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Rock, Metal aus Erfurt. Eine junge Erfurter Band mit Einflüssen von Rock, Metal, Punk und eventuell weiteren Genres mit der Arbeit an eigenen Songs. Tags. Statistik: Von The Mofos sind 0 aktuelle und 7 vergangene Konzerte auf Metalgigs eingetragen. Bandmitglieder: Keine Mitglieder bei Metalgigs bekannt. Metallica Night - August 7, Schwarzes Metall, Kirk Hammett, Star Spangled Banner ROCK N' METAL CENTRAL Emma PetterssonMetal mofos.

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A plastic AFO is a custom fabricated, molded plastic device that encloses the back of the calf and bottom of the foot. It can be fabricated with or without ankle motion.

It is worn inside a lace-up shoe. A plastic AFO is generally used with patients suffering from neurological or orthopedic conditions.

Examples of neurological conditions would be stroke, multiple sclerosis, and cerebral palsy. In these cases, the AFO functions by maintaining the affected joints in proper alignment to overcome weakness or muscle imbalance.

A variety of methods exist for inducing drug release, such as pH-response, magnetic-response, ion-response, temperature-response, and pressure response.

In Smaldone et al. Cyclodextrins can interact with appropriately sized drug molecules to yield an inclusion complex.

Subsequently, in Hartlieb et al. The group studied different methods of loading the MOF with ibuprofen as well as performing related bioavailability studies on the ibuprofen-loaded MOF.

They investigated two different methods of loading CD-MOF-1 with ibuprofen; crystallization using the potassium salt of ibuprofen as the alkali cation source for production of the MOF, and absorption and deprotonation of the free-acid of ibuprofen into the MOF.

In vivo studies in mice showed the same rapid uptake of ibuprofen as the ibuprofen potassium salt control sample with a peak plasma concentration observed within 20 minutes, and the cocrystal has the added benefit of double the half-life in blood plasma samples.

Since these developments many groups have done further research into drug delivery with water-soluble, biocompatible MOFs involving common over-the-counter drugs.

Recent research involving MOFs as a drug delivery method includes more than just the encapsulation of everyday drugs like ibuprofen and aspirin.

In early Chen et al. In researchers proved that they can create electrically conductive thin films of MOFs Cu 3 BTC 2 also known as HKUST-1 ; BTC, benzene-1,3,5-tricarboxylic acid infiltrated with the molecule 7,7,8,8-tetracyanoquinododimethane that could be used in applications including photovoltaics, sensors and electronic materials and a path towards creating semiconductors.

The team demonstrated tunable, air-stable electrical conductivity with values as high as 7 siemens per meter, comparable to bronze.

Ni 3 2,3,6,7,10,hexaiminotriphenylene 2 was shown to be a metal-organic graphene analogue that has a natural band gap , making it a semiconductor, and is able to self-assemble.

It represents a family of similar compounds. Because of the symmetry and geometry in 2,3,6,7,10,hexaiminotriphenylene HITP , the overall organometallic complex has an almost fractal nature that allows it to perfectly self-organize.

By contrast, graphene must be doped to give it the properties of a semiconductor. Biomolecules can be incorporated during the MOF crystallization process.

Enzymes encapsulated in this way were stable and active even after being exposed to harsh conditions e. Because of their small, tunable pore sizes and high void fractions, MOFs are a promising potential material for use as an adsorbent to capture CO 2.

MOFs could provide a more efficient alternative to traditional amine solvent-based methods in CO 2 capture from coal-fired power plants.

MOFs could be employed in each of the main three carbon capture configurations for coal-fired power plants: pre-combustion, post-combustion, and oxy-combustion.

In post-combustion carbon capture, the flue gas from the power plant would be fed through a MOF in a packed-bed reactor setup. CO 2 can bind to the MOF surface through either physisorption , which is caused by Van der Waals interactions , or chemisorption , which is caused by covalent bond formation.

This process is known as regeneration. In a pressure swing, the pressure would be decreased until CO 2 desorbs. In addition to their tunable selectivities for different molecules, another property of MOFs that makes them a good candidate for carbon capture is their low heat capacities.

This high heat capacity contributes to the energy penalty in the solvent regeneration step, i. In a collaborative project sponsored by the U.

The MOF Mg dobdc has a MOF membranes can mimic substantial ion selectivity. This offers the potential for use in desalination and water treatment.

As of reverse osmosis supplied more than half of global desalination capacity, and the last stage of most water treatment processes.

Osmosis does not use dehydration of ions, or selective ion transport in biological channels and it is not energy efficient. The mining industry, uses membrane-based processes to reduce water pollution, and to recover metals.

MOFs could be used to extract metals such as lithium from seawater and waste streams. MOF membranes such as ZIF-8 and UiO membranes with uniform subnanometer pores consisting of angstrom-scale windows and nanometer-scale cavities displayed ultrafast selective transport of alkali metal ions.

The windows acted as ion selectivity filters for alkali metal ions, while the cavities functioned as pores for transport. A prototype has been developed that captures water vapor from the air, and then releases it with the application of a smaller amount of heat compared to existing commercially available technologies.

Such MOFs could also be used to increase energy efficiency in room temperature space cooling applications. Therefore, air conditioning efficiency is a very desirable area for reducing future increases in energy consumption and CO2 production from producing that energy.

When cooling outdoor air, a cooling unit must deal with both the sensible heat and latent heat of the outdoor air.

Typical vapor-compression-air-conditioning VCAC units manage the latent heat of the water vapor in air through cooling fins held below the dew point temperature of the moist air at the intake.

