106-97-8Relevant articles and documents
Reductive dehydration of butanone to butane over Pt/γ-Al 2O3 and HZSM-5
Blass, Samuel D.,Rosenthal, Corey,Bhan, Aditya,Schmidt, Lanny D.
, p. 54 - 57 (2013)
We show that butanone can be reacted to form n-butane in an isothermal reactor containing a 1 wt.% Pt/γ-Al2O3 and an HZSM-5 catalyst (total mass of 12-400 mg, Si/Al = 11.5) below 160 C with up to 99% selectivity and 67% yield. The catalyst loading (12-400 mg) and temperature (100-250 C) were varied to obtain primary products whose selectivities decreased with conversion and secondary/tertiary products whose selectivities increased with conversion. As conversion increased, the selectivities of butanol and butene decreased, showing the formation of butane from butanone through a series reaction pathway: butanone → 2-butanol → butene → butane. Butane selectivity increased as the temperature was increased from 100 to 200 C when compared at similar conversions due to higher dehydration rates over the zeolite. Processing ketones at low temperatures over bifunctional catalysts may be an efficient means of obtaining high yields of stable paraffins from reactive oxygenates.
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Helmkamp et al.
, p. 844 (1956)
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Cobalt-Iron-Manganese Catalysts for the Conversion of End-of-Life-Tire-Derived Syngas into Light Terminal Olefins
Falkenhagen, Jan P.,Maisonneuve, Lise,Paalanen, Pasi P.,Coste, Nathalie,Malicki, Nicolas,Weckhuysen, Bert M.
, p. 4597 - 4606 (2018)
Co-Fe-Mn/γ-Al2O3 Fischer–Tropsch synthesis (FTS) catalysts were synthesized, characterized and tested for CO hydrogenation, mimicking end-of-life-tire (ELT)-derived syngas. It was found that an increase of C2-C4 olefin selectivities to 49 % could be reached for 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn/γ-Al2O3 with Na at ambient pressure. Furthermore, by using a 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al2O3 catalyst the selectivity towards the fractions of C5+ and CH4 could be reduced, whereas the selectivity towards the fraction of C4 olefins could be improved to 12.6 % at 10 bar. Moreover, the Na/S ratio influences the ratio of terminal to internal olefins observed as products, that is, a high Na loading prevents the isomerization of primary olefins, which is unwanted if 1,3-butadiene is the target product. Thus, by fine-tuning the addition of promoter elements the volume of waste streams that need to be recycled, treated or upgraded during ELT syngas processing could be reduced. The most promising catalyst (5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ-Al2O3) has been investigated using operando transmission X-ray microscopy (TXM) and X-ray diffraction (XRD). It was found that a cobalt-iron alloy was formed, whereas manganese remained in its oxidic phase.
Joice et al.
, p. 223,227 (1966)
Role of Ga3+promoter in the direct synthesis of iso-butanolviasyngas over a K-ZnO/ZnCr2O4catalyst
Zhang, Tao,Zeng, Chunyang,Wu, Yingquan,Gong, Nana,Yang, Jiaqian,Yang, Guohui,Tsubaki, Noritatsu,Tan, Yisheng
, p. 1077 - 1088 (2021)
The direct synthesis of iso-butanol is an important reaction in syngas (composed of CO and H2) conversion. K-ZnO/ZnCr2O4(K-ZnCr) is a commonly used catalyst. Here, Ga3+is used as an effective promoter to boost the efficiency of the catalyst and retard the production of CO2. X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet-visible diffuse reflection spectroscopy and electron microscopy were used to characterize the structural variations with different amounts of Ga3+, the results showed that the particle size of the catalyst decreases with the addition of Ga3+. The temperature-programmed desorption of NH3and CO2, and diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTs) analysis of the CO adsorption revealed that the acidity and basicity were altered owing to the different forms of Ga3+adoption. X-ray photoelectron spectroscopy and density functional theory (DFT) calculations revealed that the formation of Ga clusters that are coordinated on the exposed surfaces of ZnCr2O4, and undergo a tetra-coordinated Ga3+exchange with one of the Zn in ZnCr2O4(ZG) and ZnGa2O4, probably depends on the amount of Ga added. The structural evolution of the Ga3+promoted K-ZnO/ZnCr2O4catalysts can be described as follows: (i) the main forms are ZG and Ga coordinated ZnCr2O4, in which the amount of Ga3+is below 1.10 wt%; and (ii) the Ga3+containing compound is gradually changed from ZG to ZnGa2O4and the amount of gallium clusters increased when the amount of Ga3+was higher than 1.10 wt%. The catalytic performance evaluation results show that K-Ga1.10ZnCr exhibits the highest space time yield and selectivity of alcohols, in which the three compounds play different roles in syngas conversion: ZG is the main active site that boosts the efficiency of the catalysts, owing to the intensified CO adsorption and decreased activation energy of CHO formation through CO hydrogenation; ZnGa2O4only modifies the surface basicity and acidity on the catalyst, thereby impacting the carbon chain growth after the CO is adsorbed. The effects of Ga coordinated with ZnCr2O4shows little impact on the CO adsorption owing to the weak electron donating effects of Ga.
