Catalyst device, sample vessel and method of hydrogen exchange analysis for hydrogen isotope analysis

Abstract

The invention comprises a catalyst device (1) for hydrogen isotope exchange analysis, wherein the catalyst device (1) consists of a catalyst carrier (10) and a catalyst material (20) applied to a surface (12) of the carrier (10), wherein at least the carrier surface (12) consists of an inorganic material and the catalyst material is sputtered or electrodeposited on at least a part of the surface (12) of the carrier (10). The invention further pertains to a sample vessel (100) for hydrogen isotope exchange analysis, wherein the sample vessel (100) contains one or more catalyst devices (1) according to the invention, wherein a maximum outer diameter (D) of the catalyst device (1) is smaller than a minimum inner diameter (101) of an opening of the sample vessel (100) or of the sample vessel (100) itself. The invention also foresees a method of hydrogen isotope analysis employing the sample vessel (100) and the use of the catalyst device (1) in a method of hydrogen isotope analysis.

Description

[0001] P260996WO00 - [TP388706WO1]

[0002] - 1 -

[0003] CATALYST DEVICE, SAMPLE VESSEL AND METHOD OF HYDROGEN EXCHANGE ANALYSIS FOR HYDROGEN ISOTOPE ANALYSIS

[0004] Field

[0005] The present disclosure concerns a catalyst device for enabling a hydrogen isotope exchange reaction between hydrogen gas and hydrogen isotopes bound in a fluid. The present disclosure further concerns a sample vessel for hydrogen isotope analysis containing the catalyst device, a method of hydrogen isotope analysis employing the sample vessel and the use of the catalyst device in a method of hydrogen isotope analysis.

[0006] Background

[0007] Hydrogen isotope exchange (HIE) analysis, particularly when combined with mass spectrometry (MS), is used in a variety of fields, e.g. but not limited to biochemistry, pharmaceutical research, environmental and material sciences and forensics. The main application lies within the determination of authenticity and origin control of food, feed and beverages. Hydrogen isotope exchange analysis and in particular in combination with mass spectrometry is a versatile and highly sensitive approach for studying a wide range of scientific and industrial problems, offering detailed insights into the structure, dynamics, and interactions of molecules.

[0008] The hydrogen equilibrium reaction, particularly in the context of hydrogen isotope exchange, involves the exchange of hydrogen atoms between a liquid sample containing hydrogen isotopes, for example water, and a hydrogen gas, often facilitated by a platinum (Pt) catalyst. Hydrogen isotope exchange refers to the process of replacing one hydrogen isotope with another, such as deuterium (D) or tritium (T), within a molecule. This exchange can occur when hydrogen gas (H2) and sample molecules (e.g. H2O) are in contact with the platinum catalyst. The platinum catalyst facilitates the breaking of the H2bond and the bond of the hydrogen isotope bound in the sample. Platinum provides a surface for these reactions to occur more readily, wherein the hydrogen containing molecules (both from the hydrogen gas and the sample) adsorb onto the surface of the Pt catalyst. On the surface of the Pt catalyst, the hydrogen isotope atoms dissociate from the H2and the sample P260996WO00 - [TP388706WO1]

[0009] - 2 - molecules, the hydrogen isotope atoms exchange and recombine to H2gas and sample molecules. The newly formed H2or isotopologue such as HD and the exchanged sample molecules desorb from the Pt surface and return to their respective phases (gas and sample vapour). This is represented by equation 1 for the example of water:

[0010] Equation 1 : pt H2O (vapor) + HD (gaseous) -> HDD (vapor) + H2(gaseous) wherein H is Protium, and D is Deuterium. The rate of reaching equilibrium in equation is described by the equilibrium constant (Ki):

[0011] The sample molecules themselves are in an equilibrium between the liquid and vapour phases according to equation 2.

