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Showing papers on "Reaction rate published in 2014"


Journal ArticleDOI
TL;DR: In this paper, the effect of pH on the hydrogen oxidation and evolution reaction (HOR/HER) rates is addressed for the first time for the three most active monometallic surfaces: Pt, Ir, and Pd carbon-supported catalysts.
Abstract: The effect of pH on the hydrogen oxidation and evolution reaction (HOR/HER) rates is addressed for the first time for the three most active monometallic surfaces: Pt, Ir, and Pd carbon-supported catalysts. Kinetic data were obtained for a proton exchange membrane fuel cell (PEMFC; pH ≈ 0) using the H2-pump mode and with a rotating disk electrode (RDE) in 0.1 M NaOH. Our findings point toward: (i) a similar ≈100-fold activity decrease on all these surfaces when going from low to high pH; (ii) a reaction rate controlled by the Volmer step on Pt/C; and (iii) the H-binding energy being the unique and sole descriptor for the HOR/HER in alkaline electrolytes. Based on a detailed discussion of our data, we propose a new mechanism for the HOR/HER on Pt-metals in alkaline electrolytes.

1,070 citations


Journal ArticleDOI
TL;DR: In this article, reaction kinetics were studied to quantify the effects of polar aprotic organic solvents on the acid-catalyzed conversion of xylose into furfural.
Abstract: Reaction kinetics were studied to quantify the effects of polar aprotic organic solvents on the acid-catalyzed conversion of xylose into furfural. A solvent of particular importance is g-valerolactone (GVL), which leads to signifi- cant increases in reaction rates compared to water in addition to increased product selectivity. GVL has similar effects on the kinetics for the dehydration of 1,2-propanediol to propanal and for the hydrolysis of cellobiose to glucose. Based on results obtained for homogeneous Bronsted acid catalysts that span a range of pKa values, we suggest that an aprotic organic solvent affects the reaction kinetics by changing the stabiliza- tion of the acidic proton relative to the protonated transition state. This same behavior is displayed by strong solid Bronsted acid catalysts, such as H-mordenite and H-beta. The use of organic solvents is pervasive in the chemical industry, and recently it has been shown that organic solvents are beneficial in the chemical conversion of lignocellulosic biomass. (1-3) One such solvent is g-valerolactone (GVL), which can be produced from biomass and displays significant improvements in reaction performance for biomass conver- sion reactions compared to conversion in aqueous media, such as increased catalytic activity and higher selectivity to desired reaction products. (2, 3) Furthermore, we have reported that the simultaneous conversion of hemicellulose and cellulose can be achieved using GVL as a solvent in a single reactor, eliminating the need for pretreatment and/or sepa- ration steps. (4) Recently, we have taken advantage of accel- erated rates of cellulose and hemicellulose deconstruction in GVL-H2O solvent mixtures to develop a processing strategy to produce streams of C5 and C6 sugars (e.g., 130 g l � 1 ) from biomass. (5) Other polar aprotic solvents, such as g-lactones and tetrahydrofurans, have also shown comparable benefits to GVL in biomass conversion processes. (3) Herein, we report the effects of GVL and other polar aprotic solvents on acid-catalyzed biomass conversion reac- tions using acid catalysts that span a range of pKa values. The liquid-phase dehydration of xylose to furfural is catalyzed by Bronsted acids and serves as a probe reaction in the present study. We compare the reactivity trends displayed by these homogeneous acid catalysts in the liquid phase with the performance of solid acid catalysts, the latter of which have been shown to span a range of catalytic activities for the gas-

361 citations


Journal ArticleDOI
TL;DR: In this article, a detailed study of Ni-Cu bimetallic catalyst supported on nanopowder CeO2 is extensively investigated to suppress the methanation reaction as well as maintain high WGS reaction rate.

249 citations


Journal ArticleDOI
TL;DR: A simple method is reported to extract the charge transfer rates in carbon-coated LiFePO4 porous electrodes from chronoamperometry experiments, obtaining curved Tafel plots that contradict the Butler-Volmer equation but fit the Marcus-Hush-Chidsey prediction over a range of temperatures.
Abstract: Electrochemical kinetics are usually described by the Butler–Volmer equation. Bai and Bazant propose a method to extract reaction rates for porous electrodes from experiments and show the necessity of using Marcus charge transfer theory in place of the conventional kinetics.