These fins condense the water, dehydrating the air and thus reducing the heat content of the air substantially.

Unfortunately, the energy usage of the cooler is highly dependent on the temperature of the cooling coil and would be improved greatly if the temperature of this coil could be raised above the dew point.

One such means is by adsorbing the water from the air into a desiccant coated onto the heat exchangers, using the waste heat exhausted from the unit to desorb the water from the sorbent and thus regenerate the desiccant for repeated usage.

The conclusion is that a desiccant which can adsorb a large amount of water and then easily release that water would be ideal for this application. Some MOFs also exhibit spontaneous electric polarization, which occurs due to the ordering of electric dipoles polar linkers or guest molecules below a certain phase transition temperature.

This material property is highly interesting for construction of memory devices with high information density. From Wikipedia, the free encyclopedia.

Redirected from Metal-organic framework. Dimensionality of Organic. Main article: Hydrogen storage. Six diamond-shaped channels upper with diameter of Hydrogen storage capacity: 7.

MOF has larger pores, so hydrogen is compressed within holes rather than adsorbed to the surface. This leads to higher total gravimetric uptake but lower volumetric storage density compared to MOF MOF-5 has received much attention from theorists because of the partial charges on the MOF surface, which provide a means of strengthening the binding hydrogen through dipole -induced intermolecular interactions; however, MOF-5 has poor performance at room temperature 9.

It has relatively strong metal-hydrogen interactions, attributed to a spin state change upon binding or to a classical Coulombic attraction.

Main article: carbon capture and storage. Pure and Applied Chemistry. Journal of Solid State Chemistry. Bibcode : JSSCh. Bibcode : Sci Chemical Society Reviews.

Chemical Communications 46 : — Angewandte Chemie. European Journal of Inorganic Chemistry. Accounts of Chemical Research. Journal of the American Chemical Society.

Microporous and Mesoporous Materials. New Journal of Chemistry. RSC Advances. Nature Materials. Bibcode : NatMa..

Chemistry of Materials. Chemical Communications. Retrieved 22 June Faraday Discussions. Bibcode : FaDi..

Journal of Physical Chemistry C. Washington, D. Energie, pollution de l'air et developpement durable. Louvain-la-Neuve: Presses Universitaires de Louvain.

Dalton Transactions. Tetrahedron Letters. Chemical Physics Letters. Bibcode : CPL New York: Kluwer Academic. Physical Chemistry Chemical Physics.

Bibcode : PCCP The Journal of Chemical Physics. Bibcode : JChPh. Türker and S. International Journal of Heat and Mass Transfer.

Physical Chemistry: A Molecular Approach. Journal of Materials Chemistry. Springer Netherlands. Die Naturwissenschaften. Bibcode : NW Zeolites and Catalysis: Synthesis, Reactions and Applications.

Journal of Catalysis. Chemical Communications 35 : —4. Inorganica Chimica Acta. Chemical Communications 11 : —9. Bibcode : Natur.

Chemical Communications 14 : —7. Nature Communications. Bibcode : NatCo Chemical Communications 24 : —5. Chemical Communications 3 : —6.

The Journal of Physical Chemistry B. Chemical Reviews. Inorganic Chemistry. Materials Today Chemistry. Advanced Science. Nature Energy. Advanced Materials Interfaces.

ACS Catalysis. Bibcode : PNAS.. Chemical Science. Journal of Materials Chemistry A. ACS Central Science. Advanced Materials.

Drug Discovery Today. Molecular Pharmaceutics. ACS Omega. Energy Procedia. Introduction to Carbon Capture and Sequestration.

London: Imperial College Press. February 9, Retrieved Science Advances. Bibcode : SciA Nature Sustainability. I had my first bass lesson in I played guitar as well in the early 80s.

I was never comfortable with it. Lemmy was never comfortable with guitar either. As he said, he got away with murder playing it in the 60s.

It was all rock and roll stuff and basic understanding of riff patterns then solos and stuff. He was very clever.

Bass guitar was all over those albums. So in Lightforce, my early band, I could do a lot more playing around the neck.

MM: Your bass playing is definitely a big part of Mortification. It really stands out. You can hear the bass prominently in every song.

I certainly like Destruction though. Why do you have a bass player? SR: Well, just the guitarist playing in the band is designed to be a rumble, you know?

Like Bolt Thrower for example. He over uses distortion which should make it stick out, but he uses a fat distortion sound. If he plays on his own you can hear him, but it just becomes a roar in the background really.

For example when Kreator came out with Pleasure to Kill bass guitar was all over it. It was just awesome because it was chaotic, you know?

Then they came out with Extreme Aggression and I was like, really? Not like when you hear the really early Kreator stuff.

SR: I usually come up with a concept. All my lyrics are based on the Christian faith and Biblical perspectives. So, that made it pretty different.

We started in the 80s in what was called the Christian music scene so in America our music would be placed in big bookstores and places like Walmart in the Gospel section.

We released all this extreme music and it would be sold in Walmart under Gospel. And we sold a lot of it.

I said to the record company, why are you sticking us under Gospel music? They said because the people who are buying your albums are the moms who are buying for their sons and daughters because, Oh my kid is listening to Morbid Angel or Metallica or something, and they would probably like this because they came from a church and wanted their kid to hear something more Gospel oriented.

So we sold a lot of records that way. When in Europe, on the Nuclear Blast label, we would sit between Morbid Angel and Motorhead, which is a good place to sit in the record stores.

