Clathrate compound

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A clathrate is a chemical substance consisting of a lattice that traps or contains molecules. The word clathrate is derived from the Latin clathratus (clatratus), meaning 'with bars, latticed'. [1] Most clathrate compounds are polymeric and completely envelop the guest molecule, but in modern usage clathrates also include host–guest complexes and inclusion compounds. [2] According to IUPAC, clathrates are inclusion compounds "in which the guest molecule is in a cage formed by the host molecule or by a lattice of host molecules." [3] The term refers to many molecular hosts, including calixarenes and cyclodextrins and even some inorganic polymers such as zeolites.

Contents

Clathrate cavities. For example, 5 (dodecahedral) and 5 6 (tetrakaidecahedral) make up a Type I (sI) structure. Clathrate hydrate cages.svg
Clathrate cavities. For example, 5 (dodecahedral) and 5 6 (tetrakaidecahedral) make up a Type I (sI) structure.

Clathrates can be divided into two categories: clathrate hydrates and inorganic clathrates. Each clathrate is made up of a framework and guests that reside the framework. Most common clathrate crystal structures can be composed of cavities such as dodecahedral, tetrakaidecahedral, and hexakaidecahedral cavities.

The molar fraction of water of most clathrate hydrates is 85%. Clathrate hydrates are derived from organic hydrogen-bonded frameworks. These frameworks are prepared from molecules that "self-associate" by multiple hydrogen-bonding interactions. Small molecules or gases (i.e. methane, carbon dioxide, hydrogen) can be encaged as a guest in hydrates. The ideal guest/host ratio for clathrate hydrates range from 0.8 to 0.9. The guest interaction with the host is limited to van der Waals forces. Certain exceptions exist in semiclathrates where guests incorporate into the host structure via hydrogen bonding with the host structure. Hydrates form often with partial guest filling and collapse in the absence of guests occupying the water cages. Like ice, clathrate hydrates are stable at low temperatures and high pressure and possess similar properties like electrical resistivity. Clathrate hydrates are naturally occurring and can be found in the permafrost and oceanic sediments. Hydrates can also be synthesized through seed crystallization or using amorphous precursors for nucleation. [4]

Unlike hydrates, inorganic clathrates have a covalently bonded framework of inorganic atoms with guests typically consisting of alkali or alkaline earth metals. Due to the stronger covalent bonding, the cages are often smaller than hydrates. Guest atoms interact with the host by ionic or covalent bonds. Therefore, partial substitution of guest atoms follow Zintl rules so that the charge of the overall compound is conserved. Most inorganic clathrates have full occupancy of its framework cages by a guest atom to be in stable phase. Inorganic clathrates can be synthesized by direct reaction using ball milling at high temperatures or high pressures. Crystallization from melt in another common synthesis route. Due to the wide variety of composition of host and guest species, inorganic clathrates are much more chemically diverse and possess a wide range of properties. Most notably, inorganic clathrates can be found to be both an insulator and a superconductor (Ba8Si46). A common property of inorganic clathrates that has attracted researchers is low thermal conductivity. Low thermal conductivity is attributed to the ability of the guest atom to "rattle" within the host framework. The freedom of movement of the guest atoms scatters phonons that transport heat. [4]

Crystal structure of Na8Si46. Example of a Type I clathrate consisting of dodecahedral (orange) and tetrakaidecahedral (yellow) silicon cavities containing sodium atoms. Na8Si46 inorganic clathrate structure with coordination polyhedra.png
Crystal structure of Na8Si46. Example of a Type I clathrate consisting of dodecahedral (orange) and tetrakaidecahedral (yellow) silicon cavities containing sodium atoms.

Examples

Portion of the lattice of the clathrate xenon-paraquinol. Xenon-paraquinol (JAMKEN) clathrate.png
Portion of the lattice of the clathrate xenon-paraquinol.

Clathrates have been explored for many applications including: gas storage, gas production, gas separation, desalination, thermoelectrics, photovoltaics, and batteries.

Cd(CN)2*CCl4: Cadmium cyanide clathrate framework (in blue) containing carbon tetrachloride (C atoms in gray and disordered Cl positions in green) as guest. Cd(CN)2CCl4.jpg
Cd(CN)2·CCl4: Cadmium cyanide clathrate framework (in blue) containing carbon tetrachloride (C atoms in gray and disordered Cl positions in green) as guest.
MOF-5, an example of a metal organic framework: the yellow sphere represents the guest cavity. IRMOF-1 wiki.png
MOF-5, an example of a metal organic framework: the yellow sphere represents the guest cavity.

