Compendium

MOF, COF, and Perovskite Catalog

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MOF, COF, and Perovskite Catalog

Tier 3 family index for three crystalline-but-modular materials classes that have shifted from academic curiosity to commercial products in the 2020s: metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and the perovskite family (oxide and halide).

1. MOFs — Metal-Organic Frameworks

1.1 Definition

Porous crystalline materials built from inorganic metal nodes (SBUs — secondary building units) linked by multitopic organic linkers through coordination bonds. The combination of a small metal-cluster vertex and a long organic edge produces extended frameworks with high crystallinity, tunable pore sizes (typically 5-100 Å), and exceptional internal surface area. The record for measured BET surface area is ~7,000-10,400 m²·g⁻¹ (DUT-60, NU-110, MOF-210), exceeding zeolites (~700 m²·g⁻¹) and activated carbons (~3,000 m²·g⁻¹) by an order of magnitude.

1.2 Foundational MOFs (Yaghi laboratory)

Yaghi at Arizona State / Michigan / UCLA / Berkeley developed the canonical examples:

  • Zn-BDC (1995) — first coordination polymer with permanent porosity; the prototype.
  • MOF-2 (1998) — Zn(BDC)·DMF; 2D layered.
  • MOF-5 / IRMOF-1 (1999) — Zn₄O(BDC)₃; cubic 3D; first true MOF demonstrating large pores (~12 Å) and high surface area (~3,800 m²·g⁻¹ BET); proof-of-principle that organic-linker frameworks are not just zeolite analogues but their own class.
  • MOF-177 — Zn₄O(BTB)₂; 4,500 m²·g⁻¹; mesoporous; H₂ storage benchmark.
  • MOF-200 — Zn₄O(BBC)₂; 4,530 m²·g⁻¹.
  • MOF-210 — Zn₄O(BTE)(BPDC); 6,240 m²·g⁻¹ BET, 10,400 m²·g⁻¹ Langmuir — record-holder.

The naming pattern: “IRMOF” = isoreticular MOF; same topology (pcu cubic), different linker length.

1.3 MIL series — Materials of Institut Lavoisier (Férey, UVSQ)

  • MIL-100(Cr/Fe/Al) — supertetrahedral; mesoporous cages 25-29 Å; ~2,800 m²·g⁻¹.
  • MIL-101(Cr) — Cr₃O(BDC)₃; mesoporous; ~5,900 m²·g⁻¹; water-stable; benchmark for many applications.
  • MIL-53(Cr/Al/Fe) — “breathing” MOF; open and narrow-pore states switch reversibly under gas pressure or temperature.
  • MIL-88 — flexible carboxylate framework.

1.4 HKUST-1 (Hong Kong University of Science and Technology)

Cu₃(BTC)₂, also called Cu-BTC; Chui-Lo-Charmant-Orpen-Williams, Science 283 (5405), 1148-1150 (Feb 1999). Cu paddlewheel SBU; ~1,900 m²·g⁻¹; commercially available from Sigma-Aldrich and BASF; widely used as the reference MOF for adsorption and storage studies.

1.5 ZIFs — Zeolitic Imidazolate Frameworks

Park et al. (Yaghi group), PNAS 103 (27), 10186-10191 (Jul 2006). Tetrahedral metals (Zn, Co) bridged by imidazolate ligands at ~145° M-Im-M angle, mimicking the Si-O-Si angle in zeolites; ZIFs adopt zeolite-like topologies (sod, rho, lta, mer, etc.).

  • ZIF-8 — Zn(2-methylimidazolate)₂; sodalite topology; 1,630 m²·g⁻¹; hydrothermally and chemically robust; the most widely-used ZIF.
  • ZIF-67 — Co(2-methylimidazolate)₂; sodalite; magnetic; catalysis precursor.
  • ZIF-7, ZIF-11 — narrower pores; molecular-sieve membranes.