People would buy Morbid Angel and Mortification at the same time. Of course I caught my fair share of hatred over the years as you can imagine.

Why are so many metal bands, especially extreme metal bands, like Morbid Angel for example so involved in that and so anti-Christianity?

I was brought up in a very conservative Baptist home. I go to a Presbyterian church now. The church I go to is just your average conservative Bible church.

They were quite conservative. They were more open to talking about new ideas about Christianity through different genres.

I certainly remain a pretty mild mannered dude. Andrew has played drums in Mortification as well. Since the classic era of Mortification Lincoln Bowen, guitar has been the biggest part of the rest of it.

When we did Envision Evangeline album he was I was MM: Can you tell me a bit about the Envision Evangeline album? That album started a move a way from the heavier death metal sound to more of a straight up metal and thrash type of sound.

You had the opening 18 minute epic track. Can you tell me how this came about? SR: Well, I never really wanted to be boxed in to anything.

I never wanted to stick with just any one thing. I have so many influences going back to the 70s, and I wanted to combine making extreme metal music with different influences.

Why not mix in a traditional metal style song? All 16 Mortification albums sound completely different. SR: Even Blood World is really crusty.

Primitive Rhythm Machine was a take on Sepultura or something. I just wanted to enjoy life. Then there are a lot of fans who like everything and like the changes.

Envision Evangeline or Relentless? They sound similar. Which one do you think is the best? Then the real hardcore fans love Scrolls of the Megilloth and the self titled album.

I was listening to Primitive Rhythm Machine the other day, and I really love the drums on that album especially with the title track. They have a cool tribal sound.

SR: That was kind of a progression from Blood World in that we needed to use the real drums rather than trying to get perfection.

Whereas Scrolls, Blood World , and Primitive Rhythm Machine were played with me guiding the drummer so it sounded more live.

Post Momentary Affliction was recorded to a click track. I was just trying different ways of doing it. The very first thing we did, Break the Curse , was recorded in two 12 hour sessions.

We did 5 songs in 12 hours then again for the second 12 hours. It was released originally as a demo then in Nuclear Blast asked if we had anything older they could release.

SR: Cool. Yeah, I have it here. So it was recorded in those two 12 hour sessions. We did PM — AM with no lock out. We had to come in, do everything in 12 hours, and get out.

We set up and recorded 5 songs with bass and drums live, then we did leads, then vocals. Then we mixed the first take basically on most things.

When you have a really good drummer like Jayson Sherlock… you need to have a very good drummer to go in and do that. You have to be very well rehearsed.

Back in the 90s we would rehearse 12 hours per week. We did two 6 hour sessions. Now we rehearse probably 4 hours every two weeks.

It depends on the people in the band. Mick Carlisle who played on early Mortification albums basically played like a black metal guitarist.

I thought this is going to be an adventure here. SR: For me, my faith is the foundation of everything. Always has been.

When I was 19 someone played me Resurrection Band, which is a Christian heavy rock band. I went into the Christian bookstore and found this other heavy rock stuff like Jerusalem then of course Stryper came along and the whole world changed, you know?

Back in the day we were involved in a lot of controversy. He calls it unBlack metal. Nuclear Blast received death threats from people in the black metal scene about the record Everything he touches is brilliant musically.

He and I are on a bit different perspectives musically. He wants everything to be brutal and serious.

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Cu 3 BTC 2 can be quickly synthesised in this way in quantitative yield. In the case of Cu 3 BTC 2 the morphology of the solvent free synthesised product was the same as the industrially made Basolite C It is thought that localised melting of the components due to the high collision energy in the ball mill may assist the reaction.

The formation of acetic acid as a by-product in the reactions in the ball mill may also help in the reaction having a solvent effect [15] in the ball mill.

It has been shown that the addition of small quantities of ethanol for the mechanochemical synthesis of Cu 3 BTC 2 significantly reduces the amounts of structural defects in the obtained material.

A recent advancement in the solvent-free preparation of MOF films and composites is their synthesis by chemical vapor deposition.

In a first step, metal oxide precursor layers are deposited. In the second step, these precursor layers are exposed to sublimed ligand molecules, that induce a phase transformation to the MOF crystal lattice.

Formation of water during this reaction plays a crucial role in directing the transformation. This process was successfully scaled up to an integrated cleanroom process, conforming to industrial microfabrication standards.

High-Throughput HT methods are a part of combinatorial chemistry and a tool for increasing efficiency. Basically, there are two synthetic strategies within the HT-methods: On the one hand the combinatorial approach, here all reactions take place in one vessel, which leads to product mixtures and on the other hand the parallel synthesis, here the reactions take place in different vessels.

Furthermore, a distinction is made between thin films and solvent-based methods. Solvothermal synthesis can be carried out conventionally in a teflon reactor in a convection oven or in glass reactors in a microwave oven high-throughput microwave synthesis.

The use of a microwave oven changes, in part dramatically, the reaction parameters. In addition to solvothermal synthesis, there have been advances in using supercritical fluid as a solvent in a continuous flow reactor.

Supercritical water was first used in to synthesize copper and nickel-based MOFs in just seconds. In high-throughput solvothermal synthesis, a solvothermal reactor with eg 24 cavities for teflon reactors is used.

Such a reactor is sometimes referred to as a multiclav. The reactor block or reactor insert is made of stainless steel and contains 24 reaction chambers, which are arranged in four rows.

With the miniaturized teflon reactors, volumes of up to 2 mL can be used. The reactor block is sealed in a stainless steel autoclave; for this purpose, the filled reactors are inserted into the bottom of the reactor, the teflon reactors are sealed with two teflon films and the reactor top side is put on.