[0012] Equation 2:

[0013] HDD (vapor) + H2O (liquid) HDD (liquid) + H2O (vapor)

[0014] The process continues until the rate of the hydrogen isotope exchange reaction in one direction equals the rate in the opposite direction, achieving equilibrium. At equilibrium, the isotopic composition of hydrogen in the gas phase and the liquid phase are constant and reflect the equilibrium isotope fractionation. The reaction rate and equilibrium state are influenced by temperature and pressure. Higher temperatures typically increase the reaction rate. Another crucial factor for the efficiency of the isotope exchange is the surface area of the Pt catalyst.

[0015] A method known in the art for achieving the hydrogen equilibrium is the Dual Inlet Technique. The dual inlet technique involves two separate gas inlets that allow alternating introduction of sample gas and reference gas into a mass spectrometer. Liquid samples are converted to hydrogen gas by passing them over a Pt catalyst in a controlled environment. The generated hydrogen gas from the sample is alternately introduced into P260996WO00 - [TP388706WO1]

[0016] - 3 - the mass spectrometer along with a reference gas of known isotopic composition using two separate inlets. The mass spectrometer measures the isotopic ratios of the sample gas and the reference gas in an alternating manner, allowing for precise and accurate determination of the hydrogen isotope ratios by comparing the sample to the reference.

[0017] Another technique for hydrogen isotope exchange analysis is the continuous flow technique. In continuous flow IRMS using helium, the hydrogen is prepared with the sample in a closed vessel and continuously flushed with helium or any other noble gas or inert gas such as nitrogen before the introduction of the hydrogen gas to the mass spectrometer.

[0018] The Thermo Scientific™ GasBench™ II or GasBench Plus™ System is a closed-vessel continuous flow system and used for stable isotope analysis, including hydrogen isotope analysis. In the GasBench™ system, the hydrogen gas is introduced into a reaction vessel by using a hydrogen gas mixture with a reactive inert gas such as helium. The hydrogen is a purchased mixed gas cylinder with helium (sample flush gas) at atmospheric pressure conditions at common flow rates of helium at 120 ml / min or slightly higher. The flow of the sample flush gas is dependent on the ratio of the sample volume versus the reaction vessel volume. The ratio determines the sufficient flow rate to enable complete exchange of atmospheric air with the helium carrier gas and hydrogen gas. The reaction vessel contains atmospheric air before closure of the reaction vessel which must be exchanged to allow the gas isotope ratio determination.

[0019] The closed vessel process involves the introduction of the prepared liquid water sample into the vessel. A platinum catalyst is added to the vessel and the vial is securely sealed after the catalyst has been added to ensure that the sample remains contained throughout the process. The hydrogen / helium mixture described above is introduced in the sealed vial or sample vessel with a flush or purge needle. The isotope exchange happens until the hydrogen isotopes within the water sample equilibrate with the hydrogen gas of the sample bound hydrogen, such as water from a sample, and the reaction vessel remains within the GasBench™ system, which provides a temperature-controlled environment. After the equilibration period, a small portion of the gas within the closed vessel is extracted and introduced into an isotope ratio mass spectrometer (IRMS) for analysis by a measurement needle. The IRMS measures the isotopic composition of the extracted gas, providing information about the hydrogen isotopic composition of the original water sample. P260996WO00 - [TP388706WO1]

[0020] - 4 -

[0021] The closed vessel process in this context enables precise control over the hydrogen isotope exchange reaction, ensuring accurate and reproducible measurements of the isotopic composition of samples containing water. It allows for the analysis of stable isotopes, such as deuterium and hydrogen, providing valuable insights into the origin, authenticity, and other parameters of the analysed samples.