1.6 UiO series (University of Oslo)

Cavka, Jakobsen, Olsbye, Guillou, Lillerud, Bordiga, Lamberti, JACS 130 (42), 13850-13851 (Oct 2008). Zr₆O₄(OH)₄ SBU coordinated by 12 dicarboxylate linkers; remarkably thermally (decomposition ~540 °C) and hydrothermally stable; the benchmark Zr-MOF family.

  • UiO-66 — Zr₆ + terephthalate (BDC); pore ~6-7 Å; ~1,200 m²·g⁻¹; the most-studied Zr-MOF.
  • UiO-67 — Zr₆ + biphenyldicarboxylate (BPDC); larger pore; ~3,000 m²·g⁻¹.
  • UiO-68 — even longer terphenyldicarboxylate linker.
  • UiO-66-NH₂, UiO-66-NO₂, UiO-66-Br — functionalized variants for tunable adsorption and catalysis.

1.7 NU series (Northwestern University, Hupp and Farha groups)

Zr-based ultra-high-surface-area MOFs:

  • NU-1000 — Zr₆ + 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene linker; pore 31 Å; 2,200 m²·g⁻¹; benchmark for catalyst encapsulation.
  • NU-1500 — Fe / Cr nodes with 6-connected hexacarboxylate linker; 3,500 m²·g⁻¹.
  • NU-1501 — Fe / Al; 7,310 m²·g⁻¹ BET — among the highest measured.

1.8 PCN series (Porous Coordination Network; Texas A&M, Zhou group)

  • PCN-222 / MOF-545 — Zr + porphyrinic linker; catalyst MOF.
  • PCN-250 — Fe / Co + ABTC linker; methane storage.
  • PCN-700 — Zr; thermally robust.
  • PCN-14 — Cu paddlewheel + 5,5’-(9,10-anthracenediyl)diisophthalate; methane storage benchmark.

1.9 Other notable MOFs

  • MOF-74 family (also CPO-27) — M₂(dobdc), M = Mg, Mn, Fe, Co, Ni, Zn; 1D channels with exposed open metal sites; benchmark for gas adsorption with chemical interaction.
  • MOF-808 — Zr-trimesate; ~2,000 m²·g⁻¹; defect-engineered Lewis acid catalyst.
  • CALF series (Calgary Framework; Shimizu).
  • PCP (porous coordination polymers; Kitagawa, Kyoto) — Japanese terminology for what English-language groups call MOFs.
  • Pillared paddlewheel MOFs — DABCO or BiPy pillared Zn / Cu paddlewheels; PCN-14, MMOF, DMOF.

1.10 Topology and reticular chemistry

The Reticular Chemistry Structure Resource (RCSR; rcsr.net; O’Keeffe, Yaghi) catalogues the underlying nets:

  • pcu — simple cubic (MOF-5, IRMOF series).
  • sql — square-grid 2D.
  • fcu — face-centered cubic (UiO-66).
  • bcu — body-centered cubic.
  • ssp, soc, rht-net — higher-coordinated nets, mostly for very high-surface-area MOFs.
  • sod — sodalite (ZIF-8).
  • acs, ftw — high-connectivity Zr nets.

1.11 Synthesis routes

RouteScaleNotes
Solvothermalg - kgDMF / DEF / water at 80-180 °C, 12-72 h; default lab method
Microwave-assistedgMinutes vs. hours; smaller crystals
Electrochemicalkg - tBASF method for HKUST-1 — anodic dissolution of Cu electrode into ligand solution
Mechanochemicalg - kgBall-milling with minimal solvent; green chemistry route
Continuous flowkg+mof-Xtra, framergy; tubular reactors with mixed solvents at 60-150 °C
SonochemicalgUltrasound-driven nucleation; smaller particle size
Slow evaporationgSingle-crystal growth for SCXRD structure solution