229 citations


Journal ArticleDOI
TL;DR: In this article, a series of Pt/CeO2 catalysts with different Pt contents were prepared using an incipient wetness impregnation method and tested for CO oxidation, suggesting a Mars van-Krevelen type reaction on these catalysts and the interfacial Pt-O-Ce ensembles being the active sites.

175 citations


Journal ArticleDOI
TL;DR: The important role of hydroxyl for these two oxidation reactions catalyzed by gold, in terms of its influence on the turnover frequency is discussed, and the use of water as a "green" solvent becomes an attractive choice.
Abstract: Although gold is generally considered to be a relatively inert metal, supported gold nanoparticles have demonstrated exceptionally high catalytic activity for the oxidation of carbon monoxide and alcohols at modest temperatures. In both cases, the presence of hydroxyl groups substantially promotes the reaction rate, presumably by participating in the reaction. Direct comparisons of CO oxidation to alcohol oxidation over gold catalysts have been difficult for scientists to explain. The former reaction is usually performed with gas phase reagents, whereas the latter reaction is often performed in the condensed phase. In this Account, we discuss the important role of hydroxyl for these two oxidation reactions catalyzed by gold, in terms of its influence on the turnover frequency. During CO oxidation over gold, a hydroxyl can directly react with CO to form COOH, which eventually decomposes to CO2. The gas phase CO oxidation reaction likely occurs at the gold-support interface, where adsorbed hydroxyl groups can be found after the addition of water to the feed. When we perform CO oxidation in liquid water, increasing the pH substantially promotes the reaction rate by providing an external source of hydroxyl. Likewise, we can also promote alcohol oxidations over gold catalysts in aqueous media by increasing the pH of the system. Since the hydroxyl groups are supplied through the reaction medium instead of on the support surface, the gold-support interface is much less important in the aqueous phase reactions. Even bulk gold powder becomes an active oxidation catalyst in alkaline water. The role of O2 in both CO and alcohol oxidation in aqueous media is to remove electrons from the gold surface that are deposited during oxidation, maintaining electroneutrality. Thus, the oxidation of CO and alcohols in water at high pH is analogous to the electrochemical oxidation reactions performed on gold electrodes. As the field of chemistry continues to encourage the development of sustainable chemical processes utilizing environmentally benign reaction conditions, the use of water as a "green" solvent becomes an attractive choice. In general, however, heterogeneous catalysts that scientists have developed over the last century for the petrochemical industry have not been optimized for use in aqueous media. Given the active role of water in oxidation reactions catalyzed by gold, additional research is needed to understand how water affects other catalytic transformations on traditional transition metal catalysts.

170 citations


Journal ArticleDOI
TL;DR: In this paper, a combination of experimental measurements and numerical simulations are used to characterize the mechanical and electrochemical response of thin film amorphous Si electrodes during cyclic lithiation.
Abstract: A combination of experimental measurements and numerical simulations are used to characterize the mechanical and electrochemical response of thin film amorphous Si electrodes during cyclic lithiation. Parameters extracted from the experiment include the variation of elastic modulus and the flow stress as functions of Li concentration; the strain rate sensitivity; the diffusion coefficient for Li transport in the electrode; the free energy of mixing as a function of Li concentration in the electrode; the exchange current density for the Lithium insertion reaction; as well as reaction rates and diffusion coefficients characterizing the rate of formation of solid-electrolyte interphase layer at the electrode surface. Model predictions are compared with experimental measurements; and the implications for practical Si based electrodes are discussed.

168 citations


Journal ArticleDOI
TL;DR: In this paper, the Meerwein-Ponndorf-Verley (MPV) reduction of methyl levulinate (ML) to 4-hydroxypentanoates and subsequent lactonization to γ-valerolactone (GVL) catalyzed by Lewis acid zeolites was investigated.

166 citations


Journal ArticleDOI
Jie Li1, Yun Cheng1, Ming Jia1, Yiwei Tang1, Yue Lin1, Zhian Zhang1, Yexiang Liu1 
TL;DR: In this article, an electrochemical-thermal model is developed to predict electrochemical and thermal behaviors of commercial LiFePO4 battery during discharging process, and a series of temperatures and lithium ion concentrations dependent parameters relevant to the reaction rate and Li+ transport are employed in this model.