[0022] Closed-vessel continuous-flow method uses a Pt catalyst, which is introduced into the sample vessel. A commercial catalyst is Pt on a spherical divinyl-benzene ethyl styrene copolymer ("Porapak") substrate or carrier. Such a catalyst has been manufactured by Shoko Ltd. (Japan) under the trade name "Hoko beads". For the closed-vessel continuous- flow method, the Hoko beads are glued on a PEEK tube (diameter: 4 mm) carrier by means of an epoxy resin. The Hoko beads contain the hydrophilic Pt catalyst in the hydrophobic porous structure of the polymer carrier. This combination enhances the hydrogen exchange equilibration reactions, and the surface of the Pt catalyst is not deactivated by liquid water on the Pt catalytic metal.

[0023] The performance of any new carrier / Pt catalyst can be assessed by comparing the isotope ratio accuracy and external reproducibility (standard deviation) obtained with the new catalyst / carrier combination versus a benchmark analysis using the Hoko Bead approach. It is important that the exchange reaction equilibrates stable over the analysis time for a rack of vessels without deactivation of the catalyst over time due to water condensation on the catalyst, wherein the equilibration time should be less than 2 hours. The carrier / catalyst should be robust and reusable.

[0024] The substrate for the Pt catalyst and the application substance (glue) for adhering the carrier on a substrate may influence the catalytic performance of the Pt. In particular, it has been found that Pt on an AI2O3 carrier was instead not as performant as the Hoko Beads because its powder structure favoured the deactivation of Pt by water condensation on the active surface of the catalyst. Acidic components such as acetic acid dilutes the resin glue and the Hoko beads are loosened from the surface, so that those cannot be used anymore.

[0025] Pt (0) EnCat40 (Sigma Aldrich, Art.No.: 681504-100g) consists of platinum on EnCat nanoparticles (Pt in a porous polyurea matrix). Polyurea is a highly porous material matrix but also highly hydrophilic. The Pt catalyst reactive surface is immediately deactivated by P260996WO00 - [TP388706WO1]

[0026] - 5 - impregnated glue in the pores, if the material is glued on a carrier for introduction into a sample vessel. Even if the glue is removed by abrasive methods (such as grinding) the surface activity is still too low, and because of the hydrophilic property of the polyurea all activity is immediately deactivated by water molecules condensation.

[0027] An alternative carrier / Pt catalyst combination is required as a catalyst for hydrogen isotope exchange reaction in use with sample vessels for closed-vessel continuous-flow systems. Particularly, it is required to provide a carrier for the Pt catalyst, wherein the catalyst is not deactivated by water condensation on the Pt surface from water contained in the sample or by the glue for application to a substrate, which is used to introduce the Pt with the carrier in a sample vessel.

[0028] US 3,888,974 A (W. H. Stevens) addresses a bithermal process for hydrogen isotope exchange between gaseous hydrogen and liquid water using a catalytically active metal, wherein the solution inhibits to some extent the deactivation of the catalytically active metal by liquid water. The catalyst is provided with a substantially liquid-water-repellent organic resin or polymer coating permeable to water vapour and hydrogen gas. Catalytic hydrogen isotope exchange can be described by two reaction mechanisms:

[0029] 1 . A hydrophobic reaction, i.e. the catalysis of the hydrogen exchange with a catalyst such as platinum and

[0030] 2. The equilibration of a hydrogen isotope signal of hydrogen gas in a vapour phase (hydrophilic reaction) in a head space over a liquid sample phase.

[0031] The first reaction is impaired by condensed water, which causes the catalysis to immediately stop.

[0032] In order to further inhibit the deactivation of the catalytically active metal by contact with liquid water US 4,025,560 A (J. H. Rolston, et al.) discloses a similar process to that described in US 3,888,974 A and allowing a greater rate of hydrogen isotope exchange by using a metallic catalyst consisting of at least one Group VIII metal, deposited in the pores of a porous, inherently hydrophobic support. Such a support substantially prevents the catalyst from being in contact with a stream of liquid water while allowing hydrogen gas and water vapour to come into rapid contact with the catalyst.