1.12 MOF applications

Gas storage

  • H₂ — MOF-5, MOF-177, IRMOF-20, IRMOF-993 reach 6-7 wt% H₂ uptake at 77 K and 50 bar (DOE 2025 ultimate target 6.5 wt% system gravimetric — onboard fuel storage). At ambient temperature uptake collapses; MOFs have not yet met room-T storage targets.
  • CH₄ — HKUST-1, Ni-MOF-74, UTSA-76, PCN-14 hold ~200-260 cm³(STP)·cm⁻³ at 65 bar / 298 K, near DOE 263 cm³·cm⁻³ target for adsorbed natural gas vehicles.
  • CO₂ — mmen-Mg₂(dobpdc) — diamine-functionalized variant of Mg-MOF-74; Smit-Long, Berkeley 2015; sharp step in isotherm at 0.4 mbar CO₂ partial pressure due to cooperative chemisorption (“molecular trapdoor”); basis of Mosaic Materials’ DAC and post-combustion capture technology (acquired Baker Hughes 2022).
  • NH₃ — MFM-300(Al/In/V/Sc) — Forgan, Manchester; capacity > 16 mmol·g⁻¹; chemically stable to NH₃ unlike many MOFs.

Gas separation

  • H₂ / N₂ / CO₂ / CH₄ — kinetic and thermodynamic separations in ZIF-8 membranes.
  • CO₂ / CH₄ — natural gas upgrading; ZIF-8 commercialized for CO₂ removal.
  • Olefin / paraffin (C₂H₄ / C₂H₆, C₃H₆ / C₃H₈) — energy-intensive cryogenic distillation today; MAF-23 (Chen et al., Nature 2018, reversed selectivity ethane > ethylene), Y-fum-fcu-MOF, NbOFFIVE-1-Ni offer alternatives.
  • Xe / Kr — SBMOF-1; high Xe/Kr selectivity for nuclear used-fuel reprocessing off-gas.
  • C₈ aromatics (xylene isomers) — MIL-47, MOF-74 for para-xylene purification.

Water harvesting (DAC of water)

  • MOF-303 — Al(fumarate)(OH); water sorption isotherm with sharp step at 13% RH; field demos in Mojave Desert (Yaghi, LBNL, 2017-2020); basis of Atoco (Yaghi spinout) and SOURCE Global Hydropanels (Cody Friesen, ASU) — hybrid PV + sorbent panels delivering 2-5 L water per panel-day.
  • MOF-801 — Zr-fumarate; first-generation harvester.
  • MOF-313 — newer variant with sharper step and higher uptake.

Catalysis

  • MOF-74 + MIL-100 — open metal sites act as Lewis acids.
  • UiO-66-NH₂ — amine-functionalized; basic catalysis.
  • UiO-66-Pd encapsulation — Pd nanoparticles inside MOF cages for cross-coupling.
  • CO₂ to formate (CR5; Berkeley) — MOF-electrocatalysts.
  • Methane to methanol — Ni-MOF-74 (Bell-Long, Berkeley); selective C-H oxidation on isolated single-metal sites.
  • Mn-porphyrin MOFs — biomimetic oxidation.

Drug delivery

Horcajada et al., Nature Materials 9, 172-178 (Feb 2010) — MIL-100(Fe) and MIL-101(Fe) loaded with ibuprofen, busulfan, azidothymidine; biocompatible iron carboxylate framework; releases drug over days. Subsequent work on cisplatin, doxorubicin in ZIF-8.

Sensing

  • Luminescent Ln-MOFs — Eu³⁺, Tb³⁺ frameworks; Allendorf at Sandia; selective fluorescence quenching by explosives, VOCs.
  • Conductive MOFs — Ni₃(HITP)₂, Cu₃(HHTP)₂ — porous and electrically conductive; chemiresistive gas sensors (NO₂, NH₃, H₂S).

Electrochemistry

  • MOF-derived carbons — pyrolysis of MOF templates → high-surface-area N-doped carbon for Li-S, Li-air, ORR electrocatalysts.
  • Direct MOF electrodes — cobalt-MOFs and Ni-MOFs as supercapacitor electrodes.