Enzymatic Electrosynthesis of Alkanes by Bioelectrocatalytic Decarbonylation of Fatty Aldehydes
Abdellaoui, Sofiene,Macazo, Florika C.,Cai, Rong,De Lacey, Antonio L.,Pita, Marcos,Minteer, Shelley D.
, p. 2404 - 2408 (2018)
An enzymatic electrosynthesis system was created by combining an aldehyde deformylating oxygenase (ADO) from cyanobacteria that catalyzes the decarbonylation of fatty aldehydes to alkanes and formic acid with an electrochemical interface. This system is able to produce a range of alkanes (octane to propane) from aldehydes and alcohols. The combination of this bioelectrochemical system with a hydrogenase bioanode yields a H2/heptanal enzymatic fuel cell (EFC) able to simultaneously generate electrical energy with a maximum current density of 25 μA cm?2 at 0.6 V and produce hexane with a faradaic efficiency of 24 %.
Skeletal Rearrangement of Alkanes over Ir/Al2O3. Transformation of n-Pentane, 2-Methylbutane and 2,2-Dimethylbutane
Sarkany, Antal
, p. 1511 - 1522 (1989)
Transformation of n-pentane, 2-methylbutane and 2,2-dimethylbutane has been investigated as a function of the H2/hydrocarbon ratio over a 10 wtpercent Ir/Al2O3 catalyst of 14 percent dispersion.The selectivity of isomer formation has been observed to decrease with the increase of the H2/hydrocarbon ratio and follow the sequence n-pentane > 2-methylbutane >> 2,2-dimethylbutane.The effect of the experimental conditions on the product selectivity has been interpreted considering the actual surface state of the working catalyst.
Catalytic behavior of graphite nanofiber supported nickel particles. 3. The effect of chemical blocking on the performance of the system
Park, Colin,Baker, R. Terry K.
, p. 2453 - 2459 (1999)
Graphite nanofibers are a newly developed type of material produced by the catalytic decomposition of carbon containing gases at high temperatures. The individual components of these conformations, small-sized graphite crystallites, are arranged in such a manner that only the edge regions are exposed. The carbon atoms at these sites that are arranged in two conformations, `armchair' or `zigzag', act as templates for the nucleation of metal crystallites. Treatment of graphite with certain phosphorus compounds is a process that is known to result in preferential blocking of the `armchair' faces, whereas boron oxide selectively substitutes into the `zigzag' faces. In the current investigation pretreatment in phosphorus oxide was found to exert little or no effect on the subsequent catalytic performance of graphite nanofiber supported nickel with respect to hydrogenation of ethylene and 1-butene. In contrast, incorporation of boron into the carbonaceous support, which resulted in blockage of the `zigzag' sites of the graphite nanofibers rendered the supported metal system virtually inactive toward hydrogenation of either of the olefins. These results suggest that the active state of nickel is one where the particles are preferentially located on the `zigzag' faces of the nanofiber structures. Under these conditions the metal particles adopt a crystallographic arrangement that is favorable toward reaction with both reactant molecules. It is evident that one can control the catalytic behavior of a given metal by careful tailoring the support structure at the atomic level.
