A DFT study on enhanced adsorption of H2 on Be-decorated porous graphene nanosheet and the effects of applied electrical fields

The adsorption of the hydrogen molecule on the pure porous graphene nanosheet (P-G) or the one decorated with Be atom (Be-G) was investigated by the first-principle DFT calculations. The Be atom was adsorbed on the P-G with a binding energy of ?1.287 eV to successfully establish the reasonable Be-G. The P-G was a poor substrate to interact weakly with the H₂, whereas the Be-G showed a high affinity to the adsorbed H₂ with an enhanced adsorption energy and transferred electrons of ?0.741 eV and 0.11 e, respectively. A molecular dynamics simulation showed that the H₂ could also be adsorbed on the Be-G at room temperature with a reasonable adsorption energy of ?0.707 eV. The interaction between the adsorbed H₂ and the Be-G was further enhanced with the external electrical fields. The applied electrical field of ?0.4 V/Å was found to be the most effective to enhance the adsorption of H₂ on the Be-G with the modified adsorption energy and the improved transferred electrons being ?0.708 eV and 0.17 e, respectively. Our study shows that the Be-G is a promising substrate to interact strongly with the H₂ and could be applied as a high-performance hydrogen gas sensor, especially under the external electrical field.     

Decomposition of hydrogen sulfide (H2S) on Ni(100) and Ni3Al(100) surfaces from first-principles

Spin-polarized density functional theory studies of hydrogen sulfide (H₂S) adsorption and decomposition on Ni(100) and Ni₃Al(100) surfaces were conducted to understand the aluminum (Al) alloying effect on H₂S dissociation. For such purpose, we first determined the near surface structure of fully ordered Ni₃Al alloy along the [100] direction by calculating the Al segregation energy to the surface and then examined the adsorption energies of the adsorbates (H₂S, HS, S, and H) and the activation barriers for the H₂S and HS decomposition by using Climbing Image-Nudged Elastic Band method. We found that regardless of the way to terminate the surface, Al atom in bimetallic Ni₃Al(100) tends to exist in the first surface layer, rather than in the second or third layer, and the Ni₃Al(100) surface can substantially retard the H₂S decomposition by reducing the adsorption energy of sulfur compounds compared to the pure Ni(100) case. Finally, we presented how the Al in Ni₃Al modifies the activity of surface Ni atoms toward the sulfur compounds by calculating the local density of states and charge distribution in alloying components. This work hints the importance of knowing how to properly tailor the reactivity of Ni based materials to enhance the resistance for sulfur poisoning.     

Promoted photoinduced charge separation and directional electron transfer over dispersible xanthene dyes sensitized graphene sheets for efficient solar H2 evolution

Directional electron transfer and effective charge separation facilitated by graphene sheets have provided an inspiring approach to enhance the efficiencies of photoelectric conversion and photocatalysis. Herein, we demonstrated the feasibility of constructing a high-performance of the dye-sensitized H₂ evolution system using dispersible graphene sheets as both efficient electron transfer carrier and catalyst scaffold. Among the xanthene dyes sensitized H₂ evolution catalysts in this study, photocatalyst of Rose Bengal (RB) sensitized graphene decorated with Pt is the most active one and exhibits the highest apparent quantum efficiency (AQE) of 18.5% at wavelength of 550 nm and rather long-term stability for H₂ evolution. Dispersible graphene sheets can not only capture electrons from the excited dye and then transfer them to the decorated catalysts efficiently for improving charge separation with a small energy loss, but also afford large interfaces for highly dispersing catalyst nanoparticles with more active sites, thereby significantly enhancing the H₂ evolution efficiency than graphite oxide (GO) and multiwall carbon nanotubes (MWCNTs). This work proposes a potential strategy to develop efficient photocatalytic systems for solar-energy-conversion and provides a new insight into mechanistic study of photoinduced electron transfer by effective synergetic combination of dispersible graphene sheets with an efficient dye and a H₂ evolution catalyst.     