1.13 Commercial MOF companies

  • NuMat Technologies (Northwestern + Penn spinout, 2012) — ION-X cylinders: MOF-filled gas cylinders for ultra-high-purity specialty gases (AsH₃, PH₃, BF₃) used in semiconductor fab; allows sub-atmospheric storage of toxic dopants for safer handling at Intel, TSMC, Samsung fabs.
  • MOF Technologies (Belfast, UK spinout from Queen’s University) — mechanochemical MOF synthesis; CO₂ capture for industrial flue gas.
  • framergy (Texas A&M Zhou-group spinout) — MOF-74 and PCN materials for natural-gas storage and water harvesting.
  • Mosaic Materials (UC Berkeley spinout, Long-Smit) — diamine-Mg₂(dobpdc) for CO₂ capture; acquired by Baker Hughes in 2022.
  • Nuada (UK) — MOF-303 water harvesting.
  • Atoco (Yaghi UCLA spinout) — MOF water harvesting.
  • BASF (Ludwigshafen) — early industrial MOF producer; HKUST-1 (Basolite C-300), MIL-53 (Basolite A-100), Fe-BTC (Basolite F-300) at multi-kg scale.
  • Cargill + Promethean Particles — pilot MOF scale-up.

2. COFs — Covalent Organic Frameworks

2.1 Definition

All-organic crystalline porous polymers; the all-organic analogue of MOFs. The first COF was reported by Côté, Benin, Ockwig, O’Keeffe, Matzger, Yaghi, Science 310 (5751), 1166-1170 (Nov 2005) — COF-1 (B-O linkage from self-condensation of benzene-1,4-diboronic acid) and COF-5 (boronate ester from BDBA and HHTP). The breakthrough: dynamic-covalent-bond chemistry allows error-correction during framework formation, producing crystalline rather than amorphous polymers.

2.2 Topology

  • 2D COFs — sheet topologies stacked in eclipsed (AA) or staggered configurations; the majority of reported COFs.
  • 3D COFs — full 3D nets; rarer because three-fold or four-fold rigid linkers are harder to design.

2.3 Linkage chemistry

  • Boroxine, boronate ester — first generation (Yaghi 2005); high crystallinity but moisture-sensitive; not durable.
  • Imine (Schiff base) — most common modern chemistry; Dichtel, Northwestern, JACS 2011 (COF-LZU1); reversible C=N bond enables crystallization; modestly acid/water-stable.
  • Hydrazone — variant of imine; more hydrolytically stable.
  • β-ketoenamine (ketoenamine tautomer) — Banerjee, NCL Pune, JACS 2012 (TpPa-1); irreversible after enol→keto tautomerization; stable in 9 N HCl and 9 N NaOH.
  • Squaraine — π-conjugated; visible-light absorbing.
  • Triazine (CTF, Covalent Triazine Framework) — Kuhn-Antonietti, Angewandte Chemie 2008; ZnCl₂-melt trimerization of dinitriles at 400 °C; very stable but often poorly crystalline.
  • Olefin (sp²-carbon COFs) — Jiang, Kyoto / Hong Kong; Knoevenagel condensation; fully π-conjugated 2D backbones; semiconducting.

2.4 COF applications

  • Gas separation — H₂ / CO₂, CO₂ / N₂; COF membranes (Dichtel).
  • Ion conduction — Li-COFs for solid-state battery electrolytes (Dichtel, Zhuang).
  • Heterogeneous catalysis — imine COFs as supports for Pd, Ru.
  • Photocatalysis — sp²-COFs and CTFs for visible-light water splitting and CO₂ reduction.
  • Drug delivery — porous biocompatible imine COFs.
  • Sensing — fluorescent COFs for explosive and pollutant detection.

2.5 Notable COF researchers

Yaghi (UCLA), Dichtel (Northwestern), Banerjee (NCL Pune), Jiang (Kyoto / Hong Kong), Lotsch (Max Planck Munich), Zhuang (Shanghai Jiao Tong), El-Kaderi (VCU), Cooper (Liverpool).