150 citations


Journal ArticleDOI
TL;DR: In this article, a detailed account of the kinetics and rechargeability of sodium-air batteries through a series of carefully designed tests on a treated commercial carbon material was provided, which indicated that discharge capacity is linearly correlated with surface area while morphology of the solid discharge product is strongly dependent on specific surface area and pore size.
Abstract: Rechargeable metal–air batteries are widely considered as the next generation high energy density electrochemical storage devices. The performance and rechargeability of these metal–air cells are highly dependent on the positive electrode material, where oxygen reduction and evolution reactions take place. Here, for the first time, we provide a detailed account of the kinetics and rechargeability of sodium–air batteries through a series of carefully designed tests on a treated commercial carbon material. Surface area and porous structure of the positive electrode material were controlled in order to gain detailed information about the reaction kinetics of sodium–air batteries. The results indicate that discharge capacity is linearly correlated with surface area while morphology of the solid discharge product is strongly dependent on specific surface area and pore size. Furthermore, it was found that the chemical composition of discharge products as well as charging overpotential is affected by discharge reaction rate.

146 citations


Journal ArticleDOI
TL;DR: For both regimes, the direct measurement of the spatial distribution of the pore scale reaction rate and conservative component concentration is shown to be crucial to understanding the departure from the Fickian scaling as well as quantifying the basic mechanisms that govern the mixing and reaction dynamics at the pORE scale.
Abstract: We propose a new experimental set up to characterize mixing and reactive transport in porous media with a high spatial resolution at the pore scale. The analogous porous medium consists of a Hele-Shaw cell containing a single layer of cylindrical solid grains built by soft lithography. On the one hand, the measurement of the local, intrapore, conservative concentration field is done using a fluorescent tracer. On the other hand, considering a fast bimolecular reaction A + B → C occurring as A displaces B, we quantify the rate of product formation from the spatially resolved measurement of the pore scale reaction rate, using a chemiluminescent reaction. The setup provides a dynamical measurement of the local concentration field over 3 orders of magnitude and allows investigating a wide range of Peclet and Damkohler numbers by varying the flow rate within the cell and the local reaction rate. We use it to study the kinetics of the reaction front between A and B. While the advection-dispersion (Fickian) theory, applied at the continuum scale, predicts a scaling of the cumulative mass of product C as MC ∝ √t, the experiments exhibit two distinct regimes in which the produced mass MC evolves faster than the Fickian behavior. In both regimes the front rate of product formation is controlled by the geometry of the mixing interface between the reactants. Initially, the invading solute is organized in stretched lamellae and the reaction is limited by mass transfer across the lamella boundaries. At longer times the front evolves into a second regime where lamellae coalesce and form a mixing zone whose temporal evolution controls the rate of product formation. In this second regime, the produced mass of C is directly proportional to the volume of the mixing zone defined from conservative species. This interesting property is indeed verified from a comparison of the reactive and conservative data. Hence, for both regimes, the direct measurement of the spatial distribution of the pore scale reaction rate and conservative component concentration is shown to be crucial to understanding the departure from the Fickian scaling as well as quantifying the basic mechanisms that govern the mixing and reaction dynamics at the pore scale.

Journal ArticleDOI
TL;DR: It is demonstrated that measurements of a single isotope are insufficient to constrain ab initio calculations, making the kinetic isotope effect in the cold regime necessary to remove ambiguity among possible potential energy surfaces.
Abstract: Quantum phenomena in the translational motion of reactants, which are usually negligible at room temperature, can dominate reaction dynamics at low temperatures. In such cold conditions, even the weak centrifugal force is enough to create a potential barrier that keeps reactants separated. However, reactions may still proceed through tunnelling because, at low temperatures, wave-like properties become important. At certain de Broglie wavelengths, the colliding particles can become trapped in long-lived metastable scattering states, leading to sharp increases in the total reaction rate. Here, we show that these metastable states are responsible for a dramatic, order-of-magnitude-strong, quantum kinetic isotope effect by measuring the absolute Penning ionization reaction rates between hydrogen isotopologues and metastable helium down to 0.01 K. We demonstrate that measurements of a single isotope are insufficient to constrain ab initio calculations, making the kinetic isotope effect in the cold regime necessary to remove ambiguity among possible potential energy surfaces.