History

Clathrate hydrates were discovered in 1810 by Humphry Davy. [9] Clathrates were studied by P. Pfeiffer in 1927 and in 1930, E. Hertel defined "molecular compounds" as substances decomposed into individual components following the mass action law in solution or gas state. Clathrate hydrates were discovered to form blockages in gas pipelines in 1934 by Hammerschmidt that led to increase in research to avoid hydrate formation. [10] In 1945, H. M. Powell analyzed the crystal structure of these compounds and named them clathrates. Gas production through methane hydrates has since been realized and has been tested for energy production in Japan and China. [4]

Inclusion compounds are often molecules, whereas clathrates are typically polymeric[ citation needed ]. Intercalation compounds are not 3-dimensional, unlike clathrate compounds. Photolytically-sensitive caged compounds have been examined as containers for releasing a drug or reagent. [11]

Zeolites are another type of crystalline structures that form a framework with cavities in which guest species can reside. Unlike clathrates, zeolites are defined by the tetrahedra linking of four oxygen atoms surrounding a cation.[ citation needed ] The guests are also not required to fill the open cavities. Zeolite structures are defined by the diverse building units of the framework, as opposed to cavity structures in clathrates. Similar applications have been explored.

Silica clathrasil are compounds structurally similar to clathrate hydrates with a SiO2 framework and can be found in a range of marine sediment. [12]

See also

Related Research Articles

<span class="mw-page-title-main">Clathrate hydrate</span> Crystalline solid containing molecules caged in a lattice of frozen water

Clathrate hydrates, or gas hydrates, clathrates, or hydrates, are crystalline water-based solids physically resembling ice, in which small non-polar molecules or polar molecules with large hydrophobic moieties are trapped inside "cages" of hydrogen bonded, frozen water molecules. In other words, clathrate hydrates are clathrate compounds in which the host molecule is water and the guest molecule is typically a gas or liquid. Without the support of the trapped molecules, the lattice structure of hydrate clathrates would collapse into conventional ice crystal structure or liquid water. Most low molecular weight gases, including O2, H2, N2, CO2, CH4, H2S, Ar, Kr, and Xe, as well as some higher hydrocarbons and freons, will form hydrates at suitable temperatures and pressures. Clathrate hydrates are not officially chemical compounds, as the enclathrated guest molecules are never bonded to the lattice. The formation and decomposition of clathrate hydrates are first order phase transitions, not chemical reactions. Their detailed formation and decomposition mechanisms on a molecular level are still not well understood. Clathrate hydrates were first documented in 1810 by Sir Humphry Davy who found that water was a primary component of what was earlier thought to be solidified chlorine.

In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was understood.

Zeolites are microporous, crystalline aluminosilicate materials commonly used as commercial adsorbents and catalysts. They mainly consist of silicon, aluminium, oxygen, and have the general formula Mn+
1/n
(AlO
2
)
(SiO
2
)
x
・yH
2
O
where Mn+
1/n
is either a metal ion or H+. These positive ions can be exchanged for others in a contacting electrolyte solution. H+
exchanged zeolites are particularly useful as solid acid catalysts.

In chemistry, noble gas compounds are chemical compounds that include an element from the noble gases, group 18 of the periodic table. Although the noble gases are generally unreactive elements, many such compounds have been observed, particularly involving the element xenon.

<span class="mw-page-title-main">Thermoelectric materials</span> Materials whose temperature variance leads to voltage change

Thermoelectric materials show the thermoelectric effect in a strong or convenient form.

<span class="mw-page-title-main">Catenation</span> Bonding of atoms of the same element into chains or rings

In chemistry, catenation is the bonding of atoms of the same element into a series, called a chain. A chain or a ring shape may be open if its ends are not bonded to each other, or closed if they are bonded in a ring. The words to catenate and catenation reflect the Latin root catena, "chain".

In chemistry, water(s) of crystallization or water(s) of hydration are water molecules that are present inside crystals. Water is often incorporated in the formation of crystals from aqueous solutions. In some contexts, water of crystallization is the total mass of water in a substance at a given temperature and is mostly present in a definite (stoichiometric) ratio. Classically, "water of crystallization" refers to water that is found in the crystalline framework of a metal complex or a salt, which is not directly bonded to the metal cation.

<span class="mw-page-title-main">Intercalation (chemistry)</span> Reversible insertion of an ion into a material with layered structure

In chemistry, intercalation is the reversible inclusion or insertion of a molecule into layered materials with layered structures. Examples are found in graphite and transition metal dichalcogenides.

<span class="mw-page-title-main">Sodium aluminate</span> Chemical compound

Sodium aluminate is an inorganic chemical that is used as an effective source of aluminium hydroxide for many industrial and technical applications. Pure sodium aluminate (anhydrous) is a white crystalline solid having a formula variously given as NaAlO2, NaAl(OH)4 (hydrated), Na2O·Al2O3, or Na2Al2O4. Commercial sodium aluminate is available as a solution or a solid.
Other related compounds, sometimes called sodium aluminate, prepared by reaction of Na2O and Al2O3 are Na5AlO4 which contains discrete AlO45− anions, Na7Al3O8 and Na17Al5O16 which contain complex polymeric anions, and NaAl11O17, once mistakenly believed to be β-alumina, a phase of aluminium oxide.