[0033] US 4,126,667 A (J. P. Butler et al.) suggest that higher overall hydrogen isotope exchange rates between hydrogen and liquid water can be achieved when the catalyst packed bed P260996WO00 - [TP388706WO1]

[0034] - 6 - consists of a hydrophilic packing structure interspersed with a hydrophobic catalyst structure. The addition of hydrophilic surfaces into the packed bed increases the exchange rate of hydrogen isotopes between water vapour and liquid water because the contact surface area is increased, so that the overall exchange rate between gaseous hydrogen and liquid water in the two-step exchange process as shown in US 3,888,974 A is not retarded by the exchange rate between water vapour and liquid water.

[0035] To further increase the rate of the water vapour / liquid water exchange reaction, US 4,471 ,014 A foresees an ordered bed catalytic packing module for the combination of both catalytic and gas-liquid transfer reactions, comprising alternate layers of plane and corrugated sheet coiled together to form a roll, and providing unobstructed fluid passages between the plane and corrugated sheets. The plane sheet is of a woven, knitted felted cloth of a textile, wicking material which will provide an uninterrupted wicking path, between the ends of the roll. The plane sheet is substantially catalytically inactive with respect to the gas and the liquid, and the corrugated sheet comprises an open mesh carrier with an outer surface layer comprising a high molecular weight, organic, polymeric substance which will be inherently hydrophobic with respect to the liquid. Catalyst crystallites of at least one element selected from Group VIII of the Periodic Table are dispersed in and partially enclosed by the porous matrix so that the porous matrix will substantially inhibit the contact of liquid water.

[0036] The bond breakage of C-C bonds in organic molecules is favoured in combination with catalysts containing gold (Au) alloys by different concentrations of the platinum and the other alloy metal, e.g., gold (Broensted-Evans-Polnayi relationship). For alcoholic beverages, this leads to a difference in products from such a C-C bond breakage (Hao Li, et al.: Ethanol Decomposition on Pd-Au Alloy Catalysts, J Phys C 2018, 122, 22024 — 22032), e.g. H2, CH4, CO. Especially, methane is produced from beverages containing alcohols such as ethanol or diols. Methane is created as a highly concentrated product which inhibits the measurement of H2because it resides on the analytical column and additional hydrogen is produced which is added to the hydrogen of the mixed gas and changes the hydrogen isotope ratio between the H2O / H2equilibration.

[0037] The invention thus seeks to provide a new catalyst device, which is formed in a new way, for use in hydrogen isotope exchange analysis and in particular a device, which can be reused in closed-vessel hydrogen isotope exchange analysis and addresses the above- P260996WO00 - [TP388706WO1]

[0038] - 7 - mentioned challenges encountered with the proposed catalyst / carrier combinations of the prior art. The invention also provides a sample vessel, a method of hydrogen isotope analysis and the use of the catalyst device in hydrogen isotope analysis.

[0039] Summary

[0040] The invention comprises a catalyst device for hydrogen isotope exchange analysis, wherein the catalyst device consists of a catalyst carrier and a catalyst material applied to a surface of the carrier, wherein at least the carrier surface consists of an inorganic material and the catalyst material is sputtered or electrodeposited on at least a part of the surface of the carrier. In a further development of the invention, it is provided that at least the carrier surface consists of a metal or metal-alloy.

[0041] The use of an inorganic carrier, and in particular a carrier made of or consisting of a metal or a metal alloy with a sputtered or electrodeposited catalyst, which is preferably a coating on at least a part of the surface of the carrier, has the advantage of a strong bond between the carrier and the catalyst. In particular, it is not necessary to foresee any glue like e.g. epoxy glue, or any further intermediate material to which the catalyst is embedded. The abrasion resistance of sputtered or electrodeposited materials is superior to the abrasion resistance of adhesively bonded materials. Thus, if the catalyst device is removed out of a sample vessel, the catalyst is not removed or abraded from the carrier when the device is taken out through the vessel opening. The re-usability of the catalyst device is therefore improved. Furthermore, the carrier itself made of or consisting of a metal or a metal alloy has a high strength and is therefore durable. To further promote the sputtering or electrodeposition with the catalyst, the catalyst carrier material may have a surface, which has a protective coating and / or a coating to enhance the adhesion of the catalyst material. Such a coating may be, by way of example, inorganic and in particular a titanium or titanium alloy coating.

