effects responsible for generating the fundamental property-function relationship. To achieve this goal, we propose to develop a synthetic biomimetic mucin using a layer-by-layer (LBL) deposition approach. In this work, a hierarchical 3-dimensional structures resembling natural mucin networks was generated …

Designed Synthesis Of Nanoporous Organic Polymers For Selective Gas Uptake And Catalytic Applications, Pezhman Arab

Theses and Dissertations

Design and synthesis of porous organic polymers have attracted considerable attentions during the past decade due to their wide range of applications in gas storage, gas separation, energy conversion, and catalysis. Porous organic polymers can be pre-synthetically and post-synthetically functionalized with a wide variety of functionalities for desirable applications. Along these pursuits, we introduced new synthetic strategies for preparation of porous organic polymers for selective CO₂ capture.

Porous azo-linked polymers (ALPs) were synthesized by an oxidative reaction of amine-based monomers using copper(I) as a catalyst which leads to azo-linkage formation. ALPs exhibit high surface areas of up to 1200 …

Integrated Nanoscale Imaging And Spatial Recognition Of Biomolecules On Surfaces, Congzhou Wang

Theses and Dissertations

Biomolecules on cell surfaces play critical roles in diverse biological and physiological processes. However, conventional bulk scale techniques are unable to clarify the density and distribution of specific biomolecules in situ on single, living cell surfaces at the micro or nanoscale. In this work, a single cell analysis technique based on Atomic Force Microscopy (AFM) is developed to spatially identify biomolecules and characterize nanomechanical properties on single cell surfaces. The unique advantage of these AFM-based techniques lies in the ability to operate in situ (in a non-destructive fashion) and in real time, under physiological conditions or controlled micro-environments.

First, AFM-based …

Platinum Hollow Nanospheres With Different Sizes: Controllable Synthesis And Electrocatalytic Oxidation Toward Methanol, Xuan Lin, Mei-Qin Cheng, Zhong-Jin Shang, Ting Xiong, Xian-Tu Zhang, Wei Tian, Jian-Yun Lin, Qi-Ling Zhong, Bin Ren

Journal of Electrochemistry

The selenium (Se) templates and hollow platinum (Pthollow) nanospheres with different sizes were controllably synthesized by adjusting the concentration of sodium dodecyl sulphonate (SDSN) (CSDSN, μmol·L-1) which was used as a surfactant. Accordingly, the Pthollow nanospheres modified glassy carbon (GC) electrode (Pthollow/GC) was prepared. The morphology and composition of Pthollow nanospheres were characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM), energy dispersive X-ray spectroscopy (EDX), high resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and X-ray diffraction (XRD) techniques. The electrocatalytic activities of Pthollow/GC and electrodeposited Pt nanoparticles modified glassy carbon electrode (Ptnano/GC) toward methanol oxidation …

Direct Electrochemistry And Glucose Biosensing Of Glucose Oxidase-Gold Nanoparticles Composite Synthesized By Enzyme Method, Fang He, Xiao-Li Qin, Ying-Chun Fu, Chao Chen, Qing-Ji Xie, Shou-Zhuo Yao

Journal of Electrochemistry

Glucose oxidase (GOx)-gold nanoparticles (AuNPs) composite was synthesized by the one-pot enzyme reaction in the mixture solution of NaAuCl₄, GOx and glucose, and a Nafion/GOx-AuNPs/glassy carbon electrode was fabricated by the cast-coating method to examine the direct electrochemistry of GOx and the biosensing performance on this electrode. Such a GOx-AuNPs composite showed good direct-electrochemistry activity and bioactivity of GOx, probably because the enzyme-mediated AuNPs are close to the redox active centers of GOx. This enzyme electrode exhibited a linear amperometric response to glucose concentration (0.54 mmol·L^-1) at -0.4 V (vs. SCE), and a detection limit of …

Recycling Wastewater For Hydraulic Fracturing By Use Of Nanofiltration Membranes, Haley D. Cleous

Chemical Engineering Undergraduate Honors Theses

Hydraulic fracturing creates large volumes of produced water, contaminated with organics, suspended solids, and dissolved minerals. This water must either be disposed of in injection wells or treated for reuse. One option is to use a combination of ultrafiltration and nanofiltration to treat this water and reuse it in future hydraulic fracturing wells. The object of this study was to test and characterize commercial nanofiltration membranes. The work done for this project will lead to future work in modifying membranes to improve the rejection of desired components.

Low Molecular Weight Glucosamine/L-Lactide Copolymers As Potential Carriers For The Development Of A Sustained Rifampicin Release System: Mycobacterium Smegmatis As A Tuberculosis Model, Jorge Ragusa

Department of Chemical and Biomolecular Engineering: Dissertations, Theses, and Student Research

Tuberculosis, a highly contagious disease, ranks as the second leading cause of death from an infectious disease, and remains a major global health problem. In 2013, 9 million new cases were diagnosed and 1.5 million people died worldwide from tuberculosis. This dissertation aims at developing a new, ultrafine particle-based efficient antibiotic delivery system for the treatment of tuberculosis. The carrier material to make the rifampicin (RIF)-loaded particles is a low molecular weight star-shaped polymer produced from glucosamine (molecular core building unit) and L-lactide (GluN-LLA). Stable particles with a very high 50% drug loading capacity were made via electrohydrodynamic atomization. Prolonged …

Influence Of Pt:Ru Ratio In Nanotubes Array Structures On The Electrocatalytic Activity Of Methanol Oxidation, Jin-Hua Yuan, Feng-Bin Wang, Xing-Hua Xia

Journal of Electrochemistry

Bimetallic PtRu nanotubes array electrodes (NTAEs) with varied Pt to Ru atomic ratios have been prepared by electrochemical codeposition in 3-aminopropyltri-methoxysilane modified porous anodic alumina (PAA) membranes. The structure and morphology of the catalysts were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. Electrochemical results showed that the NTAEs with varied atomic ratios could be achieved by controlling the precursor concentration for deposition. The prepared nanoarrays composed of Pt or PtRu alloy promoted the mass-normalized activity toward the sluggish electrooxidation reaction of methanol due to the increased catalytic activity and real surface area, as well as the …