The autoclave is then closed in a hydraulic press. The sealed solvothermal reactor can then be subjected to a temperature-time program.

The reusable teflon film serves to withstand the mechanical stress, while the disposable teflon film seals the reaction vessels.

After the reaction, the products can be isolated and washed in parallel in a vacuum filter device. On the filter paper, the products are then present separately in a so-called sample library and can subsequently be characterized by automated X-ray powder diffraction.

The informations obtained are then used to plan further syntheses. Although the three-dimensional structure and internal environment of the pores can be in theory controlled through proper selection of nodes and organic linking groups, the direct synthesis of such materials with the desired functionalities can be difficult due to the high sensitivity of MOF systems.

Thermal and chemical sensitivity, as well as high reactivity of reaction materials, can make forming desired products challenging to achieve.

The exchange of guest molecules and counter-ions and the removal of solvents allow for some additional functionality but are still limited to the integral parts of the framework.

Post-synthetic modification techniques can be used to exchange an existing organic linking group in a prefabricated MOF with a new linker by ligand exchange or partial ligand exchange.

Some of these uses include fine-tuning the material for selective adsorption, gas storage, and catalysis. The exchange often requires heat and occurs on the time scale of a few days.

Post-synthetic modification techniques can also be used to exchange an existing metal ion in a prefabricated MOF with a new metal ion by metal ion exchange.

The complete metal metathesis from an integral part of the framework has been achieved without altering the framework or pore structure of the MOF.

Similarly to post-synthetic ligand exchange post-synthetic metal exchange is performed by washing prefabricated MOF crystals with solvent and then soaking the crystal in a solution of the new metal.

In addition to modifying the functionality of the ligands and metals themselves, post-synthetic modification can be used to expand upon the structure of the MOF.

Using post-synthetic modification MOFs can be converted from a highly ordered crystalline material toward a heterogeneous porous material.

Core-shell MOFs and other layered MOFs have been prepared where layers of have unique functionalization but in most cases are crystallographically compatible from layer to layer.

In some cases MOF metal node has an unsaturated environment, and it is possible to modify this environment using different techniques. If the size of the ligand matches the size of the pore aperture, it is possible to install additional ligands to existing MOF structure.

For instance, it was shown that metal node can perform an extension, and create a bond with the uranyl cation. Another approach to increasing adsorption in MOFs is to alter the system in such a way that chemisorption becomes possible.

This functionality has been introduced by making a composite material, which contains a MOF and a complex of platinum with activated carbon.

In an effect known as hydrogen spillover , H 2 can bind to the platinum surface through a dissociative mechanism which cleaves the hydrogen molecule into two hydrogen atoms and enables them to travel down the activated carbon onto the surface of the MOF.

This innovation produced a threefold increase in the room-temperature storage capacity of a MOF; however, desorption can take upwards of 12 hours, and reversible desorption is sometimes observed for only two cycles.

Molecular hydrogen has the highest specific energy of any fuel. However unless the hydrogen gas is compressed, its volumetric energy density is very low, so the transportation and storage of hydrogen require energy-intensive compression and liquefaction processes.

Compared to an empty gas cylinder , a MOF-filled gas cylinder can store more hydrogen at a given pressure because hydrogen molecules adsorb to the surface of MOFs.

Furthermore, MOFs are free of dead-volume, so there is almost no loss of storage capacity as a result of space-blocking by non-accessible volume.

No large activation barriers are required when liberating the adsorbed hydrogen. The extent to which a gas can adsorb to a MOF's surface depends on the temperature and pressure of the gas.

In general, adsorption increases with decreasing temperature and increasing pressure until a maximum is reached, typically bar, after which the adsorption capacity decreases.

The U. Department of Energy DOE has published a list of yearly technical system targets for on-board hydrogen storage for light-duty fuel cell vehicles which guide researchers in the field 5.

A benchmark material to this end is MOF which was found to store hydrogen at 7. Another exemplary material is PCN which exhibits a hydrogen uptake of 6.

Despite these promising MOF examples, the classes of synthetic porous materials with the highest performance for practical hydrogen storage are activated carbon and covalent organic frameworks COFs.

Practical applications of MOFs for hydrogen storage are met with several challenges. For hydrogen adsorption near room temperature, the hydrogen binding energy would need to be increased considerably.

Carboxylate-based MOFs have by far received the most attention because. Lighter main group metal ions have also been explored. Be 12 OH 12 BTB 4 , the first successfully synthesized and structurally characterized MOF consisting of a light main group metal ion, shows high hydrogen storage capacity, but it is too toxic to be employed practically.

The following is a list of several MOFs that are considered to have the best properties for hydrogen storage as of May in order of decreasing hydrogen storage capacity.

Therefore, it is not yet known whether materials with high surface areas, small pores, or di- or trivalent metal clusters produce the most favorable MOFs for hydrogen storage.

Hydrogen storage capacity at 77 K : 8. High hydrogen uptake is attributed to overlapping attractive potentials from multiple copper paddle-wheel units: each Cu II center can potentially lose a terminal solvent ligand bound in the axial position, providing an open coordination site for hydrogen binding.

To date, hydrogen storage in MOFs at room temperature is a battle between maximizing storage capacity and maintaining reasonable desorption rates, while conserving the integrity of the adsorbent framework e.

There are two major strategies governing the design of MOFs for hydrogen storage:. The general trend in MOFs used for hydrogen storage is that the greater the surface area, the more hydrogen the MOF can store.

