Hexane Isomers Research Articles

The Last Piece of the Puzzle: Access to 7‐Connected Zirconium Metal‐Organic Frameworks for Hexane Separation

Zirconium metal‐organic frameworks (Zr‐MOFs) exhibit a wide range of Zr6 cluster connectivities, from 3‐connected to 12‐connected, enabling diverse structural designs. However, odd‐numbered connectivities, especially the 7‐connected Zr‐MOFs, are exceptionally rare due to geometric symmetry challenges. To address this, we developed a geometric pre‐assembly strategy to achieve targeted cluster connectivity. Using this approach, we synthesized NU‐5001 {[Zr6O4(OH)4(H4‐L)2]}, a Zr‐MOF featuring 7‐connected Zr6 clusters, derived from the precursor 6‐connected Zr‐MOF, NU‐5000 {[Zr6O4(OH)4(H3‐L)2]}. NU‐5000, constructed with a tritopic chiral linker H3‐L {(R)‐4,4',4''‐[6'‐chloro‐2,2'‐diethoxy‐(1,1'‐binaphthalene)‐4,4',6‐triyl]tribenzoic acid}, forms a (3,6)‐connected ant topology. Introducing a tetratopic chiral linker, 1,1'‐bi‐2‐naphthol tetracarboxylic acid H4‐L {(R)‐4,4',4'',4'''‐[2,2'‐diethoxy‐(1,1'‐binaphthalene)‐4,4',6,6'‐tetrayl]tetrabenzoic acid}, enabled an additional connection, resulting in NU‐5001 with a (3,4,7)‐connected topology. The H4‐L linker acts as either fully 4‐connected or 3‐connected with one arm uncoordinated. Additionally, NU‐5001M {[Zr6O4(OH)4(H4‐L) (H3‐L)]}, an isostructural variant, was synthesized using a mix of H3‐L and H4‐L linkers. NU‐5001’s unique pore structure and slight flexibility enable distinct adsorption behaviors for hexane isomers, highlighting its potential for kinetic separations. This work completes the Zr6 cluster connectivity landscape and demonstrates the feasibility of tuning Zr‐MOF connectivities through rational linker design, paving the way for rare, low‐symmetry frameworks with tailored properties.

The Last Piece of the Puzzle: Access to 7-Connected Zirconium Metal-Organic Frameworks for Hexane Separation.

Zirconium metal-organic frameworks (Zr-MOFs) exhibit a wide range of Zr6 cluster connectivities, from 3-connected to 12-connected, enabling diverse structural designs. However, odd-numbered connectivities, especially the 7-connected Zr-MOFs, are exceptionally rare due to geometric symmetry challenges. To address this, we developed a geometric pre-assembly strategy to achieve targeted cluster connectivity. Using this approach, we synthesized NU-5001 {[Zr6O4(OH)4(H4-L)2]}, a Zr-MOF featuring 7-connected Zr6 clusters, derived from the precursor 6-connected Zr-MOF, NU-5000 {[Zr6O4(OH)4(H3-L)2]}. NU-5000, constructed with a tritopic chiral linker H3-L {(R)-4,4',4''-[6'-chloro-2,2'-diethoxy-(1,1'-binaphthalene)-4,4',6-triyl]tribenzoic acid}, forms a (3,6)-connected ant topology. Introducing a tetratopic chiral linker, 1,1'-bi-2-naphthol tetracarboxylic acid H4-L {(R)-4,4',4'',4'''-[2,2'-diethoxy-(1,1'-binaphthalene)-4,4',6,6'-tetrayl]tetrabenzoic acid}, enabled an additional connection, resulting in NU-5001 with a (3,4,7)-connected topology. The H4-L linker acts as either fully 4-connected or 3-connected with one arm uncoordinated. Additionally, NU-5001M {[Zr6O4(OH)4(H4-L) (H3-L)]}, an isostructural variant, was synthesized using a mix of H3-L and H4-L linkers. NU-5001's unique pore structure and slight flexibility enable distinct adsorption behaviors for hexane isomers, highlighting its potential for kinetic separations. This work completes the Zr6 cluster connectivity landscape and demonstrates the feasibility of tuning Zr-MOF connectivities through rational linker design, paving the way for rare, low-symmetry frameworks with tailored properties.