[0042] Any intermediate carrier particles (coated with the catalyst material), which would need to be bonded to the actual carrier structure or embedded in a holding material (glue or organic holding material) as shown in the prior art, are avoided by an embodiment according to the invention. This has the further advantage that there is a reduced likelihood of interactions of any intermediate materials like glue, intermediate carriers or holding material with the sample (e.g. dissolution of a glue or organic holding material such as PTFE by acidic P260996WO00 - [TP388706WO1]

[0043] - 8 - samples) or interaction of those materials with the hydrogen isotope exchange reactions themselves. The resulting hydrogen isotope signal is therefore not impeded by such second-order effects and much cleaner using a carrier surface of an inorganic material sputtered or electrodeposited with the catalyst material.

[0044] An embodiment comprising a coating of pure platinum or a platinum alloy enables hydrogen isotope ratio determination of water in alcoholic beverages. In embodiments with a pure platinum or optionally with an adhesive metal coated before the finishing platinum layer, the C-C bond cleavage is reduced while the concentration of methane or hydrogen is significantly reduced, enabling the measurement of hydrogen isotopes in water in alcoholic beverages.

[0045] In certain applications, such as the analysis of alcoholic beverages, and as an embodiment of the invention, a catalyst is preferably used for analysing samples containing hydroxyl organic compounds. Such analyses involve a C-C bond break and the formation of methane, CO and hydrogen. Methane exerts e.g. side effects in an ion source of mass spectrometry analysis, and it may also reside in a chromatographic analytical column and inhibit a proper separation of hydrogen from co-eluted gas compounds. As a result of this, hydrogen cannot be measured. The methane falsifies the analysis of sample-hydrogen molecules through its own hydrogen atoms. A pure platinum or palladium coating (by sputtering or electrodeposition) is therefore preferably used. As an alternative alloys of platinum or palladium with Fe, Ni, Cr, or PtAu may be used.

[0046] The invention can be embodied by a bar-shaped carrier. According to an optional embodiment, it may be provided that the carrier is a solid rod and in a further optional embodiment it may be provided that the rod-shaped carrier has cone-shaped ends.

[0047] A bar-shape, which may be a solid bar or a tube is a preferable carrier geometry, as the bar shape allows a sufficient surface area for the catalyst application. The catalyst is preferably applied on the lateral surface of a bar-shaped carrier. The bar-shape can be of a circular, ellipsoid, flat or polygonal shape in a cross-sectional profile. The bar-shaped carrier can preferably be embodied with cone-shaped ends, which may also be of frustoconical form, as those allow an easier introduction of the catalyst device in sample vessels. P260996WO00 - [TP388706WO1]

[0048] - 9 -

[0049] The invention may further comprise that the carrier has at least one threaded surface. According to a further optional embodiment, it may be provided that the carrier has at least one roughened surface. The threaded or roughened surface significantly increases the surface area compared to a smooth surface. This enhancement in surface area is primarily due to the additional geometry introduced by the thread(s) or roughness sections, which creates more peaks, valleys, and ridges along the surface. The increase in surface area has the primary technical effect that the increased surface area allows for more substantial contact with the surrounding material, thereby improving the efficiency of the catalysis reaction of hydrogen isotope exchange.

[0050] When threads or roughening are applied preferably to a lateral surface of the catalyst carrier, the technical effects are particularly noticeable. In addition to the increased surface area, the roughened surface can enhance the bonding of the catalyst coating. In that way, a physical surface activation is achieved, which may be a prerequisite for forming a strong and uniform bond. The activation increases the surface energy of the carrier, especially for but not limited to electroplating, and creates micro-scale anchor points for interlocking with the deposited catalyst material, resulting in a stronger and more durable connection. The benefit of such an activated surface is a reduced risk of delamination or flaking of the catalyst layer during use or subsequent regeneration cycles, thereby improving the overall long-term stability and reusability of the catalyst device.