Journal ArticleDOI
TL;DR: In this paper, the authors reported a systematic study on dehydrogenation of perhydro-N-ethylcarbazole over several important supported noble metal catalysts to identify the optimal catalyst for temperature-controlled de-hydrogenation.

Journal ArticleDOI
TL;DR: In this article, the effect of temperature, partial steam pressure, and particle size on the intrinsic hydration and dehydration reaction kinetics when natural materials are used was investigated, at reaction temperatures between 400 and 560 °C and partial steam pressures between 0 and 100 kPa.
Abstract: The calcium oxide hydration/dehydration reaction is proposed as a suitable reaction couple for thermochemical energy storage systems. However, limited work has been reported on the reaction kinetics of CaO/Ca(OH)2 under appropriate operation conditions for storage applications involving fluidized beds. This study focuses on the effect of temperature, partial steam pressure, and particle size upon the intrinsic hydration and dehydration reaction kinetics when natural materials are used. The experimental data have been fitted satisfactorily to a shrinking core model for both hydration and dehydration reactions, at reaction temperatures between 400 and 560 °C and partial steam pressures between 0 and 100 kPa. The reaction rates measured are higher than those previously reported in the literature. In the case of large particle sizes of natural material, particle attrition has been detected indicating the need to develop more suitable materials for thermochemical energy storage applications.

Journal ArticleDOI
TL;DR: In this article, a study of electro-oxidation of ethanol in alkaline medium over the carbon supported PdxNiy catalyst formulations synthesized by simultaneous reduction of the precursors using sodium borohydride as the reducing agent.
Abstract: The present investigation is based on a study of electro-oxidation of ethanol in alkaline medium over the carbon supported PdxNiy catalyst formulations synthesized by simultaneous reduction of the precursors using sodium borohydride as the reducing agent. X-ray diffraction studies of the PdNi/C nano-particles reveal formation of the face-centered cubic crystalline Pd, NiO and Ni(OH)2 on a meso porous carbon support whereas XPS confirmed the presence of metallic Ni and the oxide phases NiO, Ni(OH)2, NiOOH in the catalyst matrix. The structure and morphology of the binary matrix and the role of Ni and its oxide as a catalytically contributing entity in the oxidation process was ascertained by the help of respective analytical techniques like transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), voltammetry and chronoamperometry. Sequential oxidation steps were suggested involving dimeric (NiO)2 as one of the intermediate species during the oxidation reaction proceeding towards aldehyde formation and further to carbonate production via the intermediate formation of a six member ring, thereby increasing the reaction rates. This phenomenon has been discussed at molecular level using the results obtained from XPS analysis. The observations were further accomplished by extending the work to ion chromatography for quantitative analysis of the products formed during oxidation of ethanol. All the above results are congruent with the mechanistic interpretation and reflect the paramount significance of NiO existing in the binary catalyst matrix for accelerating ethanol oxidation reaction kinetics at a temperature 40 °C and above.

Journal ArticleDOI
TL;DR: In this paper, the catalytic properties of Pd@ZrO2 core-shell catalysts supported on Si-modified alumina were studied for application to methane oxidation and compared to the analogous Pd/CeO2 catalysts.
Abstract: The catalytic properties of Pd@ZrO2 core–shell catalysts supported on Si-modified alumina were studied for application to methane oxidation and compared to the analogous Pd@CeO2 catalysts. In the absence of water (dry conditions), both Pd@ZrO2 and Pd@CeO2 were highly active and showed nearly identical reaction rates and thermal stabilities. However, unlike catalysts based on Pd@CeO2, the Pd@ZrO2 catalysts were also very stable in the presence of high concentrations of water vapor. By means of Coulometric titration and pulse-reactor studies, we demonstrate that ZrO2 in contact with Pd can be reduced. Additionally, Coulometric titration showed that the Pd-PdO equilibrium at 600 °C is shifted to much lower P(O2) in the Pd@ZrO2 catalyst compared to conventional Pd/ZrO2 or Pd/Al2O3 catalysts. Because PdO is more active for methane oxidation, this observation provides a possible explanation for the superior performance of the Pd@ZrO2 catalyst.

Journal ArticleDOI
15 Mar 2014-Fuel
TL;DR: In this article, burnout simulations of coal char particles were carried out, adopting apparent char reactivity and a single-film model that includes the Stefan flow effect on mass and energy transfer.