Hydrogen storage capacities of alkali and alkaline-earth metal atoms on SiC monolayer: A first-principles study

A detailed theoretical Density-Functional-Theory-based investigation of hydrogen adsorption on silicon carbide monolayers (SiC-ML) decorated with alkali and alkaline-earth metal atoms is presented. The results show that the favourable position for all adsorbed metal atoms is above a Si atom. These metal atoms are chemisorbed to the SiC-ML, except for Mg which is physisorbed. The adsorbed atoms act in turn as adsorption sites for H₂ molecules. The single-sided K-functionalized SiC-ML can store up to six H₂ molecules. For double-side K-decorated SiC-ML, up to ten H₂ molecules can be captured. In all cases, the H₂ molecules are physisorbed. This is beneficial because the breaking of chemical bonds, which otherwise would be needed to make use of the stored H₂, is energetically expensive. These results find decorated SiC-ML as a promising material for hydrogen storage systems.     

Light metal functionalized two-dimensional siligene for high capacity hydrogen storage: DFT study

In this work, the hydrogen storage capacities of two-dimensional siligene (2D-SiGe) functionalized with alkali metal (AM) and alkali-earth metal (AEM) atoms were studied using density functional theory calculations. One AM (Li, Na, K) or AEM (Be, Mg, Ca) atom was placed on the 2D-SiGe surface, and several H₂ molecules were placed in the vicinity of the adatom. The results demonstrate that the most favorable siligene site for the adsorption of Li, Na, K and Be atoms is the hollow site, while for the Mg and Ca atoms is the down site. The AM atoms are the only ones with considerable binding energies on the SiGe nanosheets. Pristine 2D-SiGe slightly adsorbs one H₂ molecule per hollow site and, therefore, it is not suitable for hydrogen storage. In some of the AM- and AEM-decorated 2D-SiGe, several hydrogen molecules can be physisorbed. In particular, the Na-, K- and Ca-functionalized 2D-SiGe can adsorb six hydrogen molecules, whereas Li and Mg atoms adsorbed three hydrogen molecules, and the Be adatom only adsorbed one hydrogen molecule. The complexes formed by hydrogen molecules adsorbed on the analyzed metal decorated 2D-SiGe are energetically stable, indicating that functionalized 2D-SiGe could be an efficient molecular hydrogen storage media.     

The enhancement of hydrogen storage capacity in Li,Na and Mg-decorated BC3 graphene by CLICH and RICH algorithms

New hydrogen adsorption states on Li, Na, and Mg-decorated graphene-type BC₃ sheet have been investigated by first-principles calculations. The structural, electronic and binding properties, metal binding and nH₂ (n = 1–10) adsorption states of these systems are studied in detail with the Mulliken analysis, charge density differences, and partial density of states. To enhance the number of the adsorbed H₂ molecules per metal atom, and also to generate the better initial coordinates for reducing the simulation time, we present two masthematical algorithms (CLICH and RICH). The tested results on BC₃ sheet and boron-doped graphene (C₃₀B₂) show that these algorithms can increase the number of adsorbed hydrogen molecules by minimizing the computational time. It is seen that nH₂ (n = 1–10) adsorbed Li,/Na and/Mg-decorated BC₃ single- and double-sided systems are industrial materials for hydrogen storage technology, their adsorption energies fall into the acceptable adsorption energy range (0.20–0.60 eV/H₂). It is concluded from the optimized geometries and charge density differences for the higher number of H₂ adsorbed systems that not only decorated metal atom but also the sheet plays an important role in hydrogen storage process, because the boron atoms in the sheet expand the induced electric field between the adatoms and BC₃ sheet. From Mulliken analysis, there is a charge transfer mechanism between H₂ molecules and metal atoms. Moreover, the resonant peaks for the sheet, metal atoms and H₂ molecules in partial density of states curves indicate the possible hybridizations. Additionally, these adsorption processes are supported by charge density difference plots.     

Hydrogen adsorption on pristine and platinum decorated graphene quantum dot: A first principle study

