Reduction of NO x /SO2 by Wire-plate Type Pulsed Discharge Reactor with Pulsed Corona Radical Shower

Pulsed discharge deNO _x /deSO₂ process has been studied for over 20 years, but how to achieve higher removal rate at lower cost remains one of the crucial issues for realization of its industrial application. This paper presents a novel deNO _x /deSO₂ process that combines a wire-plate type pulsed discharge reactor and a corona radical shower. Our aim is to increase the deNO _x /deSO₂ rate of wire-plate type reactor by enhancing the generation of radicals with pulsed corona radical shower. Effect of a nozzle electrode on the production of OH radical was studied by emissive spectrum, and deNO _x /deSO₂ experiments using a wire-plate reactor with pulsed corona radical shower were conducted. The experimental results demonstrated that corona radical shower could enhance the production of radicals and the deNO _x /SO₂ performance of a wire-plate reactor. This study will play a positive role in the industrial application of wire-plate pulsed discharge deNO _x /deSO₂ reactor.     

Flame Spray Pyrolysis for Finding Multicomponent Nanomaterials with Superior Electrochemical Properties in the CoOx‐FeOx System for Use in Lithium‐Ion Batteries

High‐temperature flame spray pyrolysis is employed for finding highly efficient nanomaterials for use in lithium‐ion batteries. CoO_x‐FeO_x nanopowders with various compositions are prepared by one‐pot high‐temperature flame spray pyrolysis. The Co and Fe components are uniformly distributed over the CoO_x‐FeO_x composite powders, irrespective of the Co/Fe mole ratio. The Co‐rich CoO_x‐FeO_x composite powders with Co/Fe mole ratios of 3:1 and 2:1 have mixed crystal structures with CoFe₂O₄ and Co₃O₄ phases. However, Co‐substituted magnetite composite powders prepared from spray solutions with Co and Fe components in mole ratios of 1:3, 1:2, and 1:1 have a single phase. Multicomponent CoO_x‐FeO_x powders with a Co/Fe mole ratio of 2:1 and a mixed crystal structure with Co₃O₄ and CoFe₂O₄ phases show high initial capacities and good cycling performance. The stable reversible discharge capacities of the composite powders with a Co/Fe mole ratio of 2:1 decrease from 1165 to 820 mA h g^?1 as the current density is increased from 500 to 5000 mA g^?1; however, the discharge capacity again increases to 1310 mA h g^?1 as the current density is restored to 500 mA g^?1.     

In situ X‐ray Diffraction Studies of Cation and Anion Inter­calation into Graphitic Carbons for Electrochemical Energy Storage Applications

Graphite is a redox‐amphoteric intercalation host and thus capable to incorporate various types of cations and anions between its planar graphene sheets to form so‐called donor‐type or acceptor‐type graphite intercalation compounds (GICs) by electrochemical intercalation at specific potentials. While the LiC_x/C_x donor‐type redox couple is the major active compound for state‐of‐the‐art negative electrodes in lithium‐ion batteries, acceptor‐type GICs were proposed for positive electrodes in the “dual‐ion” and “dual‐graphite” cell, another type of electrochemical energy storage system. In this contribution, we analyze the electrochemical intercalation of different anions, such as bis(trifluoromethanesulfonyl) imide or hexafluorophosphate, into graphitic carbons by means of in situ X‐ray diffraction (XRD). In general, the characterization of battery electrode materials by in situ XRD is an important technique to study structural and compositional changes upon insertion and de‐insertion processes during charge/discharge cycling. We discuss anion (X^–) and cation (M⁺) intercalation/de‐intercalation into graphites on a comparative basis with respect to the M_x⁺C_n^– and C_n⁺X_n^– stoichiometry, discharge capacity, the intercalant gallery height/gallery expansion and the M–M or X–X in‐plane distances.     