Robust Aluminum-Based Metal–Organic Framework Adsorbents with Heteroatom-Functionalized Nanochannels for Hexane Isomer Separation

Robust Aluminum-Based Metal–Organic Framework Adsorbents with Heteroatom-Functionalized Nanochannels for Hexane Isomer Separation

Synergistic global and local flexibilities in Zr-based metal-organic frameworks enable sequential sieving of hexane isomers.

Separating hexane isomers based on the branching degree is crucial for their efficient utilization in the petrochemical industry, yet remains challenging due to their similar properties. Here we report a temperature-responsive Zr-based metal-organic framework, Zr-fum-FA, capable of sequentially sieving linear, mono-, and di-branched hexane isomers. Notably, the pore structure of Zr-fum-FA dynamically transforms from segmented triangular channels to an integrated rhombic configuration as the temperature increases, leading to distinct sieving effects. At low temperatures, the narrow triangular pores allow the exclusive adsorption of n-hexane while excluding branched isomers. In contrast, the expanded rhombic pores at high temperatures enable the sieving of mono- and di-branched isomers. Mechanistic studies reveal that this unique dual-sieving behavior originates from the synergistic effects of the global framework flexibility and the local dynamics of pendent hydroxyl groups. Furthermore, we demonstrate the decoupling of global and local flexibilities via two strategies: incorporating steric hindrance to dampen the global framework dynamics and enhancing the metal node rigidity to limit the local vibrations. These findings not only provide a promising adsorbent for the challenging separation of hexane isomers but also offer rational design principles for harnessing flexibility in MOFs.

Influence of palladium state on the efficiency of hexane isomerization catalysts

In this work, the catalytic properties of palladium catalysts based on Al2O3, SiO2, their mechanical mixtures with SO4-ZrO2 and the Pd/SO4-ZrO2-Al2O3 catalyst in the hexane isomerization reaction were studied. The catalysts were characterized by low-temperature nitrogen adsorption, X-ray diffraction, transmission electron microscopy, temperature-programmed reduction, IR spectroscopy of adsorbed CO, and XPS. It has been shown that the nature of the palladium support and precursor influences the size and charge state of palladium particles in catalysts. It has been established that the most active in the hexane isomerization reaction are catalytic systems in which positively charged forms of palladium are present.

Delayed linker addition (DLA) synthesis of dual linker ZIF-8 for separation mono- and di-branched isomers of hexane

The separation of mono- and di-branched C6 alkane isomers is one of the most challenging industrial processes for the production of high-octane gasoline components. In this work, ZIF-8 with dual ligands of imidazole (IM) and 2-methylimidazole (2-MIM), named as DLA-ZIF-8-IM, was synthesized by the method of delayed linker addition, and the microstructure of DLA-ZIF-8-IM was analyzed. Adsorption thermodynamic, kinetic and separation properties of C6 alkane isomers were investigated. The results show that compared with SALE-ZIF-8-IM prepared by the solvent-assisted ligand exchange method, the synthesis method of DLA-ZIF-8-IM is simpler and the BET specific surface area and pore volume (2136 m2·g−1 and 0.72 cm3·g−1) of DLA-ZIF-8-IM are increased by 21 % and 14 %, which is more conducive to adsorption and diffusion of 3-methylpentane (3MP) on DLA-ZIF-8-IM. The equilibrium adsorption capacity of 3MP on DLA-ZIF-8-IM reaches up to 2.89 mmol·g−1, which is 1.1 times than that on SALE-ZIF-8-IM, and the ratio of diffusion time constants between 3MP and 2,3-dimethylbutane (23DMB) on DLA-ZIF-8-IM (5.13) is 2.2 times than that on SALE-ZIF-8-IM. Moreover, at 30℃, the breakthrough adsorption capacity of 3MP on DLA-ZIF-8-IM is 1.46 mmol·g−1, which is 1.6 times more than that of SALE-ZIF-8-IM (0.90 mmol·g−1), while the breakthrough adsorption capacity of 23DMB is basically the same. The separation factor between 3MP and 23DMB on DLA-ZIF-8-IM is 2.96 via the synergy of thermodynamic and kinetic mechanism and the dynamic adsorption capacity of 3MP reaches 1.46 mmol·g−1. DLA-ZIF-8-IM achieves complete separation of C6 alkane mixtures for obtaining single high-purity product. This work provides a novel synthesis strategy for developing C6 alkane (clear) adsorption separation materials by modulating microporous structures of dual-ligand MOFs.