A robust platinum carbonyl cluster anion [Pt3(CO)6]52- encapsulated in an ordered mesoporous channel of FSM-16: FTIR/EXAFS/TEM characterization and catalytic performance in the hydrogenation of ethene and 1,3-butadiene
Yamamoto, Takashi,Shido, Takafumi,Inagaki, Shinji,Fukushima, Yoshiaki,Ichikawa, Masaru
, p. 3866 - 3875 (1998)
A robust trigonal prismatic cluster anion [Pt3(CO)6]52- (vCO = 2078, 1878 cm-1; ??max = 405 and 702 nm; R1(Pt - Pt) = 2.68 Aì? (CN = 2.0); R2(Pt - Pt) = 3.08 Aì? (CN = 1.5)) is selectively synthesized in the ordered hexagonal channel of FSM-16 by the reductive carbonylation of H2PtCl6TNR4+/FSM-16 under a CO + H2O atmosphere at 323 K. The Pt cluster anion extracted in THF solution by cation metathesis was identified as [Pt3(CO)6]52- by FTIR and UV - vis spectroscopic data. TEM observation showed that [Pt3(CO)6]52- was uniformly dispersed and aligned in the mesoporous channels of FSM-16. The Pt15 cluster anions formed in FSM-16 were relatively stabilized by the coimpregnated quaternary alkylammonium cations as NR4+ in the following order for the alkyl groups: butyl > ethyl > methyl, methyl viologen (MV) > hexyl a?? no countercations. The EXAFS and FTIR studies demonstrated that [Pt3(CO)6]52- in FSM-16 was transformed by the controlled removal of CO at 300-343 K into the partially decarbonylated Pt15 cluster (R1(Pt - Pt) = 2.69 Aì?, CN = 2.2; R2(Pt - Pt) = 3.10 Aì?, CN = 1.4). This sample showed IR spectra indicating a linear CO (vCO = 2062 cm-1) without a bridged one. The Pt carbonyl cluster was eventually converted by thermal evacuation exceeding 463 K to naked Pt particles (15 Aì? diameter; R(Pt - Pt) = 2.76 Aì?, CN = 7.8). The controlled removal of CO from [Pt3(CO)6-x]52- in FSM-16 by thermal evacuation at 300-423 K yields samples with marked catalaytic activities for hydrogenation of ethene and 1,3-butadiene at 300 K. 1,3-Butadiene is selectively hydrogenated to 1-butene on the partially decarbonylated Pt carbonyl clusters in FSM-16, whereas it is preferentially converted to n-butane on the naked Pt particles in FSM-16.
Selective hydrogenation of 1,3-butadiene on PdNi bimetallic catalyst: From model surfaces to supported catalysts
Hou, Ruijun,Yu, Weiting,Porosoff, Marc D.,Chen, Jingguang G.,Wang, Tiefeng
, p. 1 - 10 (2014)
The selective hydrogenation of 1,3-butadiene serves as a means to purify the butene stream generated from cracking naphtha or gas oil. To identify selective hydrogenation catalysts, 1,3-butadiene was studied on single crystal Ni/Pd(1 1 1) bimetallic surfaces, utilizing density functional theory (DFT) calculations and temperature-programmed desorption (TPD). DFT calculations predicted that the Pd-terminated bimetallic surface should be more active and selective to produce 1-butene, which were verified experimentally using TPD. The promising results on model surfaces were extended to γ-Al 2O3-supported catalysts using both batch and flow reactors. Extended X-ray absorption fine structure (EXAFS) and transmission electron microscopy (TEM) confirmed the formation of bimetallic nanoparticles. The PdNi bimetallic catalyst showed higher hydrogenation activity and 1-butene selectivity than the monometallic catalysts. The excellent correlation between model surfaces and supported catalysts demonstrates the feasibility of designing effective bimetallic catalysts for selective hydrogenation reactions.