High surface area materials tend to exhibit increased micropore volume and inherently low bulk density, allowing for more hydrogen adsorption to occur.

High hydrogen adsorption enthalpy is also important. Synthetically, this may be achieved by using ligands whose geometries prevent the metal from being fully coordinated, by removing volatile metal-bound solvent molecules over the course of synthesis, and by post-synthetic impregnation with additional metal cations.

A problem with this approach is that MOFs with exposed metal surfaces have lower concentrations of linkers; this makes them difficult to synthesize, as they are prone to framework collapse.

This may diminish their useful lifetimes as well. MOFs are frequently sensitive to moisture in the air. Studies on metal analogues have unraveled the ability of metals other than Zn to stand higher water concentrations at high temperatures.

To compensate for this, specially constructed storage containers are required, which can be costly. Strong metal-ligand bonds, such as in metal-imidazolate, -triazolate, and -pyrazolate frameworks, are known to decrease a MOF's sensitivity to air, reducing the expense of storage.

In a microporous material where physisorption and weak van der Waals forces dominate adsorption, the storage density is greatly dependent on the size of the pores.

At this width, exactly two layers of hydrogen molecules adsorb on opposing surfaces with no space left in between.

Structural defects also play an important role in the performance of MOFs. Room-temperature hydrogen uptake via bridged spillover is mainly governed by structural defects, which can have two effects:.

Structural defects can also leave metal-containing nodes incompletely coordinated. This enhances the performance of MOFs used for hydrogen storage by increasing the number of accessible metal centers.

Adsorption is the process of trapping atoms or molecules that are incident on a surface; therefore the adsorption capacity of a material increases with its surface area.

In three dimensions, the maximum surface area will be obtained by a structure which is highly porous, such that atoms and molecules can access internal surfaces.

This simple qualitative argument suggests that the highly porous metal-organic frameworks MOFs should be excellent candidates for hydrogen storage devices.

Adsorption can be broadly classified as being one of two types: physisorption or chemisorption. In both cases, the adsorbate atoms or molecules i.

The degree of orbital overlap then determines if the interactions will be physisorptive or chemisorptive. Adsorption of molecular hydrogen in MOFs is physisorptive.

A complete explanation of the H 2 sorption mechanism in MOFs was achieved by statistical averaging in the grand canonical ensemble, exploring a wide range of pressures and temperatures.

Two hydrogen-uptake measurement methods are used for the characterization of MOFs as hydrogen storage materials: gravimetric and volumetric.

To obtain the total amount of hydrogen in the MOF, both the amount of hydrogen absorbed on its surface and the amount of hydrogen residing in its pores should be considered.

The increased mass of the MOF due to the stored hydrogen is directly calculated by a highly sensitive microbalance.

Thus, this "weight loss" has to be corrected using the volume of the MOF's frame and the density of hydrogen. The changing of amount of hydrogen stored in the MOF is measured by detecting the varied pressure of hydrogen at constant volume.

Of these, high-pressure gas cylinders and liquid hydrogen in cryogenic tanks are the least practical ways to store hydrogen for the purpose of fuel due to the extremely high pressure required for storing hydrogen gas or the extremely low temperature required for storing hydrogen liquid.

The other methods are all being studied and developed extensively. MOFs have potential as heterogeneous catalysts , although applications have not been commercialized.

Zeolites are extraordinarily useful in catalysis. Fewer than zeolites are known. Furthermore, mild synthetic conditions typically employed for MOF synthesis allow direct incorporation of delicate functionalities into the framework structures.

Such a process would not be possible with zeolites or other microporous crystalline oxide-based materials because of the harsh conditions typically used for their synthesis e.

Zeolites still cannot be obtained in enantiopure form, which precludes their applications in catalytic asymmetric synthesis , e.

Enantiopure chiral ligands or their metal complexes have been incorporated into MOFs to lead to efficient asymmetric catalysts.

Even some MOF materials may bridge the gap between zeolites and enzymes when they combine isolated polynuclear sites, dynamic host—guest responses, and a hydrophobic cavity environment.

MOFs might be useful for making semi-conductors. Theoretical calculations show that MOFs are semiconductors or insulators with band gaps between 1.

Like other heterogeneous catalysts , MOFs may allow for easier post-reaction separation and recyclability than homogeneous catalysts.

In some cases, they also give a highly enhanced catalyst stability. Additionally, they typically offer substrate-size selectivity. Nevertheless, while clearly important for reactions in living systems, selectivity on the basis of substrate size is of limited value in abiotic catalysis, as reasonably pure feedstocks are generally available.

A second set of examples was based on a two-dimensional, square-grid MOF containing single Pd II ions as nodes and 2-hydroxypyrimidinolates as struts.

At a minimum, these reactions necessarily entail redox oscillations of the metal nodes between Pd II and Pd 0 intermediates accompanying by drastic changes in coordination number, which would certainly lead to destabilization and potential destruction of the original framework if all the Pd centers are catalytically active.

The observation of substrate shape- and size-selectivity implies that the catalytic reactions are heterogeneous and are indeed occurring within the MOF.

Furthermore, para alkylation is strongly favored over ortho alkylation, a behavior thought to reflect the encapsulation of reactants by the MOF.

The coordinated water molecules are easily removed, leaving open Cu II sites. Kaskel and co-workers showed that these Lewis acid sites could catalyze the cyanosilylation of benzaldehyde or acetone.