3. Perovskites

3.1 Structure

ABX₃ formula: A 12-coordinate cation, B 6-coordinate cation, X anion. The B-X bonds form corner-sharing octahedra; A sits in the cuboctahedral cavity. Cubic ideal structure has Goldschmidt tolerance factor:

t = (r_A + r_X) / [√2 · (r_B + r_X)]

with 0.90 ≤ t ≤ 1.00 for cubic. Lower t → orthorhombic / rhombohedral distortions; higher t → hexagonal polytypes.

3.2 Oxide perovskites

X = O²⁻; A and B are typically alkaline-earth + 4d/5d or 3d transition metal.

  • SrTiO₃ — cubic; quantum paraelectric; epitaxial substrate for thin-film oxide growth.
  • BaTiO₃ — ferroelectric below 393 K; classical piezoelectric; MLCC (multi-layer ceramic capacitor) dielectric — Murata, TDK, Samsung Electro-Mechanics; ~10¹³ MLCCs/year globally.
  • PbTiO₃ — ferroelectric Tc ~ 763 K; piezoelectric.
  • PMN-PT — Pb(Mg₁/₃Nb₂/₃)O₃-PbTiO₃ relaxor ferroelectric single crystal; the highest-performance piezoelectric (d₃₃ > 2000 pC/N); used in medical ultrasound transducers (Philips, GE Vingmed) and SONAR; CTS, H.C. Materials.
  • KNbO₃ — lead-free piezoelectric.
  • LSCF — La₀.₆Sr₀.₄Co₀.₂Fe₀.₈O₃₋δ — mixed ionic-electronic conductor; SOFC cathode (Bloom Energy, Ceres Power).
  • LSC, LSM — La₁₋ₓSrₓCoO₃, La₁₋ₓSrₓMnO₃ — older SOFC cathode materials.
  • LSCM — La₀.₇₅Sr₀.₂₅Cr₀.₅Mn₀.₅O₃₋δ — SOFC anode for hydrocarbon fuels.
  • LaMnO₃, LaCoO₃ — catalysts for hydrocarbon oxidation; CMR (colossal magnetoresistance) when Sr-doped.
  • YBa₂Cu₃O₇₋δ (YBCO) — Wu-Chu-Ashburn-Torng-Hor-Meng-Gao-Huang-Wang-Chu, Physical Review Letters 58 (9), 908-910 (Mar 1987) — cuprate superconductor with Tc = 92 K, the first material superconducting above 77 K (the boiling point of liquid nitrogen). Layered perovskite (cuprate planes + Ba/Y/CuO chains). Foundation of the entire cuprate field. Coated-conductor wires from American Superconductor, SuperPower, Sumitomo, Fujikura, Theva, SuperOx.

3.3 Halide perovskites — photovoltaics

X = Cl⁻, Br⁻, I⁻; A typically methylammonium (MA, CH₃NH₃⁺), formamidinium (FA, HC(NH₂)₂⁺), or Cs⁺; B = Pb²⁺ or Sn²⁺.

  • MAPbI₃ — Kojima-Teshima-Shirai-Miyasaka 2009 dye-sensitized solar cell with 3.8% PCE; Park (Sungkyunkwan) 9.7% solid-state 2012; Snaith (Oxford) and Grätzel (EPFL) rapid follow-on.
  • FAPbI₃ — higher thermal and operational stability than MAPbI₃.
  • Mixed cation, mixed halide — CsₓMAᵧFA_zPb(IₓBr₁₋ₓ)₃ — current state-of-the-art for top cells in tandems.
  • Single-junction perovskite cell efficiency: 26.7% certified (2024, Cu Wenchao group, Shanghai, Nature) — approaching the practical limit for the bandgap (~30%).
  • Perovskite / silicon tandem: 33.9% certified at NREL (LONGi, Aug 2024) — the highest two-terminal tandem; above the Shockley-Queisser limit for single-junction Si (~29%).
  • First commercial perovskite-Si tandem product — Oxford PV (Snaith spinout, 2010); Brandenburg, Germany pilot line ~100 MW/yr commissioned 2024; targeting residential and utility markets.