In the ever growing demand of future energy resources, hydrogen production reaction has attracted much attention among the scientific community. In this work, we have investigated the hydrogen evolution reaction (HER) activity on an open-shell polyaromatic hydrocarbon (PAH), graphene quantum dot “triangulene” using first principles based density functional theory (DFT) by means of adsorption mechanism and electronic density of states calculations. The free energy calculated from the adsorption energy for graphene quantum dot (GQD) later guides us to foresee the best suitable catalyst among quantum dots. Triangulene provides better HER with hydrogen placed at top site with the adsorption energy as −0.264 eV. Further, we have studied platinum decorated triangulene for hydrogen storage. Three different sites on triangulene were considered for platinum atom adsorption namely top site of carbon (C) atom, hollow site of the hexagon carbon ring near triangulene's unpaired electron and bridge site over C–C bond. It is found that the platinum atom is more stable on the hollow site than top and bridge site. We have calculated the density of states (DOS), highest occupied molecular orbitals (HOMO), lowest unoccupied molecular orbitals (LUMO) and HOMO-LUMO gap of hydrogen molecule adsorbed platinum decorated triangulene. Our results show that the hydrogen molecule (H₂) dissociates instinctively on all three considered sites of platinum decorated triangulene resulting in D-mode. The fundamental understanding of adsorption mechanism along with analyses of electronic properties will be important for further spillover mechanism and synthesis of high-performance GQD for H₂ storage applications.     

Hydrogen storage on Ti decorated SiC nanostructures: A first principles study

In the present study we report the hydrogen adsorption behavior of two SiC nanostructures; a planar sheet and a nanotube (10, 0) of 1 nm diameter decorated by Ti atoms on it. All calculations have been performed using a plane-wave based pseudopotential method. The lowest energy structure of the Ti adsorbed SiC sheet shows that Ti atom distorts the sheet in such a way that one of the Si atoms goes down the plane and the Ti atom bind with nearest three C atoms. The interaction of this Ti decorated sheet with hydrogen suggests that each Ti atom can bind up to four hydrogen molecules (all hydrogens are adsorbed in the molecular form) with an average binding energy of 0.37 eV. For SiC nanotube, the adsorption of Ti favors the hexagonal hollow site. Moreover, on interaction of this Ti decorated tube with hydrogen leads to dissociation of the first hydrogen molecule in the atomic form and thereafter adsorbs hydrogen in the molecular form. The average binding energy of hydrogen molecules on this Ti decorated tube is estimated to be 0.65 eV. Based on these results we infer that the Ti decorated SiC nanostructures moderately bind with hydrogen molecules (within the energy window for hydrogen storage materials) and therefore, can be considered as one of the potential hydrogen storage material.     

Hydrogen storage of dual-Ti-doped single-walled carbon nanotubes

The hydrogen adsorption capacity of dual-Ti-doped (7, 7) single-walled carbon nanotube (Ti-SWCNTs) has been studied by the first principles calculations. Ti atoms show different characters at different locations due to local doping environment and patterns. The dual-Ti-doped SWCNTs can stably adsorb up to six H₂ molecules through Kubas interaction at the Ti₂ active center. The intrinsic curvature and the different doping pattern of Ti-SWCNTs induce charge discrepancy between these two Ti atoms, and result in different hydrogen adsorption capacity. Particularly, eight H₂ molecules can be adsorbed on both sides of the dual-Ti decorated SWCNT with ideal adsorption energy of 0.198 eV/H₂, and the physisorption H₂ on the inside Ti atom has desirable adsorption energy of 0.107 eV/H₂, ideal for efficient reversible storage of hydrogen. The synergistic effect of Ti atoms with different doping patterns enhances the hydrogen adsorption capacity 4.5H₂s/Ti of the Ti-doped SWCNT (VIII), and this awaits experimental trial.     

H2S removal from biogas for fuelling MCFCs: New adsorbing materials

Cu and Zn modified 13X zeolites prepared by ion exchange or impregnation and activated carbons (ACs) treated with KOH, NaOH or Na₂CO₃ solutions were studied as H₂S sorbents for biogas purification for fuelling molten carbonate fuel cells. H₂S sorption was studied in a new experimental set-up equipped with a high sensitivity potentiometric system for the analysis of H₂S. Breakthrough curves were obtained at 40 °C with a fixed bed of 20 mg of the samples under a stream (6 L h⁻¹) of 8 ppm H₂S/He mixture. The adsorption properties of 13X zeolite improved with addition of Cu or Zn:Cu exchanged zeolite showed the best performances with a breakthrough time of 580 min at 0.5 ppm H₂S, that is 12 times longer than the parent zeolite. In general, unmodified and modified ACs were more effective H₂S sorbents than zeolites. Treating ACs with NaOH, KOH, or Na₂CO₃ solutions improved the H₂S adsorption properties: AC treated with Na₂CO₃ was the most effective sorbent, showing a breakthrough time of 1222 min at 0.5 ppm, that is twice the time of the parent AC.     