Lewis acid -catalyzed pathways, the product selectivity are distinctive for three reactions: isomerization of a-pinene oxide, cyclization of citronellal, and rearrangement of a-bromoacetals, indicating that indeed [Cu 3 btc 2 ] functions primarily as a Lewis acid catalyst.

The product selectivity and yield of catalytic reactions e. In principle, either of the two types of Mn II sites could function as a catalyst.

Noteworthy features of this catalyst are high conversion yields for small substrates and good substrate-size-selectivity, consistent with channellocalized catalysis.

The MOF encapsulation approach invites comparison to earlier studies of oxidative catalysis by zeolite-encapsulated Fe porphyrin [75] as well as Mn porphyrin [76] systems.

The difference is likely mechanistically significant, thus complicating comparisons. In addition, for the MOF-based system, it is conceivable that oxidation proceeds via both oxygen transfer from a manganese oxo intermediate as well as a manganese -initiated radical chain reaction pathway.

Regardless of mechanism, the approach is a promising one for isolating and thereby stabilizing the porphyrins against both oxo-bridged dimer formation and oxidative degradation.

Most examples of MOF-based catalysis make use of metal ions or atoms as active sites. Among the few exceptions are two nickel - and two copper -containing MOFs synthesized by Rosseinsky and co-workers.

The coordination chemistry is such that the amine group of the aspartate cannot be protonated by added HCl , but one of the aspartate carboxylates can.

Thus, the framework-incorporated amino acid can exist in a form that is not accessible for the free amino acid.

While the nickel -based compounds are marginally porous , on account of tiny channel dimensions, the copper versions are clearly porous.

Superior homogeneous catalysts exist however. The nodes consist of single cadmium ions, octahedrally ligated by pyridyl nitrogens.

From a catalysis standpoint, however, the most interesting feature of this material is the presence of guest-accessible amide functionalities.

The amides are capable of base-catalyzing the Knoevenagel condensation of benzaldehyde with malononitrile. Reactions with larger nitriles , however, are only marginally accelerated, implying that catalysis takes place chiefly within the material's channels rather than on its exterior.

A noteworthy finding is the lack of catalysis by the free strut in homogeneous solution, evidently due to intermolecular H-bonding between bptda molecules.

Thus, the MOF architecture elicits catalytic activity not otherwise encountered. A third approach has been described by Kim Kimoon and coworkers.

POST-1 possesses 1D channels whose cross sections are defined by six trinuclear zinc clusters and six struts.

While three of the six pyridines are coordinated by zinc ions , the remaining three are protonated and directed toward the channel interior.

When neutralized, the noncoordinated pyridyl groups are found to catalyze transesterification reactions, presumably by facilitating deprotonation of the reactant alcohol.

The absence of significant catalysis when large alcohols are employed strongly suggests that the catalysis occurs within the channels of the MOF.

The metals in the MOF structure often act as Lewis acids. The metals in MOFs often coordinate to labile solvent molecules or counter ions which can be removed after activation of the framework.

The Lewis acidic nature of such unsaturated metal centers can activate the coordinated organic substrates for subsequent organic transformations.

The use of unsaturated metal centers was demonstrated in the cyanosilylation of aldehydes and imines by Fujita and coworkers in The Cd II centers in this MOF possesses a distorted octahedral geometry having four pyridines in the equatorial positions, and two water molecules in the axial positions to form a two-dimensional infinite network.

On activation, two water molecules were removed leaving the metal centers unsaturated and Lewis acidic. The Lewis acidic character of metal center was tested on cyanosilylation reactions of imine where the imine gets attached to the Lewis-acidic metal centre resulting in higher electrophilicity of imines.

For the cyanosilylation of imines, most of the reactions were complete within 1 h affording aminonitriles in quantitative yield. Kaskel and coworkers [83] carried out similar cyanosilylation reactions with coordinatively unsaturated metals in three-dimensional 3D MOFs as heterogeneous catalysts.

The resulting framework after removal of two water molecules from axial positions possesses porous channel. But this strategy suffers from some problems like 1 the decomposition of the framework with increase of the reaction temperature due to the reduction of Cu II to Cu I by aldehydes ; 2 strong solvent inhibition effect; electron donating solvents such as THF competed with aldehydes for coordination to the Cu II sites, and no cyanosilylation product was observed in these solvents; 3 the framework instability in some organic solvents.

Several other groups have also reported the use of metal centres in MOFs as catalysts [74] [85] Again, electron-deficient nature of some metals and metal clusters makes the resulting MOFs efficient oxidation catalysts.

Mori and coworkers [86] reported MOFs with Cu 2 paddle wheel units as heterogeneous catalysts for the oxidation of alcohols. The catalytic activity of the resulting MOF was examined by carrying out alcohol oxidation with H 2 O 2 as the oxidant.

It also catalyzed the oxidation of primary alcohol, secondary alcohol and benzyl alcohols with high selectivity. Hill et al. Functional linkers can be also utilized as catalytic sites.

Ferey et al. The entrapment of catalytically active noble metals can be accomplished by grafting on functional groups to the unsaturated metal site on MOFs.

Ethylenediamine ED has been shown to be grafted on the Cr metal sites and can be further modified to encapsulate noble metals such as Pd.

Ruthenium nanoparticles have catalytic activity in a number of reactions when entrapped in the MOF-5 framework. The same catalyst was used in the hydrogenation of benzene to cyclohexane.

MOFs might prove useful for both photochemical and polymerization reactions due to the tuneability of the size and shape of their pores.

This molecule was found to have a variety of photochemical reaction properties including the production of cyclopentanol.