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Cason,Way
, p. 31,33, 35 (1949)
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A low temperature reaction sequence for methane conversion
Koerts,van Santen
, p. 1281 - 1283 (1991)
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Yao et al.
, p. 21,23, 25 (1979)
Quantitative determination of volatile products formed in electrolyses of organic compounds
Pritts, Wayne A.,Vieira, Kenneth L.,Peters, Dennis G.
, p. 2145 - 2149 (1993)
A straightforward and accurate procedure has been developed for the quantitation of volatile products that are formed from electrolyses of organic compounds. This methodology, which eliminates the need for external cold traps, utilizes an internal standard that is present in both the solution and gas phases of a gas-tight electrochemical cell. By sampling the gas and solution phases of the cell at the end of an electrolysis and by using gas chromatography to determine the quantities of the various volatile products in each phase with respect to the internal standard, one can ascertain the absolute yield of each product derived from the electrolysis of the starting material. In this paper, we present the theoretical background for this technique, including the formulation and use of experimentally measured gas chromatographic response factors, and we demonstrate the applicability of the approach for the quantitation of seven volatile products that are formed by the electrolytic reduction of 1,4-dibromobutane at a reticulated vitreous carbon cathode in dimethylformamide containing tetramethylammonium perchlorate. This method can be readily adapted to any compound whose electrolysis gives rise to volatile products.
SPIROANNELATION VIA GEM-DIHALOCYCLOPROPANE SUBSTRATES AND A CYCLOCUPRATE SPECIES
Scott, Frederick,Mafunda, Brownlee G,Normant, Jean F.,Alexakis, Alexandre
, p. 5767 - 5770 (1983)
The dialkylation of gem-dibromocyclopropanes with a new 'cyclocuprate' species to yield spiro compounds is possible if the reaction is performed in the presence of a lithium acetylide.
Gent,Gibson
, p. 1835,1837, 1839 (1949)
Catalytic Properties of Low-valent Lanthanide Species introduced into Y-Zeolite
Baba, Toshida,Kim, Geon Joong,Ono, Yoshio
, p. 891 - 897 (1992)
Low-valent ytterbium or europium species were introduced into Y-zeolites by impregnation from ytterbium or europium metal dissolved in liquid ammonia.The zeolites thus loaded with ytterbium or europium have a high catalytic activity for the isomerization of but-1-ene at 273 K, when they were heated under vacuum at ca. 500 K.Their catalytic activities are strongly influenced by the alkali-metal cations present in the Y-zeolite.The isomerization proceeds via an allylic carbanion-type intermediate.On the other hand, the zeolites heated under vacuum around 900 K areactive for the hydrogenation of ethene at 273 K, and buta-1,3-diene at 323 K.The photoluminescence of europium supported on zeolites and temperature-programmed desorption spectra of gases desorbed from zeolites loaded with europium or ytterbium suggest that metal imides such as EuNH, and metal-like species may be formed by the zeolites under vacuum at ca. 500 and 900 K, respectively.
Bimetallic Au-Pd alloy nanoparticles supported on MIL-101(Cr) as highly efficient catalysts for selective hydrogenation of 1,3-butadiene
Guo, Luxia,Jiang, Shuai,Li, Yingjie,Liu, Lili,Tai, Xishi,Yan, Shijuan,Zhou, Xiaojing
, p. 33417 - 33427 (2020)
Gold-palladium (Au-Pd) bimetallic nanoparticle (NP) catalysts supported on MIL-101(Cr) with Au : Pd mole ratios ranging from 1 : 3 to 3 : 1 were prepared through coimpregnation and H2reduction. Au-Pd NPs were homogeneously distributed on the MIL-101(Cr) with mean particle sizes of 5.6 nm. EDS and XPS analyses showed that bimetallic Au-Pd alloys were formed in the Au(2)Pd(1)/MIL-101(Cr). The catalytic performance of the catalysts was explored in the selective 1,3-butadiene hydrogenation at 30-80 °C on a continuous fixed bed flow quartz reactor. The bimetallic Au-Pd alloy particles stabilized by MIL-101(Cr) presented improved catalytic performance. The as-synthesized bimetallic Au(2)Pd(1)/MIL-101(Cr) with 2 : 1 Au : Pd mole ratio showed the best balance between the activity and butene selectivity in the selective 1,3-butadiene hydrogenation. The Au-Pd bimetallic-supported catalysts can be reused in at least three runs. The work affords a reference on the utilization of a MOF and alloy nanoparticles to develop high-efficiency catalysts.