Mechanisms of H2 generation for metal doped Al16M (M = Mg and Bi) clusters in water

We have systematically investigated the hydrolysis mechanism of metal doped Al₁₆M (M = Al, Mg and Bi) clusters with H₂O molecules and proposed a reasonable elucidation for the experimentally observed fast H₂ generation rate and high H₂ yield in the Al–Bi based composite. Mg and Bi showed negative effect on the dissociation process of the first H₂O molecule, but accelerated further H₂ generation process. The investigation of persistent hydrolysis reactions demonstrated that the proton-transfer way makes the aluminum–water reaction a lasting process in the long-term H₂ generation in existence of Bi atom, which explains not only the previously observed fast H₂ generation rate but also high H₂ yields in the Bi added Al powder. Our experimental results of hydrogen generation form Al–Bi (Mg) mixture and water are in good agreement with the theory prediction. The facilitated hydrolysis reaction in Al₁₆Bi cluster is attributed to the weakened hydroxide adsorption with the presence of Bi in the aluminum cluster, which is the key factor to accelerate the proton-transfer process.     

Influence of Pt decoration on the hydrogen storage performance of cup-stacked carbon nanotubes: A DFT study

The hydrogen adsorption behaviour of cup-stacked carbon nanotubes (CSCNTs) decorated with the platinum atom at four positions of the conical graphene layer (CGL) is investigated using density functional theory. The optimization shows that the inside lower edge position (IL) results have the best hydrogen adsorption parameters among the four positions. The Pt–H₂ distance is 1.54 Å, the H–H bond length (l_H-H) is 1.942 Å, and the hydrogen adsorption energy (E_ads) is 1.51 eV. The hydrogen adsorption of CSCNTs decorated by Pt at the IL position also has larger E_ads and l_H-H than the Pt-doped planar graphene, Pt-doped single-wall carbon nanotubes and Pt-doped carbon nanocones. The Pt atom at the IL position has a more significant polarization effect on the adsorbed H₂, it has trends to convert H₂ into two separate H atoms. While the hydrogen adsorption behaviour at other positions belongs to the Kubas coordination, the l_H-H and the E_ads increased not significantly.     

Hydrogen storage on uncharged and positively charged Mg-decorated graphene

The storage of H₂ molecules was studied theoretically on charged and uncharged Mg decorated graphene surfaces using density-functional theory and by incorporating the van der Waals (vdW) interactions. We found that an increase in the number of Mg atoms and H₂ molecule increases the net interaction of the hydrogen molecule with the surface. The Mg-Gr⁺ has the hydrogen storage capacity of up to nine H₂ molecules, with the average adsorption energy of −0.134 eV/H₂. Also, we found that hydrogen molecules play an important role in the interaction between the graphene surface and the Mg atom. The charge density difference analysis showed that electron transfer occurs from H₂ molecules to Mg atom in uncharged system. However, the Bader charge analysis showed that the positive charges in the Mg-Gr⁺ and nH₂-Mg-Gr⁺ systems are concentrated on the Mg atom. When the number of H₂ molecules reaches more than 4, the charge transfer instead occurs from the Mg atom to H₂ molecules as well as to the graphene surface. This results in better interaction between the Mg atom and the Gr⁺ surface.     

Theoretical investigation of adsorption and dissociation of H2 on (ZrO2)n (n=1-6) clusters

The structure, vibration, and electronic structure of H₂ molecule adsorbed on (ZrO₂)_n (n = 1-6) clusters were investigated with density functional theory. We found that H₂ is easily absorbed on the top Zr atoms of (ZrO₂)_n (n = 1-6) clusters. The Zr₅O₁₀H₂ cluster has the lowest binding energies in the Zr_nO_2nH₂ (n = 1-6) clusters. By analyzing vibrational frequency and Mulliken charge, the H-O and Zr-H bonds were found to be formed in different sized Zr_nO_2nH₂ clusters. The dissociation mechanism of H₂ shows that the charge transfers from (ZrO₂)_n cluster to H₂ due to the important role of the orbital hybridization between the cluster and H₂ molecule. With increasing the number of H₂ molecule adsorbed on (ZrO₂)_n clusters, the adsorption favors to the sites with low coordinate number, and these adsorption modes present a symmetrical tendency.     