3.4 Lead-free and double perovskites

Concern about Pb toxicity drives research into:

  • Sn-based — MASnI₃, FASnI₃; bandgap ~1.3 eV; promising on paper but Sn²⁺ → Sn⁴⁺ oxidation devastates carrier lifetime; champion stable Sn-perovskite cell ~14%.
  • Bi³⁺ / Sb³⁺ double perovskites — Cs₂AgBiBr₆, Cs₂AgBiCl₆, Cs₂AgInBr₆; indirect bandgap; champion ~6%; mostly used for X-ray detectors rather than solar.

3.5 Perovskite solar companies

  • Oxford PV (UK / Germany; Snaith) — perovskite-Si tandem; first commercial product 2024.
  • Saule Technologies (Poland; Olga Malinkiewicz) — flexible perovskite for IoT and small power.
  • Tandem PV (US; ex-Stanford/SLAC); certified 32% tandem 2024.
  • Caelux (US; Caltech spinout) — perovskite-on-glass tandem partner for c-Si modules.
  • Verde Technologies (US).
  • Mountain Pacific Energy (US).
  • Energy Materials Corp. (US).
  • Microquanta (China) — large-area perovskite modules.
  • UtmoLight (China; Wuxi) — 720 W large-area perovskite modules.
  • JinkoSolar — perovskite-Si tandem R&D program; 33.24% champion cell Mar 2024.
  • LONGi — record 33.9% tandem Aug 2024 (later certified).

3.6 Stability and encapsulation

Halide perovskites degrade under moisture, UV, heat, and electric field. Current outdoor lifetime targets are 25 years (matching c-Si modules); recent cells achieve 1000-2000 h at 85 °C / 85% RH under load. Stabilization strategies:

  • Cation engineering — mixing K⁺, Rb⁺, Cs⁺ with FA / MA to stabilize the cubic phase.
  • 2D / 3D heterostructures — thin 2D Ruddlesden-Popper layer on top of 3D perovskite.
  • Encapsulation — ALD Al₂O₃ + glass; barrier WVTR < 10⁻⁴ g·m⁻²·d⁻¹.
  • Passivation — surface treatment with alkylammonium halides, phosphonic acids.

3.7 Perovskite LEDs (PeLEDs)

  • MAPbBr₃ — Tan, Friend et al., Nature Nanotechnology 9, 687-692 (Sep 2014) — first perovskite LED; green emission; EQE ~0.1%.
  • CsPbBr₃ + FAPbBr₃ — Kim-Park, KAIST (2014).
  • Modern PeLEDs — > 28% EQE (green, Nature 2023, Tian-Bakr group); approaching commercial-OLED EQE.
  • Perovskite QDs in display color converters — CsPbBr₃ + CsPbCl₃ blends.

3.8 Perovskite radiation detectors

Stoumpos, Kanatzidis et al. at Northwestern, Crystal Growth & Design 13 (7), 2722-2727 (Jul 2013) demonstrated solution-grown CsPbBr₃, MAPbBr₃, MAPbI₃ single crystals for X-ray and γ-ray detection; high atomic-number Pb gives strong stopping power; bulk single-crystals up to cm size. Commercial: Kromek (UK).

3.9 Defect chemistry and ionic conduction in perovskites

  • YSZ — yttria-stabilized zirconia — Y-doped fluorite (not strictly perovskite) but the canonical oxide-ion conductor for SOFC electrolytes at 800-1000 °C.
  • BaZrO₃ doped with Y (BZY) — proton conductor at 400-600 °C; protonic SOFC electrolyte (Ceres Power).
  • Li halide perovskites — Li₃OCl, Li₃OBr — antiperovskite solid electrolyte candidates.
  • Magnetism — LaMnO₃ doped with Sr or Ca shows CMR; SrFeO₃₋δ shows magnetic-ordering tunability with oxygen vacancy.

Adjacent notes

Graph View

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