Maschke,Lampe
, p. 569,571 (1964)
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Hara et al.
, p. 1641 (1967)
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Evidence for Surface Phosphinidene Intermediates Mg> in the Heterogeneous Dechlorination of Alkyldichlorophosphanes RPCl2 by Mg Metal
Bock, Hans,Bankmann, Martin
, p. 1130 - 1132 (1989)
The heterogeneous dechlorination of alkyldichlorophosphanes by Mg metal at 600 K yields chemisorbed products which include penta-alkylcyclopentaphosphanes (RP)5, in addition to RnPH(3-n), R2P-PR2, P4, RH, and R-R, and thus provides evidence for surface phosphinidene intermediates Mg>.
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Ausloos
, p. 1709,1711 (1956)
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Catalytic reduction of iodoethane and 2-iodopropane at carbon electrodes coated with anodically polymerized films of nickel(II) salen
Dahm, Christopher E.,Peters, Dennis G.
, p. 3117 - 3123 (1994)
In acetonitrile containing tetramethylammonium tetrafluoroborate, nickel(II) salen undergoes anodic polymerization onto a carbon electrode. Nickel(II) in the polymer film exhibits reversible one-electron reduction to form nickel(I), which can catalytically reduce iodoethane or 2-iodopropane to form an ethyl or 2-propyl radical, respectively, and to regenerate nickel-(II). Kinetics studies with the aid of hydrodynamic voltammetry indicate that the catalytic reduction of iodoethane belongs to the ER regime of Saveant and co-workers, whereas catalytic reduction of 2-iodopropane is of the S classification. Controlled-potential electrolyses of iodoethane and 2-iodopropane at nickel-(II) salen-coated reticulated vitreous carbon cathodes give product distributions in accord with the relative importance of radical coupling and disproportionation. Direct reduction of iodoethane at a bare cathode generates products via a carbanion mechanism. Products obtained from direct reduction of 2-iodopropane depend on the potential employed; at a potential corresponding to the first voltammetric wave, product distributions are nearly identical with those obtained from the catalytic reduction, whereas at a potential after the second voltammetric wave, the products are derived from the 2-propyl carbanion.
ATP-independent substrate reduction by nitrogenase P-cluster variant
Lee, Chi Chung,Hu, Yilin,Ribbe, Markus W.
, p. 6922 - 6926 (2012)
The P-cluster of nitrogenase is largely known for its function to mediate electron transfer to the active cofactor site during catalysis. Here, we show that a P-cluster variant (designated P*-cluster), which consists of paired [Fe4S4]-like clusters, can catalyze ATP-independent substrate reduction in the presence of a strong reductant, europium (II) diethylenetriaminepentaacetate [Eu(II)-DTPA]. The observation of a decrease of activity in the rank ΔnifH, ΔnifBΔnifZ, and ΔnifB MoFe protein, which corresponds to a decrease of the amount of P*-clusters in these cofactor-deficient proteins, firmly establishes P*-cluster as a catalytically active metal center in Eu(II)-DTPA-driven reactions. More excitingly, the fact that P*-cluster is not only capable of catalyzing the two-electron reduction of proton, acetylene, ethylene, and hydrazine, but also capable of reducing cyanide, carbon monoxide, and carbon dioxide to alkanes and alkenes, points to a possibility of developing biomimetic catalysts for hydrocarbon production under ambient conditions.