<span class="mw-page-title-main">Tetrahedral molecular geometry</span> Central atom with four substituents located at the corners of a tetrahedron

In a tetrahedral molecular geometry, a central atom is located at the center with four substituents that are located at the corners of a tetrahedron. The bond angles are cos−1(−13) = 109.4712206...° ≈ 109.5° when all four substituents are the same, as in methane as well as its heavier analogues. Methane and other perfectly symmetrical tetrahedral molecules belong to point group Td, but most tetrahedral molecules have lower symmetry. Tetrahedral molecules can be chiral.

<span class="mw-page-title-main">Coordination polymer</span> Polymer consisting of repeating units of a coordination complex

A coordination polymer is an inorganic or organometallic polymer structure containing metal cation centers linked by ligands. More formally a coordination polymer is a coordination compound with repeating coordination entities extending in 1, 2, or 3 dimensions.

<span class="mw-page-title-main">Tin selenide</span> Chemical compound

Tin selenide, also known as stannous selenide, is an inorganic compound with the formula SnSe. Tin(II) selenide is a typical layered metal chalcogenide as it includes a group 16 anion (Se2−) and an electropositive element (Sn2+), and is arranged in a layered structure. Tin(II) selenide is a narrow band-gap (IV-VI) semiconductor structurally analogous to black phosphorus. It has received considerable interest for applications including low-cost photovoltaics, and memory-switching devices.

<span class="mw-page-title-main">Keggin structure</span> Best known structural form for heteropoly acids

The Keggin structure is the best known structural form for heteropoly acids. It is the structural form of α-Keggin anions, which have a general formula of [XM12O40]n, where X is the heteroatom, M is the addendum atom, and O represents oxygen. The structure self-assembles in acidic aqueous solution and is a commonly used type of polyoxometalate catalysts.

A Bjerrum defect is a crystallographic defect which is specific to ice, and which is partly responsible for the electrical properties of ice. It was first proposed by Niels Bjerrum in 1952 in order to explain the electrical polarization of ice in an electric field. A hydrogen bond normally has one proton, but a hydrogen bond with a Bjerrum defect will have either two protons or no proton. D-defects are more energetically favorable than L-defects. The unfavorable defect strain is resolved when a water molecule pivots about an oxygen atom to produce hydrogen bonds with single protons. Dislocations of ice Ih along a slip plane create pairs of Bjerrum defects, one D defect and one L defect.

A hydrogen clathrate is a clathrate containing hydrogen in a water lattice. This substance is interesting due to its possible use to store hydrogen in a hydrogen economy. A recent review that accounts the state-of-the-art and future prospects and challenges of hydrogen storage as clathrate hydrates is reported by Veluswamy et al. (2014). Another unusual characteristic is that multiple hydrogen molecules can occur at each cage site in the ice, one of only a very few guest molecule that forms clathrates with this property. The maximum ratio of hydrogen to water is 6 H2 to 17 H2O. It can be formed at 250K in a diamond anvil at a pressure of 300MPa (3000 Bars). It takes about 30 minutes to form, so this method is impractical for rapid manufacture. The percent of weight of hydrogen is 3.77%. The cage compartments are hexakaidecahedral and hold from two to four molecules of hydrogen. At temperatures above 160K the molecules rotate around inside the cage. Below 120K the molecules stop racing around the cage, and below 50K are locked into a fixed position. This was determined with deuterium in a neutron scattering experiment.

<span class="mw-page-title-main">Hydration number</span> Measure of solvency/solution

The hydration number of a compound is defined as the number of molecules of water bonded to a central ion, often a metal cation. The hydration number is related to the broader concept of solvation number, the number of solvent molecules bonded to a central atom. The hydration number varies with the atom or ion of interest.

Nitrogen clathrate or nitrogen hydrate is a clathrate consisting of ice with regular crystalline cavities that contain nitrogen molecules. Nitrogen clathrate is a variety of air hydrates. It occurs naturally in ice caps on Earth, and is believed to be important in the outer Solar System on moons such as Titan and Triton which have a cold nitrogen atmosphere.

<span class="mw-page-title-main">Thorium(IV) nitrate</span> Chemical compound

Thorium(IV) nitrate is a chemical compound, a salt of thorium and nitric acid with the formula Th(NO3)4. A white solid in its anhydrous form, it can form tetra- and pentahydrates. As a salt of thorium it is weakly radioactive.

<span class="mw-page-title-main">Macromolecular cages</span>

Macromolecular cages have three dimensional chambers surrounded by a molecular framework. Macromolecular cage architectures come in various sizes ranging from 1-50 nm and have varying topologies as well as functions. They can be synthesized through covalent bonding or self-assembly through non-covalent interactions. Most macromolecular cages that are formed through self-assembly are sensitive to pH, temperature, and solvent polarity.

Arsenide iodides or iodide arsenides are compounds containing anions composed of iodide (I) and arsenide (As3−). They can be considered as mixed anion compounds. They are in the category of pnictidehalides. Related compounds include the arsenide chlorides, arsenide bromides, phosphide iodides, and antimonide iodides.

References

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