[0051] Another optional embodiment of the invention foresees that the carrier consists at least partly of a sheet material. The invention may further comprise that the sheet material has a surface of a metal or metal alloy or is made of or consists of a metal or a metal alloy. In a further development of the invention, it is provided that the sheet material is rolled, preferably to form a bar-shaped carrier.

[0052] The provision of the carrier as sheet material, which is preferably rolled or folded and / or brought into a bar-shaped form, offers advantages, particularly in terms of total active surface area. Unlike a solid bar, where the surface area is limited to the external circumference and potentially the upward and downward end areas, the rolled sleeve has an additional inner surface that contributes to the total active area, in particular, if the sleeve windings have no self-contact, which is preferable. This effectively increases the available surface area. The increased surface area allows for more efficient interaction with P260996WO00 - [TP388706WO1]

[0053] - 10 - the surrounding hydrogen gas or a sample vapor, enhancing the performance of the hydrogen isotope exchange reaction.

[0054] Furthermore, the rolled sheet results in a more compact and efficient design compared to solid bars, as the carrier embodied as solid bar requires much more of the carrier material in relation to the surface area available for coating with the catalyst. Additionally, the manufacturing process of rolled sleeves can be more flexible, allowing for customization of surface textures on both the inner and outer surfaces, further enhancing their functional performance in specialized applications. The rolled sheet material may feature creases, which are applied before rolling to increase the integrity of the rolling and to prevent unrolling of the rolled sheet material.

[0055] It may optionally be foreseen that the sheet material is folded, preferably with a leporello folding or zig-zag folding. According to another embodiment it may be foreseen that the sheet material is stapled from two or more separate sheets to form a package of sheet material.

[0056] The folded sheet offers similar advantages as the rolled sheet. The folding process increases the surface area by creating multiple layers and ridges wherein it is possible to maintain the same outer dimensions as desired for the catalyst carrier. This increased surface area is especially beneficial for the catalytic conversion, as the increased surface area allows for more efficient processes.

[0057] The folded sheet's design also offers flexibility in adjusting the surface properties to meet specific application requirements. For instance, different folding patterns can be tailored to optimize fluid dynamics, ensuring that gases or liquids flow efficiently over the surfaces. This advantage does also apply to the rolled sheet as discussed above. Both embodiments facilitate the fluid passage parallel to the rolling or folding direction, while this would not be possible with a solid carrier. As long as also the inner surfaces of the folded or rolled sheet are coated with the catalyst, the active surface for catalysis is at the same time increased and made accessible to the sample vapor and the hydrogen gas for the hydrogen isotope exchange reaction. This flexibility is something a solid bar cannot match, as its surface area is inherently limited to its outer dimensions. P260996WO00 - [TP388706WO1]

[0058] - 11 -

[0059] The invention can be embodied in that the sheet material has stabilizing features parallel to a rolling or folding direction. According to an optional embodiment, it may be provided that the stabilizing features are thickened portions of the sheet material. According to a further optional embodiment, it is provided that pleats form the thickened portions of the sheet material.

[0060] Stabilizing features such as e.g. pleats or thickened material portions running preferably parallel to the folding or rolling direction of the sheet have the technical effect of particularly enhancing the structural integrity and rigidity of the fold or roll. These pleats act as reinforcement ribs, distributing stress more evenly across the sheet and reducing the risk of deformation under load. In folded or rolled configurations, where the sheet material (e.g. metal or a metal alloy) might otherwise be prone to buckling or bending, the parallel pleats provide support by increasing the sheet’s resistance to bending and / or torsional forces. This results in a more robust structure, capable of withstanding higher loads without compromising the integrity of the folded or rolled shape.