Economic assessment of biogas-to-electricity generation system with H2S removal by activated carbon in small pig farm

This study was conducted to assess the economic feasibility of electricity generation from biogas in small pig farms with and without the H₂S removal prior to biogas utilisation. The 2% potassium iodide (KI) impregnated activated carbon selected as H₂S adsorbent was introduced to a biogas-to-electricity generation system in a small pig farm in Thailand as a case study. With the average inlet H₂S concentration of about 2400 ppm to the adsorption unit, the H₂S removal efficiency could reach 100% with the adsorption capacity of 0.062 kg of H₂S/kg of adsorbent. Under the reference scenario (i.e., 45% subsidy on digester installation and fixed electricity price at 0.06 Euro/kWh) and based on an assumption that the biogas was fully utilised for electricity generation in the system, the payback period for the system without H₂S removal was about 4 years. With H₂S removal, the payback period was within the economic life of digester but almost twice that of the case without H₂S removal. The impact of electricity price could be clearly seen for the case of treated biogas. At the electricity price fixed at 0.07 Euro/kWh, the payback period for the case of treated biogas was reduced to about 5.5 years, with a trend to decrease at higher electricity prices. For both treated and untreated biogas, the governmental subsidy was the important factor determining the economics of the biogas-to-electricity systems. Without subsidy, the payback period increased to almost 7 years and about 11 years for the case of untreated and treated biogas, respectively, at the reference electricity price. Although the H₂S removal added high operation cost to the system, it is still highly recommended not only for preventing engine corrosion but also for the environment benefit in which air pollution by H₂S/SO₂ emission and impact on human health could be potentially reduced.     

Computational insights of alkali metal (Li / Na / K) atom decorated buckled bismuthene for hydrogen storage

The mechanism of hydrogen molecule adsorption on 2D buckled bismuthene (b-Bi) monolayer decorated with alkali metal atoms was studied using density functional theory based first principles calculations. The decorated atoms Li, Na and K exhibited distribution on surface of b-Bi monolayer with increasing binding energy of 2.6 eV, 2.9 eV and 3.6 eV respectively. The adsorption of H₂ molecule on the slabs appeared stable which was further improved upon inclusion of van der Waals interactions. The adsorption behaviour of H₂ molecules on the decorated slabs is physisorption whereas the slabs were able to bind up to five H₂ molecules. The average adsorption energy per H₂ molecules are in range of 0.1–0.2 eV which is good for practical applications. The molecular dynamics simulation also confirmed the thermodynamic stabilities of five H₂ molecules adsorbed on the decorated slabs. The storage capacity values are found 2.24 wt %, 2.1 wt %, and 2 wt %, for respective cases of Li, Na and K atoms decorated b-Bi. The analysis of the adsorbed cases pointed to electrostatic interaction of Li and H₂ molecule. The adsorption energies, binding energies, charge analysis, structural stability, density of states, and hydrogen adsorption percentage specifies that the decorated b-Bi may serve as an efficient hydrogen storage material and could be an effective medium to interact with hydrogen molecules at room temperature.     

An ab initio study of dissociative adsorption of H2 on FeTi surfaces

Dissociative adsorption of H₂ on clean FeTi (001), (110) and (111) surfaces is investigated via ab initio pseudopotential-plane wave method. Adsorption energies of H atom and H₂ molecule on Fe and Ti terminated (001) and (111) and FeTi (110) surfaces are calculated on high symmetry adsorption sites. It is shown that, top site is the most stable site for horizontal H₂ molecule adsorption on (001) and (111) surfaces for both terminations. The most favorable site for H atom adsorption on these surfaces however, is the bridge site. In (110) surface, the 3-fold hollow site which is composed of a long Ti–Ti bridge and an Fe atom, (Ti–Ti)_L–Fe, and again a 3-fold hollow site this time composed of a short Ti–Ti bridge and an Fe atom, (Ti–Ti)_S–Fe, are the most stable sites for H₂ and H adsorption, respectively. With the analysis of the above favorable adsorption sites, probable dissociation paths for H₂ molecule over these surfaces are proposed. Activation energies of these dissociations are also determined with the use of the dynamics of the H₂ relaxation and climbing image nudged elastic band method. It is found that H₂ dissociation on (110) and Fe terminated (111) surfaces has no activation energy barrier. On other surfaces however, activation energies are calculated to be 0.178 and 0.190 eV per H₂ molecule for Fe and Ti terminated (001) surfaces respectively, and 1.164 eV for Ti terminated (111) surface.     