A Ni4O4-cubane-squarate coordination framework for molecular recognition

Molecular recognition is a fundamental function of natural systems that ensures biological activity. This is achieved through the sieving effect, host-guest interactions, or both in biological environments. Recent advancements in multifunctional proteins reveal a new dimension of functional organization that goes beyond single-function molecular recognition, emphasizing the need for artificial multifunctional materials in industrial applications. Herein, we have designed a porous Ni4O4-cubane squarate coordination polymer as an artificial molecular recognition host, drawing inspiration from the structural and functional features of natural enzymes. A comprehensive assessment of the material’s ability to distinguish target species under different operating conditions was carried out. The results confirm its sieving function through hexane isomers separation, host-guest interaction function via xenon/krypton separation, and dual presence of sieving and interaction through carbon dioxide/nitrogen separation. Additionally, the material demonstrates good stability and feasibility for large-scale production, indicating its practical potential. Our findings provide a bio-inspired multifunctional recognition material for chemical separations as proof-of-concept while offering solutions to advance artificial multifunctional materials adaptable to other applications beyond chemical separations.

Engineering Trifluoromethyl Groups in Porous Coordination Polymers to Enhance Stability and Regulate Pore Window for Hexane Isomers Separation.

Effective separation of hexane (C6) isomers is critical for a variety of industrial applications but conventional distillation methods are energy-intensive. Adsorptive separations based on porous coordination polymers (PCPs) offer a promising alternative due to their exceptional porosity and tunable properties. However, there is still an urgent need to develop PCPs with high stability and separation performance. This study investigates how substituting a methyl (-CH3) group with a trifluoromethyl (-CF3) group can regulate pores and hydrophobicity in PCPs. This precise adjustment aims to enhance stability and improve the kinetic separation performance of hydrophobic C6 isomers by considering the size and hydrophobicity of the trifluoromethyl group. Two isostructural PCPs with pcu topology, PCP-CH3 and PCP-CF3, were synthesized to vary pore diameters and hydrophobicity based on the presence of -CH3 or -CF3 groups. PCP-CF3 showed greater stability in water compared to PCP-CH3. While PCP-CH3 had high adsorption capacities, it lacked selectivity, whereas PCP-CF3 demonstrated improved selectivity, particularly in excluding dibranched isomers. Dynamic column separation experiments revealed that PCP-CF3 could selectively adsorb linear and monobranched isomers over dibranched isomers at room temperature. These findings highlight the potential of fluorine-modified PCPs for efficient isomer separation and underscore the importance of stability improvement strategies.

A 3D Robust and Microporous B←N Framework with 8‐connected Sandwich Nodes for Efficient Separation of Hexane Isomers

Recently B←N organic frameworks (BNFs) have gained substantial attention owing to their unique dative bond energy, which imparts them with specialized functionalities across a broad spectrum of applications. Despite previous reports on BNFs with permanent porosity, research endeavors towards three‐dimensional (3D) BNFs with similar properties are scarce, with no report of robust 3D BNFs featuring permanent porosity to date. Herein, electrostatic complementarystrategy is proposed to construct the first example of 3D robust and microporous BNF, BNF‐100, featuring a reo topology with 8‐connected sandwich nodes assembled via dative B←N bonds. The activated form BNF‐100a exhibits excellent chemical stability and permanent porosity with Langmuir surface area of 645.9 m2 g−1 and pore volume of 0.23 cm3 g−1. BNF‐100a can efficiently separate hexane isomers through sieving mechanisms, as confirmed by vapor adsorption experiments and dynamic breakthrough tests, surpassing the performance of most MOF materials. Finally, we achieved the purification of different branched hexane isomers using a single breakthrough column in a combined breakthrough and purging experiment, which is the first reported instance in the literature on hexane isomer separation.

A 3D Robust and Microporous B←N Framework with 8-connected Sandwich Nodes for Efficient Separation of Hexane Isomers.

Recently B←N organic frameworks (BNFs) have gained substantial attention owing to their unique dative bond energy, which imparts them with specialized functionalities across a broad spectrum of applications. Despite previous reports on BNFs with permanent porosity, research endeavors towards three-dimensional (3D) BNFs with similar properties are scarce, with no report of robust 3D BNFs featuring permanent porosity to date. Herein, electrostatic complementary strategy is proposed to construct the first example of 3D robust and microporous BNF, BNF-100, featuring a reo topology with 8-connected sandwich nodes assembled via dative B←N bonds. The activated form BNF-100 a exhibits excellent chemical stability and permanent porosity with Langmuir surface area of 645.9 m2 g-1 and pore volume of 0.23 cm3 g-1. BNF-100 a can efficiently separate hexane isomers through sieving mechanisms, as confirmed by vapor adsorption experiments and dynamic breakthrough tests, surpassing the performance of most MOF materials. Finally, we achieved the purification of different branched hexane isomers using a single breakthrough column in a combined breakthrough and purging experiment, which is the first reported instance in the literature on hexane isomer separation.