Polymerization reactions in confined space might have different properties than polymerization in open space. Styrene , divinylbenzene , substituted acetylenes , methyl methacrylate, and vinyl acetate have all been studied by Kitagawa and coworkers as possible activated monomers for radical polymerization.

The channels were shown to stabilize propagating radicals and suppress termination reactions when used as radical polymerization sites. Several strategies exist for constructing homochiral MOFs.

Crystallization of homochiral MOFs via self-resolution from achiral linker ligands is one of the way to accomplish such a goal.

However, the resulting bulk samples contain both enantiomorphs and are racemic. Aoyama and coworkers [94] successfully obtained homochiral MOFs in the bulk from achiral ligands by carefully controlling nucleation in the crystal growth process.

Zheng and coworkers [95] reported the synthesis of homochiral MOFs from achiral ligands by chemically manipulating the statistical fluctuation of the formation of enantiomeric pairs of crystals.

Growing MOF crystals under chiral influences is another approach to obtain homochiral MOFs using achiral linker ligands.

Rosseinsky and coworkers [96] [97] have introduced a chiral coligand to direct the formation of homochiral MOFs by controlling the handedness of the helices during the crystal growth.

Morris and coworkers [98] utilized ionic liquid with chiral cations as reaction media for synthesizing MOFs, and obtained homochiral MOFs. The most straightforward and rational strategy for synthesizing homochiral MOFs is, however, to use the readily available chiral linker ligands for their construction.

Moreover, by changing the length of the linker ligands the porosity and framework structure of the MOF can be selectivily tuned. Lin and coworkers have shown that the postmodification of MOFs can be achieved to produce enantioselective homochiral MOFs for use as catalysts.

The catalytic activity of MOFs can vary depending on the framework structure. Lin and others found that MOFs synthesized from the same materials could have drastically different catalytic activities depending on the framework structure present.

Another approach to construct catalytically active homochiral MOFs is to incorporate chiral metal complexes which are either active catalysts or precatalysts directly into the framework structures.

For example, Hupp and coworkers [] have combined a chiral ligand and bpdc bpdc: biphenyldicarboxylate with Zn NO 3 2 and obtained twofold interpenetrating 3D networks.

The orientation of chiral ligand in the frameworks makes all Mn III sites accessible through the channels. The resulting open frameworks showed catalytic activity towards asymmetric olefin epoxidation reactions.

No significant decrease of catalyst activity was observed during the reaction and the catalyst could be recycled and reused several times.

Zirconium phosphonate-based chiral porous hybrid materials containing the Ru BINAP diamine Cl 2 precatalysts showed excellent enantioselectivity up to Some MOF materials may resemble enzymes when they combine isolated polynuclear sites, dynamic host—guest responses, and hydrophobic cavity environment which are characteristics of an enzyme.

In enzymatic systems, protein units show "molecular recognition", high affinity for specific substrates. It seems that molecular recognition effects are limited in zeolites by the rigid zeolite structure.

Indeed, many hybrid frameworks contain organic parts that can rotate as a result of stimuli, such as light and heat. In photocatalysis, the use of mononuclear complexes is usually limited either because they only undergo single- electron process or from the need for high-energy irradiation.

In this case, binuclear systems have a number of attractive features for the development of photocatalysts. The high surface area and atomic metal sites feature of MOFs make them a suitable candidate for electrocatalysts, especially energy-related ones.

Until now, MOFs have been used extensively as electrocatalyst for water splitting hydrogen evolution reaction and oxygen evolution reaction , carbon dioxide reduction, and oxygen reduction reaction.

Using MOFs as precursors to prepare electrocatalysts with carbon support. Using MOFs directly as electrocatalysts. Deep Purple a number of times.

Of course in the late 70s I got into Motorhead then Iron Maiden. I was there in the store in , when I was 15, waiting when the first Iron Maiden came out.

I kind of just grew up with it. And you had the really fast Manowar songs. Next thing, Metallica came along, and Megadeth, and Anthrax.

It just progressed. It was just interesting to see what people did next. By the time we got to doing Mortification which was basically , Break the Curse was based on German thrash metal.

They were a little bit more noisy before they did Harmony Corruption in So when we heard Bolt Thrower and Napalm Death that was just kind of our next step.

The interesting thing is that one some of our early albums, our first three albums, especially on Scrolls of the Megilloth which was the big one, I was doing black metal vocals before anyone else was.

I mean I was doing great deep death metal vocals, but we were doing black metal vocals before they really became a thing. MM: I notice that in your music.

Was the black metal scene an influence on that album at all? I never really got into the Florida scene. Of course in the 80s I heard Death.

I heard Scream Bloody Gore and Leprosy, and Spiritual Healing before we actually decided we were going to go that heavy. I was 21 then. I just kind of grew up with it.

You just kind of discover this stuff. Just walk into the shop and get it. It was just all the metalheads in Melbourne there to buy Metallica.

We lined up for 3 hours to get our Metallica. It was just different back then, you know? MM: Right. Even when I was a teenager in the early s this album had been out for many years and still had an impact.

SR: When they were playing it in the shop no one could believe how much a leap it was from the first album.

The first album was a classic. I think they tried really hard with their last album but the biggest loss in Metallica was definitely Cliff Burton. MM: Oh yes, of course.

He was a tremendous bass player. SR: Well, it is a background instrument unless you make it an upfront instrument. I had my first bass lesson in I played guitar as well in the early 80s.

I was never comfortable with it. Lemmy was never comfortable with guitar either. As he said, he got away with murder playing it in the 60s.