Journal ArticleDOI
TL;DR: In this article, the reaction mechanism of CO2 hydrogenation by pyridine-based Ru-PNP catalyst in the presence of DBU base promoter was studied by means of density functional theory calculations.

Journal ArticleDOI
TL;DR: Cerium dioxide was used as reactive sorbent for the degradation of the organophosphate pesticides parathion methyl, chlorpyrifos, dichlofenthion, fenchlorphos, and prothiofos, as well as of some chemical warfare agents as mentioned in this paper.

Journal ArticleDOI
TL;DR: In this article, the reduction and oxidation reactions of a highly reactive Fe-based oxygen carrier for use in Chemical Looping Combustion (CLC) of gaseous fuels containing CH 4, CO and/or H 2, e.g., natural gas, syngas and PSA-off gas.

Journal ArticleDOI
TL;DR: In this article, the results of three-dimensional Direct Numerical Simulation (DNS) of moderate, intensive low-oxygen dilution (MILD) and conventional premixed turbulent combustion conducted using a skeletal mechanism including the effects of non-unity Lewis numbers and temperature dependent transport properties are analysed to investigate combustion characteristics using scalar gradient information.

Journal ArticleDOI
TL;DR: In this article, a photo-Fenton reaction with ferrioxalate complexes was shown to reduce the formation of strong Fe(III)-antibiotic complexes, which limits the photoreduction of Fe3+, decreasing the decomposition of H2O2 in the Fenton reaction and the overall efficiency of the photo-fenton process.

Journal ArticleDOI
TL;DR: In this article, the effects of initial methanol concentration in solution (C MeOH), photocatalyst content in suspension (C cat ), and incident light intensity (I 0 ) on the reaction rate have been investigated in detail.
Abstract: The kinetics and mechanism of photo-reforming reaction of methanol have been studied over Pt/TiO 2 suspensions irradiated with near-UV light ( λ max = 365 nm). The effects of initial methanol concentration in solution ( C MeOH ), photocatalyst content in suspension ( C cat ) and incident light intensity ( I 0 ) on the reaction rate have been investigated in detail. It has been found that the reaction rate depends strongly on methanol concentration and increases by more than two orders of magnitude with increase of C MeOH from zero to 1.0 M. The dependence of the reaction rate on C MeOH can be described by saturation-type kinetics according to the Langmuir–Hinselwood model. Increase of photocatalyst content in suspension results in an increase of the reaction rate, which tends to stabilize for C cat > 3 g L −1 . The rate of hydrogen evolution varies with incident light intensity in a manner which depends on the initial methanol concentration in solution. In particular, the order of the reaction with respect to I 0 is unity for C MeOH = 100 mM and 0.5 for C MeOH = 3.0 mM. Analysis of reaction intermediates in solution and on the photocatalyst surface indicates that, under the present experimental conditions, the reaction proceeds via progressive oxidation of adsorbed methoxy species to formaldehyde, dioxymethylene and formate. These species do not desorb from the photocatalyst surface but remain in the adsorbed mode until they are completely reformed to H 2 and CO 2 .

Journal ArticleDOI
TL;DR: In this article, a halogen-free flame retardant epoxy resin was prepared consisting of DOPO-based glycidyl ether of cresol formaldehyde novolac and diglycidyl acid of bisphenol.

Journal ArticleDOI
01 Dec 2014-Fuel
TL;DR: In this article, a comprehensive one-dimensional model accounting for the effects of heat and mass transfer, chemical kinetics, and drying was developed to describe the torrefaction of a single woody biomass particle.

Journal ArticleDOI
TL;DR: In this article, the second stage combustion of n-heptane droplets in microgravity is numerically studied with detailed chemistry and transport in order to obtain insight into the features controlling the low temperature second stage burn.