Recognition and order of multiple sidechains by metal-organic framework enhances the separation of hexane isomers.

Porous materials perform molecular sorting, separation and transformation by interaction between their framework structures and the substrates. Proteins also interact with molecules to effect chemical transformations, but rely on the precise sequence of the amino acid building units along a common polypeptide backbone to maximise their performance. Design strategies that positionally order sidechains over a defined porous framework to diversify the internal surface chemistry would enhance control of substrate processing. Here we show that different sidechains can be ordered over a metal-organic framework through recognition of their distinct chemistries during synthesis. The sidechains are recognised because each one forces the common building unit that defines the backbone of the framework into a different conformation in order to form the extended structure. The resulting sidechain ordering affords hexane isomer separation performance superior to that of the same framework decorated only with sidechains of a single kind. The separated molecules adopt distinct arrangements within the resulting modified pore geometry, reflecting their strongly differentiated environments precisely created by the ordered sidechains. The development of frameworks that recognize and order multiple sidechain functionality by conformational control offers tailoring of the internal surfaces within families of porous materials to direct interactions at the molecular level.

Recognition and order of multiple sidechains by metal–organic framework enhances the separation of hexane isomers

AbstractPorous materials perform molecular sorting, separation and transformation by interaction between their framework structures and the substrates. Proteins also interact with molecules to effect chemical transformations, but rely on the precise sequence of the amino acid building units along a common polypeptide backbone to maximise their performance. Design strategies that positionally order sidechains over a defined porous framework to diversify the internal surface chemistry would enhance control of substrate processing. Here we show that different sidechains can be ordered over a metal–organic framework through recognition of their distinct chemistries during synthesis. The sidechains are recognised because each one forces the common building unit that defines the backbone of the framework into a different conformation in order to form the extended structure. The resulting sidechain ordering affords hexane isomer separation performance superior to that of the same framework decorated only with sidechains of a single kind. The separated molecules adopt distinct arrangements within the resulting modified pore geometry, reflecting their strongly differentiated environments precisely created by the ordered sidechains. The development of frameworks that recognize and order multiple sidechain functionality by conformational control offers tailoring of the internal surfaces within families of porous materials to direct interactions at the molecular level.

Six‐Membered Ring Directed Assembly of a Zirconium Zeolitic Metal–Organic Framework for Efficient Separation of Hexane Isomers

AbstractThe synthesis of zirconium MOFs with zeolite net is quite challenging due to the high connectivity of Zr6 clusters, which is far from tetrahedral connection, a requisite for zeolite net. In this work, we demonstrate a six‐membered ring (6MR) strategy through mimicking of mineral zeolites with mixed ditopic and tritopic carboxylate linkers. With this strategy, the ditopic linker cross‐links Zr6 clusters to form 4‐connected zeolite‐like nets, while the tritopic one is used to direct the formation of 6MR and simultaneously consumes extra coordination sites on the cluster. The feasibility of this strategy is shown by one zeolitic metal–organic framework (NNM‐5) and this strategy has also led to the synthesis of the other dia‐type zirconium MOF (NNM‐6). Interestingly, as the tritopic linker not only directs the formation of 6MR but also partitions 6MR into small segments, NNM‐5 with SOD topology shows a structural feature of small aperture and big cage, which has led to efficient separation of hexane isomers. With both exceptionally high n‐hexane uptake (65.9 cm3 g−1) and size‐exclusion selectivity, an exceptional separation capability is verified by breakthrough experiments. Calculation results demonstrate that the large difference of diffusion energy barrier due to the small aperture accounts for the underlying separation mechanism.

Six-Membered Ring Directed Assembly of a Zirconium Zeolitic Metal-Organic Framework for Efficient Separation of Hexane Isomers.