Mechanism for adsorption,dissociation and diffusion of hydrogen in hydrogen permeation barrier of α-Al2O3: A density functional theory study

Toward understanding physical interaction of hydrogen isotopes with α-Al₂O₃ barrier, adsorption, dissociation and diffusion of hydrogen in α-Al₂O₃(0001) slab have been investigated by density functional theory (DFT) and rate theory. H₂ molecule, with parallel configuration, preferentially absorbs on a top Al atom site of first atomic layer on α-Al₂O₃(0001) surface, while H atom strongly bonds at a top O atom site of the second atomic layer, H atoms recombine into molecules on top Al atom sites of the third atomic layer. The barrier for H₂ exothermic dissociation on surface is 0.79 eV. The potential energy pathways of H diffusion in α-Al₂O₃ are studied, predicting that H atom diffusion preferentially occurs via surface path rather than bulk path involving elementary reorientation and hopping steps. The surface-to-subsurface diffusion is significantly endothermic except for the surface and subsurface-to-bulk path. Mechanism, in well agreement with experimental result, of α-Al₂O₃ resisting hydrogen permeation has proposed.     

Alkali and transition metal atom-functionalized germanene for hydrogen storage: A DFT investigation

In this work, we have performed density functional theory-based calculations to study the adsorption of H₂ molecules on germanene decorated with alkali atoms (AM) and transition metal atoms (TM). The cohesive energy indicates that interaction between AM (TM) atoms and germanene is strong. The values of the adsorption energies of H₂ molecules on the AM or TM atoms are in the range physisorption. The K-decorated germanene has the largest storage capacity, being able to bind up to six H₂ molecules, whereas the Au and Na atoms adsorbed five and four H₂ molecules, respectively. Li and Ag atoms can bind a maximum of three H₂ molecules, while Cu-decorated germanene only adsorbed one H₂ molecule. Formation energies show that all the studied cases of H₂ molecules adsorbed on AM and TM atom-decorated germanene are energetically favorable. These results indicate that decorated germanene can serve as a hydrogen storage system.     

Effect of boron substitution on hydrogen storage in Ca/DCV graphene: A first-principle study

By using density functional calculations, the effects of boron are investigated in the new hydrogen storage systems, which are formed by substituting different numbers of boron atoms to the first (BDDCV-F) and the second (BDDCV-S) neighbor of double carbon-vacancy (DCV). The layered host systems of boron-substituted DCV graphene are decorated with Ca metal to increase the number of adsorbed H₂ molecules. Storing of H₂ applications are performed by using two coordinate algorithms as CLICH (Cap-Like Initial Conditions for Hydrogens) and RICH (Rotational Initial Conditions for Hydrogens). The adsorption properties of (1–14) H₂ molecules on the constructed systems are examined. The results for BDDCV-F and BDDCV-S boron-doped systems are compared with each other and those of the pure-DCV graphene. To compare the stabilities of BDDCV-systems, the formation energies are calculated. It is concluded from Mulliken charge analysis, the partial density of states and electron density differences that boron substitution process to different locations of the DCV graphene plays a crucial role on the charge transfer between Ca atom the layered host system, ionic nature and the binding properties of the systems. The herringbone-like anisotropic electron density is transformed to isotropic density with the substitution of the boron atoms. Then, the electric field, which is induced by ionic interactions and governs H₂ adsorption processes, is changed and intensified along with the sheet. In this way, it can be achieved more effective H₂ adsorption. It is seen from the adsorption energies of single- and double-side Ca-decorated systems that the processes of boron-substitution and Ca-decoration can considerably improve the hydrogen storage capability of pure-DCV graphene system, thus (8 and 10)H₂ can be adsorbed per Ca-atom in these-type systems. The high gravimetric density of 5.80% is calculated, although larger cell and empty surface states. Moreover, the average desorption temperatures are calculated by using van't Hoff equation, and it is seen that the DCV including boron-substituted systems have closer desorption temperatures to the room temperature than pure-DCV. To check the H₂ desorption of the systems, molecular dynamics simulations are performed at 200 K and 300 K temperatures.