C−−H activation on aluminum-vanadium bimetallic oxide cluster anions

Aluminum–vanadium bimetallic oxide cluster anions (BMOCAs) have been prepared by laser ablation and reacted with ethane and n‐butane in a fast‐flow reactor. A time‐of‐flight mass spectrometer was used to detect the cluster distribution before and after the reactions. The observation of hydrogen‐containing products AlVO₅H^? and Al_xV_4?xO_11?xH^? (x=1–3) strongly suggests that AlVO₅^? and Al_xV_4?xO_11?x^? (x=1–3) can react with ethane and n‐butane by means of an oxidative dehydrogenation process at room temperature. Density functional theory studies have been carried out to investigate the structural, bonding, electronic, and reactive properties of these BMOCAs. Terminal‐oxygen‐centered radicals (O_t^.) were found in all of the reactive clusters, and the O_t^. atoms, which prefer to be bonded with Al rather than V atoms, are the active sites of these clusters. All the hydrogen‐abstraction reactions are favorable both thermodynamically and kinetically. To the best of our knowledge, this is the first example of hydrogen‐atom abstraction by BMOCAs and may shed light on understanding the mechanisms of C? H activation on the surface of alumina‐supported vanadia catalysts.     

Atmospheric pressure chemical ionization of explosives using alternating current corona discharge ion source

The high‐sensitive detection of explosives is of great importance for social security and safety. In this work, the ion source for atmospheric pressure chemical ionization/mass spectrometry using alternating current corona discharge was newly designed for the analysis of explosives. An electromolded fine capillary with 115 µm inner diameter and 12 mm long was used for the inlet of the mass spectrometer. The flow rate of air through this capillary was 41 ml/min. Stable corona discharge could be maintained with the position of the discharge needle tip as close as 1 mm to the inlet capillary without causing the arc discharge. Explosives dissolved in 0.5 µl methanol were injected to the ion source. The limits of detection for five explosives with 50 pg or lower were achieved. In the ion/molecule reactions of trinitrotoluene (TNT), the discharge products of NO_x^? (x = 2,3), O₃ and HNO₃ originating from plasma‐excited air were suggested to contribute to the formation of [TNT ? H]^? (m/z 226), [TNT ? NO]^? (m/z 197) and [TNT ? NO + HNO₃]^? (m/z 260), respectively. Formation processes of these ions were traced by density functional theory calculations. Copyright © 2015 John Wiley & Sons, Ltd.     

Homologous Silver Bismuth Chalcogenide Halides (N,x)P. III. The (4, x)P, (5, x)P,and (7, x)P Structure Families of Modular Compounds with Tunable Composition and Structure

The crystal structures of six members of the homologous series with general formula [BiQX]₂[Ag_xBi_1?xQ_2?2xX_2x?1]_N+1 (Q = S, Se; X = Cl, Br; 1/2 ≤ x ≤ 1) and N = 4, 5, or 7 were determined by single‐crystal X‐ray diffraction. The series are characterized by the parameters N and x and are denoted ^{(N, x)}P. Ag₃Bi₄S₆Cl₃ (x = 0.60) (I) , Ag_3.5Bi_3.5S₅Br₄ (x = 0.70) (II) and Ag_3.65Bi_3.35Se_4.70Br_4.30 (x = 0.73) (III) belong to ^{(4, x})P series Ag_5xBi_7?5xQ_12?10xX_10x?3 and adopt the AgBi₆S₉ structure type. The ^{(5, x)}P compound Ag_3.66Bi_4.34S_6.68Br_3.32 (IV) , which corresponds to x = 0.61 in Ag_6xBi_8?6xS_14?12xBr_12x?4, crystallizes isostructurally to AgBi₃S₅. The compounds Ag_4.56Bi_5.44Se_8.88Br_3.12 (x = 0.57) (V) and Ag_5.14Bi_4.86S_7.76Br_4.24 (x = 0.64) (VI) , which are members of ^{(7, x)}P series Ag_8xBi_10?8xQ_18?16xBr_16x?6, adopt the Ag₃Bi₇S₁₂ structure type. In the monoclinic crystal structures (space group C2/m) two kinds of layered modules alternate along [001]. Modules of type A uniformly consist of paired rods of face‐sharing monocapped trigonal prisms around Bi atoms with octahedra around mixed occupied metal positions (M = Ag/Bi) between them. Modules of type B are composed of [MZ₆] octahedra, which are arranged in NaCl‐type fragments of thickness N. All structures exhibit Ag/Bi disorder in octahedrally coordinated metal positions as well as Q/X mixed occupation of some anion positions. Corresponding to their black color, all compounds are narrow‐gap semiconductors (E_g = 0.35 eV for (II) ). General characteristics of the entire class of ^{(N, x)}P compounds are gathered in a catalogue.     

