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Our Zirconium UiO-66 type Analogs and Aluminum MOFs have Outstanding Physical Properties

Functionalization of UiO-66 Analogs Leads to the Significant Improvement of the MOFs’ Substantial Parameters

Strem Chemicals expanded its metal organic framework (MOF) portfolio and introduced a new series of UiO-66 type MOFs (UiO stands for Universitetet i Oslo).  These new products are offered in collaboration with ProfMOF – a company owned by a group of scientists at the University of Oslo.  Basic Zirconium 1,4‐dicarboxybenzene (BDC) MOF[1], also known as UiO-66-BDC (40-1105), is made of [Zr6O4(OH)4] clusters linked with 1,4-benzendicarboxylic acid ligand.  UiO-66-BDC is one of our customers’  more favorable products because of its exceptional thermal, chemical and mechanical stability[2].

The physical properties of MOFs strongly depend on the nature of organic linkers. For example, readily available and low cost carboxylate ligands are preferable materials due to improved metal-ligand bond interactions that are significantly - affected by the oxidation state and the ionic radius of metal ions.  By reason of high charge density and bond polarization, there is a strong affinity between Zr(IV) and carboxylate O atoms in most carboxylate-based Zr-MOFs[3].  In addition, utilization of different ligands can allow for fine-tuning the physical properties of new MOFs (Fig. 1, Table 1).

Fig. 1

Fig. 1. Zr6O4(OH)4 clusters linked by various carboxylate ligands

Earlier, we reported about the outstanding thermal stability of highly porous Zirconium 1,4‐dicarboxybenzene UiO-66-BDC (40-1105).  As part of our new additions to this line, we offer a slightly modified UiO-66-BDC (40-1108) that has a different metal to linker ratio compared to the original product.  In addition, Zr-biphenyldicarboxylate, UiO-66-BPDC/UiO-67(40-1112), is another analog which is able to operate at an even higher temperature than UiO-66-BDC.  Moreover, UiO-66-BPDC/UiO-67 has the highest pore volumes and consequently the largest BET surface areas (see Table 1).

Recently emerged Zr-fumarate, UiO-66-FA (also known as MOF 801) represents a very promising member of UiO-66 MOF family which is offered with two different metal to linker ratios (40-1106 and 40-1114).  This material is able to adsorb 2.8 liters of water per kilogram of MOFat relative humidity levels as low as 20% and requires no additional input of energy from the atmosphere at ambient conditions using low-grade heat from natural sunlight - (1 kW per square meter)[4].

Functionalization of the BDC ligand with amino group increases the capability of UiO-66 type MOF to absorb carbon dioxide.  Indeed, ab initio calculations for Zr-aminobenezenedicarboxylate (UiO-66-BDC-NH2, 40-1109) showed that in the hydroxylated structure, the presence of one NH2 group close to the OH group led to an overall stronger interaction than that of OH alone in unfunctionalized UiO-66[5].  In addition, UiO-66-NH2 demonstrates superior catalytic activity in the decomposition of phosphonates[6].

UiO-66 functionalized with an additional –COOH group results in Zr-trimellitate, UiO-66-BDC-COOH (40-1111).  This material shows the highest selectivity and good working facility for CO2 adsorption[7] In addition, it - provides enhanced capacity for ammonia removal.[8]

Finally, Strem presents a very stable framework -  Aluminium isophthalate, CAU-10-H 13-0300 (CAU stands for Christian Albrechts-Universität) with excellent thermophysical properties[9]. Thermal conductivity measurements have revealed that this adsorbent is a suitable material for cooling applications and remains stable during several thousand adsorption and desorption cycles with water as the working fluid[10].