It was all rock and roll stuff and basic understanding of riff patterns then solos and stuff. He was very clever. Bass guitar was all over those albums.

So in Lightforce, my early band, I could do a lot more playing around the neck. MM: Your bass playing is definitely a big part of Mortification.

It really stands out. You can hear the bass prominently in every song. I certainly like Destruction though. Why do you have a bass player?

SR: Well, just the guitarist playing in the band is designed to be a rumble, you know? Like Bolt Thrower for example. He over uses distortion which should make it stick out, but he uses a fat distortion sound.

If he plays on his own you can hear him, but it just becomes a roar in the background really. For example when Kreator came out with Pleasure to Kill bass guitar was all over it.

It was just awesome because it was chaotic, you know? Then they came out with Extreme Aggression and I was like, really? Not like when you hear the really early Kreator stuff.

SR: I usually come up with a concept. All my lyrics are based on the Christian faith and Biblical perspectives.

So, that made it pretty different. We started in the 80s in what was called the Christian music scene so in America our music would be placed in big bookstores and places like Walmart in the Gospel section.

We released all this extreme music and it would be sold in Walmart under Gospel. And we sold a lot of it. I said to the record company, why are you sticking us under Gospel music?

They said because the people who are buying your albums are the moms who are buying for their sons and daughters because, Oh my kid is listening to Morbid Angel or Metallica or something, and they would probably like this because they came from a church and wanted their kid to hear something more Gospel oriented.

So we sold a lot of records that way. When in Europe, on the Nuclear Blast label, we would sit between Morbid Angel and Motorhead, which is a good place to sit in the record stores.

People would buy Morbid Angel and Mortification at the same time. Of course I caught my fair share of hatred over the years as you can imagine.

Why are so many metal bands, especially extreme metal bands, like Morbid Angel for example so involved in that and so anti-Christianity?

I was brought up in a very conservative Baptist home. I go to a Presbyterian church now. The church I go to is just your average conservative Bible church.

They were quite conservative. They were more open to talking about new ideas about Christianity through different genres. I certainly remain a pretty mild mannered dude.

Andrew has played drums in Mortification as well. Since the classic era of Mortification Lincoln Bowen, guitar has been the biggest part of the rest of it.

When we did Envision Evangeline album he was I was MM: Can you tell me a bit about the Envision Evangeline album? That album started a move a way from the heavier death metal sound to more of a straight up metal and thrash type of sound.

You had the opening 18 minute epic track. Can you tell me how this came about? SR: Well, I never really wanted to be boxed in to anything.

I never wanted to stick with just any one thing. I have so many influences going back to the 70s, and I wanted to combine making extreme metal music with different influences.

Why not mix in a traditional metal style song? All 16 Mortification albums sound completely different. SR: Even Blood World is really crusty.

Primitive Rhythm Machine was a take on Sepultura or something. I just wanted to enjoy life. Then there are a lot of fans who like everything and like the changes.

Envision Evangeline or Relentless? They sound similar. Which one do you think is the best? Then the real hardcore fans love Scrolls of the Megilloth and the self titled album.

I was listening to Primitive Rhythm Machine the other day, and I really love the drums on that album especially with the title track. They have a cool tribal sound.

SR: That was kind of a progression from Blood World in that we needed to use the real drums rather than trying to get perfection.

Whereas Scrolls, Blood World , and Primitive Rhythm Machine were played with me guiding the drummer so it sounded more live.

Post Momentary Affliction was recorded to a click track. I was just trying different ways of doing it.

The very first thing we did, Break the Curse , was recorded in two 12 hour sessions. We did 5 songs in 12 hours then again for the second 12 hours.

It was released originally as a demo then in Nuclear Blast asked if we had anything older they could release. SR: Cool. Yeah, I have it here.

So it was recorded in those two 12 hour sessions. We did PM — AM with no lock out. We had to come in, do everything in 12 hours, and get out.

We set up and recorded 5 songs with bass and drums live, then we did leads, then vocals. Then we mixed the first take basically on most things.

When you have a really good drummer like Jayson Sherlock… you need to have a very good drummer to go in and do that.

You have to be very well rehearsed. Back in the 90s we would rehearse 12 hours per week. We did two 6 hour sessions. Now we rehearse probably 4 hours every two weeks.

It depends on the people in the band. Mick Carlisle who played on early Mortification albums basically played like a black metal guitarist.

I thought this is going to be an adventure here. SR: For me, my faith is the foundation of everything. Always has been.

When I was 19 someone played me Resurrection Band, which is a Christian heavy rock band. I went into the Christian bookstore and found this other heavy rock stuff like Jerusalem then of course Stryper came along and the whole world changed, you know?

Back in the day we were involved in a lot of controversy. He calls it unBlack metal. Nuclear Blast received death threats from people in the black metal scene about the record Everything he touches is brilliant musically.

He and I are on a bit different perspectives musically. He wants everything to be brutal and serious.

SR: Yes, a band called Revulsed. They did a gig a couple weeks ago. I have some Scrolls records as well.

I just get paid for the copies the British company Soundmass sells. I just get a few copies. Most of them I give away to band members and stuff.

Mostly stealing it. I have few of your records on vinyl. Do you have an original press of Post Momentary Affliction from ? SR: Yes, I have one. Nuclear Blast released it in Europe.

Take a look at that cover. Markus Staiger Nuclear Blast executive just had that piece of art lying around. MM: I read an article from Metal Hammer recently which asked the question, Have there ever been any good Christian metal bands?

The comments from all the readers were the opposite of what I expected.

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