Journal ArticleDOI
TL;DR: The use of desilicated H-ZSM-5 as a heterogeneous acid catalyst for EL biodiesel production in a closed system (under autogeneous pressure) was studied in this paper, where the effect of reaction parameters such as ethanol to LA molar ratio (4:1 to 10:1), catalyst to LA ratio (0.10-0.25), speed of agitation (100-400 rpm), particle size (53-355 µm), reaction temperature (363-403 K), and reaction time (7
Abstract: BACKGROUND In the near future, fossil fuel will have limitations in terms of availability and also great concerns over its environmental impact. New routes and related technologies based on renewable feedstocks can overcome most of these problems associated with fossil fuel. Among current biodiesel sources, ethyl levulinate (EL) biodiesel obtained from catalytic esterification of renewable levulinic acid (LA) with ethanol has received a great deal of attention. The use of desilicated H-ZSM-5 (DH-ZSM-5) as heterogeneous acid catalyst for EL biodiesel production in a closed system (under autogeneous pressure) was studied. RESULTS The effect of reaction parameters such as ethanol to LA molar ratio (4:1 to 10:1), catalyst to LA ratio (0.10–0.25), speed of agitation (100–400 rpm), particle size (53–355 µm), reaction temperature (363–403 K) and reaction time (7 h) was investigated to maximize LA conversion. CONCLUSION Levulinic acid conversion reached 95% over DH-ZSM-5 and the catalyst was reusable for up to six cycles. This LA conversion and the catalyst reusability values are higher than others reported in the literature. A pseudo-homogeneous (P-H) kinetic model indicated that reaction rate constants increased with increasing molar ratio, catalyst to LA ratio and reaction temperature. The activation energy decreased from 73.14 to 21.08 kJ mol-1 when increasing the catalyst to LA ratio from 0.10 to 0.25, which implies a kinetically controlled reaction. © 2013 Society of Chemical Industry

Journal ArticleDOI
TL;DR: Hydrogen spillover is of great importance to understanding many phenomena in heterogeneous catalysis and has long been controversial, and well-defined nanoparticles are exploited to demonstrate its occurrence through evaluation of CO2 methanation kinetics.
Abstract: Hydrogen spillover is of great importance to understanding many phenomena in heterogeneous catalysis and has long been controversial. Here we exploit well-defined nanoparticles to demonstrate its occurrence through evaluation of CO2 methanation kinetics. Combining platinum and cobalt nanoparticles causes a substantial increase in reaction rate, but increasing the spatial separation between discrete cobalt and platinum entities results in a dramatic ∼50% drop in apparent activation energy, symptomatic of H atom surface diffusion limiting the reaction rate.

Journal ArticleDOI
27 Oct 2014-Langmuir
TL;DR: A projection of these heterogeneous kinetic rates to protein immobilization suggests that under coupling conditions in which low protein concentrations and buffers of near physiological pH are used, proteins are more likely physically adsorbed rather than covalently linked.
Abstract: N-Hydroxysuccinimide (NHS) ester terminal groups are commonly used to covalently couple amine-containing biomolecules (e.g., proteins and peptides) to surfaces via amide linkages. This one-step aminolysis is often performed in buffered aqueous solutions near physiological pH (pH 6 to pH 9). Under these conditions, the hydrolysis of the ester group competes with the amidization process, potentially degrading the efficiency of the coupling chemistry. The work herein examines the efficiency of covalent protein immobilization in borate buffer (50 mM, pH 8.50) using the thiolate monolayer formed by the chemisorption of dithiobis (succinimidyl propionate) (DSP) on gold films. The structure and reactivity of these adlayers are assessed via infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), electrochemical reductive desorption, and contact angle measurements. The hydrolysis of the DSP-based monolayer is proposed to follow a reaction mechanism with an initial nucleation step, in contrast to a simple pseudo first-order reaction rate law for the entire reaction, indicating a strong dependence of the interfacial reaction on the packing and presence of defects in the adlayer. This interpretation is used in the subsequent analysis of IR-ERS kinetic plots which give a heterogeneous aminolysis rate constant, ka, that is over 3 orders of magnitude lower than that of the heterogeneous hydrolysis rate constant, kh. More importantly, a projection of these heterogeneous kinetic rates to protein immobilization suggests that under coupling conditions in which low protein concentrations and buffers of near physiological pH are used, proteins are more likely physically adsorbed rather than covalently linked. This result is paramount for biosensors that use NHS chemistry for protein immobilization due to effects that may arise from noncovalently linked proteins.

Journal ArticleDOI
TL;DR: In this article, the influence of reaction temperature on crystal growth/assembly, structural modulation and transformation of metal-organic frameworks (MOFs) has been investigated, and the influence has been shown to have remarkable influence on the formation and structure of MOFs, especially toward the control of topology and dimensionality of the structures.