STREM #

NAME

LINKER

METAL TO   LINKER RATIO

PROPERTIES

40-1106 UiO-66-FA FA LINKER 1 BET 750-770 m2/g
Pore volume 0.30-0.32 cm3/g
Thermal Stability 200°C
Particle size 0.1-0.5 µ
Activation Tem. 150 °C 
40-1114 UiO-66-FA FA LINKER 0.66 - 0.98 BET 750-1200 m2/g
Pore volume 0.31-0.55 cm3/g
Thermal Stability 200°C
Particle size 0.1-0.5 µ
Activation Tem. 130 °C
40-1105 UiO-66-BDC BDC LINKER 1 BET 1250-1270 m2/g
Pore volume 0.50-0.52 cm3/g
Thermal Stability 400°C
Particle size 0.2-0.5 µ
Activation Tem. 300 °C
40-1108 UiO-66-BDC BDC LINKER 0.66 - 0.98 BET 1250-1400 m2/g
Pore volume 0.50-0.55 cm3/g
Thermal Stability 400°C
Particle size 0.2-0.5 µ
Activation Tem. 300 °C
40-1109 UiO-66-BDC-NH2 BDC NH2 LINKER 0.90 - 1.0 BET 800-1200 m2/g
Pore volume 0.50-0.56 cm3/g
Thermal Stability 300°C
Particle size 0.1-0.5 µ
Activation Tem. 150 °C
40-1111 UiO-66-BDC-COOH BDC COOH LINKER 0.90 - 1.0 BET 650-800 m2/g
Pore volume 0.27-0.37 cm3/g
Thermal Stability 350°C
Particle size 0.2-0.5 µ
Activation Tem. 150 °C
40-1112 UiO-66-BPDC/UiO-67 BPDC LINKER 0.90 - 1.0 BET 2400-2500 m2/g
Pore volume 0.85-0.98 cm3/g
Thermal Stability 450°C
Particle size 0.4-0.7 µ
Activation Tem. THF wash 150 °C
13-0300 CAU-10 CAU LINKER 0.90 - 1.0 BET 620-640 m2/g
Pore volume 0.25-0.27 cm3/g
Thermal Stability 400°C
Particle size 0.4-0.7 µ
Activation Tem. 150 °C

Table 1. Linkers and physical properties of UiO-66 type [Zr6O4(OH)4] MOFs

 

References:

  1.  J. Am. Chem. Soc., 2008, 139, 13850.
  2. Chem. Soc. Rev., 2016, 45, 2327.
  3. Angew. Chem. Int. Ed., 2014, 53, 815.
  4. Science, 2017, 356, 430.
  5. ChemSusChem, 2014, 7, 3382.
  6. Chem. Sci., 2016, 7, 5827.
  7. Chem. Commun., 2011, 47, 9603.
  8. J. Phys. Chem. C, 2017, 121, 3310.
  9. Chem. Mater., 2013, 25, 17.
  10. J. Mater. Chem. A, 2016, 4, 11859.

 

Product mentioned in this blog:

40-1105: Zirconium 1,4-dicarboxybenzene MOF (UiO-66) [1072413-89-8]

40-1106: Zirconium trans-1, 2-ethylenedicarboxylic acid MOF (UiO-66-FA, FA:Zr=0.9-1)

40-1108: Zirconium benzenedicarboylate MOF (UiO-66-BDC, BDC:Zr=0.66-0.98)

40-1109: Zirconium aminobenzenedicarboxylate MOF (UiO-66-BDC-NH2, BDC-NH2:Zr=0.9-1.0) [1260119-00-3]

40-1111: Zirconium trimellitate MOF (UiO-66-BDC-COOH, BDC-COOH:Zr=0.9-1.0)              

40-1112: Zirconium biphenyldicarboxylate MOF (UiO-66-BPDC/UiO-67, BPDC:Zr=0.9-1.0)

40-1114: Zirconium Fumarate MOF (UiO-66-FA, FA:Zr=0.66-0.98)

13-0300: Aluminum hydroxide isophthalate MOF (CAU-10, Isophthalate:Al=0.9-1.0) [1416330-84-1]         

     Linkers:

08-0175: [1,1'-Biphenyl]-4,4'-dicarboxylic acid, min. 98% [787-70-2]

08-1220: 2,5-Dihydroxyterephthalic acid, 98% H4DOBDC [610-92-4]

08-0195: 1,3,5-Tricarboxybenzene, min. 95% (Trimesic acid) BTC [554-95-0]

08-1165: 1,4-Phenylenediacetic acid, 97% [7325-46-4]

08-0635: 1,3,5-Tris(4-carboxyphenyl)benzene, min. 98% BTB [50446-44-1]

 

To download our literature sheet for these items please visit the link below:

UiO-66 Zirconium Building Bricks for Stable Metal Organic Frameworks

 

For a complete reference of all of our MOF products please visit the links below:

MOF Product Family

Metal Organic Frameorks and Ligands for MOF Synthesis Booklet

 

 

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