The synthesis of zirconium MOFs with zeolite net is quite challenging due to the high connectivity of Zr6 clusters, which is far from tetrahedral connection, a requisite for zeolite net. In this work, we demonstrate a six-membered ring (6MR) strategy through mimicking of mineral zeolites with mixed ditopic and tritopic carboxylate linkers. With this strategy, the ditopic linker cross-links Zr6 clusters to form 4-connected zeolite-like nets, while the tritopic one is used to direct the formation of 6MR and simultaneously consumes extra coordination sites on the cluster. The feasibility of this strategy is shown by one zeolitic metal-organic framework (NNM-5) and this strategy has also led to the synthesis of the other dia-type zirconium MOF (NNM-6). Interestingly, as the tritopic linker not only directs the formation of 6MR but also partitions 6MR into small segments, NNM-5 with SOD topology shows a structural feature of small aperture and big cage, which has led to efficient separation of hexane isomers. With both exceptionally high n-hexane uptake (65.9 cm3 g-1) and size-exclusion selectivity, an exceptional separation capability is verified by breakthrough experiments. Calculation results demonstrate that the large difference of diffusion energy barrier due to the small aperture accounts for the underlying separation mechanism.

Hydrodesulfurization and isomerization performance of model FCC naphtha over sulfided Co(Ni)–Mo/Y catalysts

The process of deep hydrodesulfurization (HDS) in gasoline typically results in the saturation of olefins, leading to significant reductions in octane number. In this work, Y-supported Co(Ni)–Mo catalysts that with different Ni–Co content were prepared by the incipient wetness impregnation method, the structure and properties were characterized and analyzed using HRTEM, XPS, H2-TPR, and NH3-TPD. The isomerization of 1-hexene and 1-octene as well as the HDS of thiophene were studied by using model FCC naphtha. The incorporation of Ni was found to enhance the number of MoS2 stacking layers, thereby improving the degree of sulfurization in Mo and subsequently increasing the desulfurization rate, with a maximum achieved desulfurization rate of 94.7%. When employing a Ni/Co ratio of 3:2, optimal synergy between Ni and Co is achieved, resulting in a greater presence of multi-layer stacked II-Co(Ni)MoS active phases. Additionally, appropriate Brønsted acidity levels are maintained to facilitate efficient olefin isomerization while preserving high HDS activity. As a result, the current isomerization yield stands at 58.2%(mass). These understandings shed light on the development of highly HDS and olefin isomerization catalysts.

Separation of C6 hydrocarbons on sodium dithionite reduced graphene oxide aerogels

The ability of reduced graphene oxide aerogels (rGOAs) for challenging gas-phase separation was investigated with hexane isomers and benzene (C6 hydrocarbons) using inverse gas chromatography (IGC). For the first, rGOAs were synthesized with sodium dithionite (DTN) as a reductant. Experiments revealed that the most optimal DTN to graphene oxide mass ratio was 2:1, resulting in the highest specific surface area of 432.3 m2 g−1 and the highest degree of graphitization among analyzed samples. C6 hydrocarbon adsorption tests demonstrated the dominant role of the kinetic effect for the adsorption of branched and cyclic hexane isomers - the partition coefficient decreased as the molecule kinetic diameter increased. The contribution of thermodynamic effects was distinguished for molecules with uneven charge distribution. A comparison of the partition coefficient ratios for different pairs of hydrocarbons demonstrated the potential of rGOAs in separating various C6 hydrocarbons. The selectivity, calculated from binary-component adsorption tests of benzene (Bz)/cC6 equimolar mixture, was 13.7, 8.5 and 2.8 for DTN4, DTN2, and DTN1. The research indicates that rGOAs may have potential as adsorbents for the selective separation of hydrocarbons, however, the competitive adsorption and performance at high surface coverages of adsorbates have to be accounted for in further research to assess the applicability of rGOAs reliably.

Efficient separation of linear and mono-branched hexane isomers using large-area silicalite-1 membranes

Membrane-based hydrocarbon isomer separation is a promising and energy-saving alternative to distillation. For the first time, tubular silicalite-1 membranes with large areas of 180 cm2 were employed in this study to separate linear and mono-branched hexane isomers. The membrane had a thickness of around 8 μm and showed highly (h0h) orientation. In binary and ternary mixtures of n-hexane (n-C6), 2-methylpentane (2MP), and 3-methylpentane (3MP), the effects of temperature and partial pressure on the separation performance of silicalite-1 membrane were examined. Moreover, the long-term stability of the membrane in binary and ternary mixture separation was also investigated. The large-area membrane showed a n-C6 permeance of 2.4 × 10-8 mol/(m2 s Pa) and n-C6/2MP and n-C6/3MP separation factors of 36 and 74 in the ternary n-C6/2MP/3MP (2.8 kPa/2.9 kPa/2.8 kPa) mixture with N2 as the balanced gas at 100 kPa absolute and 303 K, respectively. The scaling-up membranes demonstrated good and stable separation performance during the long-term test, highlighting the effectiveness and potential application of using large-area silicalite-1 membranes for the separation of hexane isomer mixtures.