A CAS study on S‐loss and O‐loss dissociation mechanisms of the SO2+ ion in the C,D, and E states

In the present work, we mainly study dissociation of the C ²B₁, D²A₁, and E²B₂ states of the SO₂⁺ ion using the complete active‐space self‐consistent field (CASSCF) and multiconfiguration second‐order perturbation theory (CASPT2) methods. We first performed CASPT2 potential energy curve (PEC) calculations for S‐ and O‐loss dissociation from the X, A, B, C, D, and E primarily ionization states and many quartet states. For studying S‐loss predissociation of the C, D, and E states by the quartet states to the first, second, and third S‐loss dissociation limits, the CASSCF minimum energy crossing point (MECP) calculations for the doublet/quartet state pairs were performed, and then the CASPT2 energies and CASSCF spin‐orbit couplings were calculated at the MECPs. Our calculations predict eight S‐loss predissociation processes (via MECPs and transition states) for the C, D, and E states and the energetics for these processes are reported. This study indicates that the C and D states can adiabatically dissociate to the first O‐loss dissociation limit. Our calculations (PEC and MECP) predict a predissociation process for the E state to the first O‐loss limit. Our calculations also predict that the E²B₂ state could dissociate to the first S‐ and O‐loss limits via the A²B₂ ← E²B₂ transition. On the basis of the 13 predicted processes, we discussed the S‐ and O‐loss dissociation mechanisms of the C, D, and E states proposed in the previous experimental studies. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

EPR Studies on Branched High‐Spin Arylnitrenes

The UV (λ>305 nm) photolysis of triazide 3 in 2‐methyl‐tetrahydrofuran glass at 7 K selectively produces triplet mononitrene 4 (g=2.003, D_T=0.92 cm^?1, E_T=0 cm^?1), quintet dinitrene 6 (g=2.003, D_Q=0.204 cm^?1, E_Q=0.035 cm^?1), and septet trinitrene 8 (g=2.003, D_S=?0.0904 cm^?1, E_S=?0.0102 cm^?1). After 45 min of irradiation, the major products are dinitrene 6 and trinitrene 8 in a ratio of ～1:2, respectively. These nitrenes are formed as mixtures of rotational isomers each of which has slightly different magnetic parameters D and E. The best agreement between the line‐shape spectral simulations and the experimental electron paramagnetic resonance (EPR) spectrum is obtained with the line‐broadening parameters Γ(E_Q)=180 MHz for dinitrene 6 and Γ(E_S)=330 MHz for trinitrene 8 . According to these line‐broadening parameters, the variations of the angles Θ in rotational isomers of 6 and 8 are expected to be about ±1 and ±3°, respectively. Theoretical estimations of the magnetic parameters obtained from PBE/DZ(COSMO)//UB3LYP/6‐311+G(d,p) calculations overestimate the E and D values by 1 and 8 %, respectively. Despite the large distances between the nitrene units and the extended π systems, the zero field splitting (zfs) parameters D are found to be close to those in quintet dinitrenes and septet trinitrenes, where the nitrene centers are attached to the same aryl ring. The large D values of branched septet nitrenes are due to strong negative one‐center spin–spin interactions in combination with weak positive two‐center spin–spin interactions, as predicted by theoretical considerations.     

New insights on the Cd UPD on Au(111)

The Cd underpotential deposition (UPD) process on Au(111) was analyzed by means of combined electrochemical measurements and in situ scanning tunneling microscopy (STM). In the underpotential range 300?ΔE (mV) ?400, 2D Cd islands are formed on the fcc regions of the Au(111)‐(√3 × 22) reconstructed surface without lifting the reconstruction. At lower underpotentials, the 2D Cd islands grow and, simultaneously, new 2D islands nucleate and coalesce with the previous ones forming a complete condensed Cd monolayer (ML). STM images and long time polarization experiments performed at ΔE = 70 mV demonstrate the formation of an Au? Cd surface alloy. At ΔE = 10 mV, the formation of the complete Cd ML is accompanied by a significant Au? Cd surface alloying and the kinetic results reveal two different solid‐state diffusion processes. The first one, with a diffusion coefficient D₁ = 4 × 10^?17 cm² s^?1, could be ascribed to the mutual diffusion of Au and Cd atoms through a highly distorted (vacancy‐rich) Au? Cd alloy layer. The second and faster diffusion process (D₂ = 7 × 10^?16 cm² s^?1) is associated with the appearance of an additional peak in the anodic stripping curves and could be attributed to the formation of another Cd_zAu_x alloy phase. Copyright © 2008 John Wiley & Sons, Ltd.     