Selective Lanthanide-catalysed Reactions. Catalytic Properties of Sm and Yb Metal Vapour Deposition Products
Imamura, Hayao,Kitajima, Keiji,Tsuchiya, Susumu
, p. 1647 - 1654 (1989)
The characteristics of lanthanide catalysts obtained when Sm and Yb were vaporized into a frozen organic (tetrahydrofuran, benzene and methylcyclohexane) matrix (77 K) were investigated.These low-valent, highly dispersed lanthanide particles (indicated as Sm/THF, Sm/benzene, Yb/THF, Yb/benzene etc.) were catalytically active and selective for hydrogenation and isomerization.Samarium usually showed a greater activity than ytterbium.Olefin hydrogenation obeyed the rate law v=kPH, suggesting that the reaction is controlled by catalytic activation of hydrogen.The molecular isotopic identity of hydrogen was conserved during the hydrogenation.Yb/THF and Yb/benzene were active for partial hydrogenation of benzene to cyclohexene.For the hydrogenation of olefins and acetylenes the substrate specificity was high; thus C-C double bonds were more readily reduced than triple bonds.The samarium and ytterbium catalysts discriminate between terminal and internal C-C triple bonds, only internal CC bonds (but-2-yne and pent-2-yne) being reduced very selectively in contrast to acetylene, methylacetylene and but-1-yne.Solid base character of the lanthanide provides a cause for these differences in catalytic properties.
Tuning crystal phase of molybdenum carbide catalyst to induce the different selective hydrogenation performance
Ding, Ziluo,Hou, Ruijun,Sun, Kening,Xu, Yamei,Yang, Qiuchen
, (2021/12/04)
α-MoC, β-Mo2C, and MoC-Mo2C were synthesized and investigated in the selective hydrogenation of 1,3-butadiene to understand the effect of crystal phases. The catalysts were characterized by XRD, N2-physisorption, SEM, TEM, XPS and chemisorptions. The adsorption properties and electronic properties over MoC(001) and Mo2C(001) were investigated by DFT calculations. The catalysts were evaluated at low and high temperatures in a fixed-bed reactor. β-Mo2C exhibits high activity and low butenes selectivity, due to the high concentration of hydrogen at each active site as well as the stronger adsorption and higher capacity of alkene; MoC-Mo2C shows better stability due to synergetic effect. At high temperature, the reaction rate is more dependent on the PH2 than PC4H6. Increasing PH2 could promote the activity and reduce oligomers formation. β-Mo2C exhibits the best performance at high temperatures concerning its high activity and the inhibition of oligomerization. This work is valuable for the non-precious metal catalyst development.
Conversion of Phenol and Lignin as Components of Renewable Raw Materials on Pt and Ru-Supported Catalysts
Bobrova, Nataliia A.,Bogdan, Tatiana V.,Bogdan, Viktor I.,Koklin, Aleksey E.,Mishanin, Igor I.
, (2022/03/01)
Hydrogenation of phenol in aqueous solutions on Pt-Ni/SiO2, Pt-Ni-Cr/Al2 O3, Pt/C, and Ru/C catalysts was studied at temperatures of 150–250? C and pressures of 40–80 bar. The possibility of hydrogenation of hydrolysis lignin in an aqueous medium in the presence of a Ru/C catalyst is shown. The conversion of hydrolysis lignin and water-soluble sodium lignosulfonate occurs with the formation of a complex mixture of monomeric products: a number of phenols, products of their catalytic hydrogenation (cyclohexanol and cyclohexanone), and hydrogenolysis products (cyclic and aliphatic C2 –C7 hydrocarbons).
A selective and stable Fe/TiO2catalyst for selective hydrogenation of butadiene in alkene-rich stream
Casale, Sandra,Delannoy, Laurent,Louis, Catherine,Méthivier, Christophe,Santander de Soto, Laura,Wang, Zhao
supporting information, p. 7031 - 7034 (2021/07/21)
The replacement of precious metals by more abundant and therefore much less expensive metals remains a very important challenge in catalysis. A Fe/TiO2catalyst prepared by deposition-precipitation with urea showed very high selectivity to alkenes (>99%), even at high conversion (>90%), in selective hydrogenation of butadiene in an excess of propene. Its activity is very stable at 175 °C whereas the catalyst deactivates at 50 °C, although it is also initially very active. The presence of metallic iron seems to be necessary to ensure these excellent performances.