UiO-66/PIM-1 Mixed-Matrix Membrane for Hexane Isomer Separation.

The separation of high-octane dibranched alkanes from naphtha is critical in the refining of gasoline. To date, research on the membrane-based separation of alkane isomers has been limited, with a particular paucity of investigations into mixed-matrix membranes. Herein, the continuous and dense UiO-66/PIM-1 mixed-matrix membrane, which was prepared through precise control of the interfacial structure, was first applied to the differentiation of C6 alkane isomers. Due to the synergistic combination of UiO-66 with differential adsorption capabilities for alkanes and PIM-1 that possesses a cross-linkable structure, the resulting UiO-66/PIM-1-(20) membrane demonstrated remarkable separation performance and high stability. Pervaporation measurements showed that the mass fraction of 2,2-dimethylbutane in the feed side was increased from 50.0 to 75.8 wt % while an excellent flux of 1700 g m-2 h-1 was maintained over a continuous 40 h period. The UiO-66/PIM-1-(20) membrane, characterized by its facile replication and processing, shows potential for large-scale fabrication. This study offers a new approach to the membrane separation of alkane isomers.

Stable CAAC-Triazenes: A New Nitrogen Ligand System With Donor and Conformational Flexibility, and With Application in Olefin Activation Catalysis.

N-heterocyclic imines such as pyridylidene amines impart high catalytic activity when coordinated to a transition metal, largely imposed by their electronic flexibility. Here, this donor flexibility has been applied for the first time to CAAC-based systems through the synthesis of CAAC-triazenes. These new ligands offer a larger π-conjugation that extends from the N-heterocyclic carbene through three nitrogens rather than just one, as observed in N-heterocyclic imines. We demonstrate the straightforward synthesis of three new CAAC-triazenes containing different substituents on the terminal triazene nitrogen. These compounds are remarkably stable up to 120 °C without loss of N2 as typically observed with similar triazenes. E-to-Z isomerization within the triazene is instigated by UV light and is partially reversible dependent on the triazene substituent. The quinoline-substituted CAAC-triazene 1-Q has been applied as an L,L'-type ligand in the synthesis of [PdCl2(1-Q)], [PdCl(Me)(1-Q)] and [Pd(Me)(H2O(1-Q)]+. E-to-Z ligand isomerization also occurs when coordinated to PdCl2, providing access to on-metal manipulation. The cationic complex [PdMe(H2O)(1-Q)]+ is a precatalyst for oligomerization of ethylene to form initially 2-butene and subsequently linear and branched C8-C12 products from butene activation. Moreover, isomerization of 1-hexene takes place efficiently with exceptionally low catalyst loading (10 ppm) and up to 74,000 turnover numbers.

Exploring affinity between organic probes and Prussian Blue Analogues via inverse gas chromatography

Prussian Blue Analogues (PBAs), which are characterized by their open structure, high stability, and non-toxic properties, have recently been the subject of research for various applications, including their use as electrode precursors for capacitive deionization, gas storage, and environmental purification. These materials can be readily tailored to enhance their affinity towards gases for integration with sensing devices. An improved understanding of PBA-gas interactions is expected to enhance material development and existing sensor deposition schemes greatly. The use of inverse gas chromatography (IGC) is a robust approach for examining the relationship between porous materials and gases. In this study, the adsorption properties of (functionalized) hydrocarbons, i.e., probe molecules, on the copper hexacyanoferrate (CuHCF) lattice were studied via IGC, demonstrating that alkylbenzenes have a higher affinity for this material than n-alkanes. This difference was rationalized by steric hindrance, π–π interactions, and vapour pressure effects. Along the same line, the five isomers of hexane showed decreasing selectivity upon increased steric hindrance. Enthalpy values for n-pentane, n-hexane and n-heptane were lower than that of toluene. The introduction of increased probe masses resulted in a surface coverage of 46% for toluene. For all n-alkane probe molecules this percentage was lower. However, the isotherms of these probes did not show saturation points and the observed linear regime proves beneficial for gas sensing. Our work demonstrates the versatility of CuHCF for gas sensing purposes and the potential of IGC to characterize the adsorption characteristics of such a porous nanomaterial.