Two novel organic–inorganic hybrid materials from tetrachloridometallate(II) salts and 4‐[(E)‐2‐(pyridin‐1‐ium‐2‐yl)ethenyl]pyridinium

Two organic–inorganic hybrid compounds have been prepared by the combination of the 4‐[(E)‐2‐(pyridin‐1‐ium‐2‐yl)ethenyl]pyridinium cation with perhalometallate anions to give 4‐[(E)‐2‐(pyridin‐1‐ium‐2‐yl)ethenyl]pyridinium tetrachloridocobaltate(II), (C₁₂H₁₂N₂)[CoCl₄], (I), and 4‐[(E)‐2‐(pyridin‐1‐ium‐2‐yl)ethenyl]pyridinium tetrachloridozincate(II), (C₁₂H₁₂N₂)[ZnCl₄], (II). The compounds have been structurally characterized by single‐crystal X‐ray diffraction analysis, showing the formation of a three‐dimensional network through X—H...Cl_nM⁻ (X = C, N⁺; n = 1, 2; M = Co^II, Zn^II) hydrogen‐bonding interactions and π–π stacking interactions. The title compounds were also characterized by FT–IR spectroscopy and thermogravimetric analysis (TGA).     

Isotopic substitution effects on the volumetric and viscosimetric properties of water-dimethylsulfoxide mixtures at 25°C

Densities and viscosities of binary mixtures (H₂O or D₂O) (1) + (DMSO or DMSO-D6)(2) have been measured over the entire mole fraction range; and the excess volumes, excess viscosities, and excess partial molar volumes Vf of the components have been obtained. All systems show negative excess volume V^e at all compositions, values for mixtures containing D₂O being more negative than those with H₂O byca. 0.03 cm³-mol^-1 at x₁, = 0.6, where a minimum is observed. The difference between DMSO and DMSO-D6 containing mixtures is negligible. The excess viscosity η^e is always positive and shows a maximum at x₁ = 0.65; at this composition, the substitution of H₂O with D₂O causes an excess viscosity increment ofca. 0.35 mPa-s, while deuteration of DMSO brings about a smaller increase,ca. 0.1 mPa-s. The trend of V ₂ ^E with concentration shows the characteristic features of moderately hydrophobic solutes in water (negative values and a minimum in the water-rich region), features that are slightly but significantly more marked in D₂O than in H₂O. The V ₂ ^E values in the water-diluted region and at x₁, =0 are more negative for D₂O than for H₂O.     

Water-absorption properties of an acetal copolymer

The kinetics of sorption from the liquid phase to equilibrium and desorption were studied over the temperature range 0–80°C. Equilibrium uptake was found to increase linearly with concentration in this range. Sorption-desorption kinetics showed the diffusion coefficients to decrease with increasing concentration, although the extent of this dependence did not appear in itself to be temperature-dependent. The apparent diffusion coefficient obeyed the law D = D₀ exp {? E/RT} over the temperature range studied, giving E = 9.9 kcal./mole and D₀ = 0.45 cm.² sec.^?1. These values are compared with corresponding values for other polymers.     

Electrochemical Fabrication and Properties of Highly Ordered Fe‐Doped TiO2 Nanotubes

Highly‐ordered Fe‐doped TiO₂ nanotubes (TiO₂nts) were fabricated by anodization of co‐sputtered Ti–Fe thin films in a glycerol electrolyte containing NH₄F. The as‐sputtered Ti–Fe thin films correspond to a solid solution of Ti and Fe according to X‐ray diffraction. The Fe‐doped TiO₂nts were studied in terms of composition, morphology and structure. The characterization included scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray diffraction, UV/Vis spectroscopy, X‐ray photoelectron spectroscopy and Mott–Schottky analysis. As a result of the Fe doping, an indirect bandgap of 3.0 eV was estimated using Tauc’s plot, and this substantial red‐shift extends its photoresponse to visible light. From the Mott–Schottky analysis, the flat‐band potential (E_fb) and the charge carrier concentration (N_D) were determined to be ?0.95 V vs Ag/AgCl and 5.0 ×10¹⁹ cm^?3 respectively for the Fe‐doped TiO₂nts, whilst for the undoped TiO₂nts, E_fb of ?0.85 V vs Ag/AgCl and N_D of 6.5×10¹⁹ cm^?3 were obtained.     

Determination of the fragmentation mechanisms of organophosphorus ions by H2O and D2O atmospheric-pressure ionization tandem mass spectrometry II—dialkyl alkylphosphonate ions

Diethyl methylphosphonate (DEMP), diisopropyl methylpbosphonate (DIMP), diethyl isopropylphosphonate (DEIP) and diethyl ethylphosphonate (DEEP) were characterized by H₂O and D₂O atmospheric pressure ionization tandem mass Spectrometry (API-MS/MS). Collision-induced dissociation (CID)/fragmentation pathways included alkyl ions by direct cleavage, alkyl radical and water loss processes and McLafferty and McLafferty-type rearrangements by six- and five-membered ring transition states, respectively. D₂O API proved particularly useful in that certain decomposition pathways (i.e. water and methanol neutral losses) had a statistical distribution as to the loss of an acid deuteron and proton(s). This phenomenon was manifested by two pairs of ions in the D₂O API daughter-ion mass spectrum for each phosphonate compound (e.g. both m/z 79/80 and 65/66 for DEMP and DIMP). The observed ion intensity ratios for these pairs of ions served as guides in the determination of their predicted ion relative abundance ratios and CID decomposition pathways. Water neutral losses as opposed to ether and alcohol neutral losses were favored for most of the protonated organophosphonate molecular ion decomposition schemes.     

Viscosity of Aqueous Solutions of n-butylamine,sec-butylamine and tert-butylamine

Abstract

Viscosities of the systems, water (W) + n-butylamine (NBA), W + sec-butylamine (SBA) and W + tert-butylamine (TBA) have been measured in the temperature range 298.15–323.15K. The viscosities (η) and excess viscosities (η^E) have been plotted against mole fraction of amines (X ₂). On addition of amines to water, viscosities first increase rapidly, then pass through maxima at 0.2 mole fraction of amines and then decline continuously as the addition of amines is continued. η^E show large positive values, with maxima also at 0.2 mole fraction of amines. The maxima of the curves of η and η^E vs. mole fraction of butylamines follow the order, W + TBA > W + SBA > W + NBA. The ascending part of the η vs. X ₂ curves in the water-rich region is explained by the hydrophobic hydration caused by the hydrocarbon tails and the hydrophilic effect due to — NH₂ group of amines. Following the maxima, amine - amine association is preferred, which accounts for the steady decrease of viscosity up to the pure state of amines.     

Thermodynamics of liquid mixtures of argon+ carbon monoxide

The heat of mixing of liquid argon (component 1) and liquid carbon monoxide has been measured by direct calorimetry for several mixtures of composition ranging from x₁ ? 0.2 to x₁ ? 0.8 at 85.79 K. At this temperature H^E is positive and an almost parabolic function of mole fraction, with a maximum value of H^E = 95.9 J mol^?1 at x₁ = 0.569.The experimental results are compared with those derived from the Gibbons-Rigby equation of state, and from conformal solution theory.     

Non‐hydrogenated amorphous germanium carbide with adjustable microstructure and properties: a potential anti‐reflection and protective coating for infrared windows

Amorphous non‐hydrogenated germanium carbide (a‐Ge_1?xC_x) films have been deposited using magnetron co‐sputtering technique by varying the sputtering power of germanium target (P_Ge). The effects of P_Ge on composition and structure of the a‐Ge_1?xC_x films have been analyzed. The FTIR spectrum shows that the C–Ge bonds were formed in the a‐Ge_1?xC_x films according to the absorption peak at ~610 cm^?1. The Raman results indicate that the amorphous films also contain both Ge and C clusters. The XPS results reveal that the carbon concentration decreased as P_Ge increased from 40 to 160 W. The fraction of sp³ C–C bonds remains almost constant when increasing P_Ge from 40 to 160 W. The sp² C–C content of a‐Ge_1?xC_x film decreases gradually to 35.9% with P_Ge up to 160 W. Nevertheless, sp³ C–Ge sites rose with increasing P_Ge. Furthermore, the hardness and the refractive index gradually increased with increasing P_Ge. The excellent optical transmission of annealed a‐Ge_1–xC_x double‐layer coating at 400 °C suggests that a‐Ge_1?xC_x films can be used as an effective anti‐reflection coating for the ZnS IR window in the wavelength region of 8–12 µm, and can endure higher temperature than hydrogenated amorphous germanium carbide do. Copyright © 2012 John Wiley & Sons, Ltd.     

Efficient Fe‐Co‐N‐C Electrocatalyst Towards Oxygen Reduction Derived from a Cationic CoII‐based Metal–Organic Framework Modified by Anion‐Exchange with Potassium Ferricyanide

Fe‐Co‐N‐C electrocatalysts have proven superior to their counterparts (e.g. Fe‐N‐C or Co‐N‐C) for the oxygen reduction reaction (ORR). Herein, we report on a unique strategy to prepare Fe‐Co‐N‐C?x (x refers to the pyrolysis temperature) electrocatalysts which involves anion‐exchange of [Fe(CN)₆]^3? into a cationic Co^II‐based metal‐organic framework precursor prior to heat treatment. Fe‐Co‐N‐C‐900 exhibits an optimal ORR catalytic performance in an alkaline electrolyte with an onset potential (E_onset: 0.97 V) and half‐wave potential (E_1/2: 0.86 V) comparable to that of commercial Pt/C (E_onset=1.02 V; E_1/2=0.88 V), which outperforms the corresponding Co‐N‐C‐900 sample (E_onset=0.92 V; E_1/2=0.84 V) derived from the same MOF precursor without anion‐exchange modification. This is the first example of Fe‐Co‐N‐C electrocatalysts fabricated from a cationic Co^II‐based MOF precursor that dopes the Fe element via anion‐exchange, and our current work provides a new entrance towards MOF‐derived transition‐metal (e.g. Fe or Co) and nitrogen‐codoped carbon electrocatalysts with excellent ORR activity.     

The Intermetalloid Clusters [Ni2Bi12]4+ and [Rh2Bi12]4+ – Ionothermal Synthesis,Crystal Structures,and Chemical Bonding

The intermetalloid clusters [M₂Bi₁₂]⁴⁺ (M = Ni, Rh) were synthesized as halogenido‐aluminates in Lewis‐acidic ionic liquids. The reaction of bismuth and NiCl₂ in [BMIm]Cl · 5AlCl₃ (BMIm = 1‐butyl‐3‐methylimidazolium) at 180 °C yielded black, triclinic (P1 ) crystals of [Ni₂Bi₁₂][AlCl₄]₃[Al₂Cl₇]. Black, monoclinic (P2₁/m) crystals of [Rh₂Bi₁₂][AlBr₄]₄ precipitated after dissolving the cluster salt Bi_12–xRhX_13–x (X = Cl, Br; 0 < x < 1) in [BMIm]Br·4.1AlBr₃ at 140 °C. In the cationic cluster [Ni₂Bi₁₂]⁴⁺, the nickel atoms center two base‐sharing square antiprisms of bismuth atoms (symmetry close to D_4h). The valence‐electron‐poorer rhodium‐containing cluster is a distorted variant of this motif: the terminating Bi₄ rings are folded to bicyclic “butterflies“ and the central square splits into two dumbbells (symmetry close to D_2h). DFT‐based calculations and real‐space bonding analyses place the intermetalloid units between a triple‐decker complex and a conjoined Wade‐Mingos cluster.     

Negative thermal expansibility change for dissociation of lysozyme variant amyloid protofibril

A disulfide‐deficient variant of hen lysozyme, 0SS, is known to form an amyloid protofibril spontaneously, and to dissociate into monomers at high hydrostatic pressure. We carried out native PAGE at various temperatures (20–35°C) and pressures (0.1–200 MPa), to characterize the dissociation equilibrium of disulfide‐deficient variant of hen lysozyme amyloid protofibril. Based on the density profiles, the partial molar volume and thermal expansibility changes for dissociation, Δv_D and Δe_D, were obtained to be ?74 cm³/mol at 25°C and ?2.3 cm³ mol^?1 K^?1, respectively. The dissociation of amyloid fibril destroys the cross β‐structure, and such conformational destruction in native protein fold rarely accompanies negative thermal expansibility change. We discussed the negative thermal expansibility change in terms of hydration and structural packing of the amyloid protofibril.