[0061] Additionally, and more importantly, the pleats contribute to maintaining the geometric stability of the folded or rolled sheets during both manufacturing and operation. They prevent unwanted shifting or flattening of the folds or rolls, ensuring that the intended surface area and shape are preserved. This is particularly important as consistent surface geometry is crucial for performance and reproducibility. By stabilizing the structure of the fold or roll, these features also improve the durability and lifespan of the carrier, as they help to minimize fatigue, wear, and disconnection of the catalyst coating that could otherwise occur due to repeated mechanical stresses. The inclusion of pleats therefore enhances the mechanical performance and reliability of folded or rolled metal sheet carriers.

[0062] The invention may further comprise that the surface of the sheet material has no selfcontact, in particular when it is rolled or folded. The invention can be embodied in that the catalyst device comprises at least one distance element in folded or rolled sections of the sheet material for spacing apart the parts of the surface. The invention may further comprise that the distance element is a sheet inlay in the folded or rolled sections of the sheet material arranged to prevent adjacent parts of the surface from contacting. According to a further optional embodiment, it is provided that the distance element is made of a material inert to the catalyst. P260996WO00 - [TP388706WO1]

[0063] - 12 -

[0064] Avoidance of self-contact in folded or rolled sheets of the carrier preserves and optimizes the surface area. When self-contact is avoided, the entire surface area of the sheet remains exposed and available for interaction with the surrounding environment, resulting in high surface efficiency. In contrast, areas of self-contact would result in portions of the surface being obscured, reducing the effective surface area. By preventing such contact, the sheet can maximize its functional performance for the catalytic conversion, where surface exposure is crucial.

[0065] The inclusion of an inlay or distance elements between the folds or rolls further supports the avoidance of self-contact by physically separating adjacent layers. This not only ensures that the surface area remains fully available but may also help to maintain the geometric integrity of the folds or rolls. The inlay can also provide additional benefits, such as acting as a thermal insulator or a spacer to control the flow of fluids or gases between the layers. The avoidance of self-contact, therefore, directly contributes to the efficiency and reliability of the component, making it well-suited for applications where maximizing surface interaction is essential.

[0066] In a further development of the invention, it is provided that the sheet material is a continuous sheet.

[0067] A continuous rolled or folded sheet offers a uniform surface area without interruptions, which enhances its performance in applications requiring consistent interaction with fluids, gases, or heat. The uninterrupted surface allows for smooth and predictable flow dynamics, reducing the likelihood of turbulence or inefficiencies that could arise from gaps or perforations. This continuity also ensures that the entire surface can be utilized effectively for processes the coating with the catalyst or later in application for the catalytic reaction, as there are no breaks or irregularities that might hinder these interactions. The result is an efficient, reliable component, which can be manufactured in a reproducible manner.

[0068] Additionally, the continuous nature of the sheet provides a stronger and more stable structure, which is beneficial in maintaining the integrity of the rolled or folded form. The absence of gaps or perforations in the material allows for even stress distribution across the surface, reducing the risk of deformation or failure under load, e.g. during manipulation of the catalyst carrier device. Moreover, the continuous surface is easier to clean and P260996WO00 - [TP388706WO1]

[0069] - 13 - maintain, as there are no small openings where debris or contaminants could accumulate, further extending the lifespan and efficiency of the component.

[0070] The invention can be embodied in that the sheet material is a mesh.

[0071] A mesh sheet allows for greater permeability and flow through the material and the mesh also provides flexibility in tailoring the size and shape of the openings to meet specific performance requirements, such as e.g. optimizing flow rates. The mesh sheet, with its perforated design, impacts the overall surface area by creating additional edges and contours around each perforation, i.e. opening. The increased edge surface area around each perforation can contribute to enhancing the catalysis reaction, wherein the edges provide additional active sites. The overall surface area of the mesh and, if coated with the catalyst material, the active area of the catalyst device may be approximately the same as for a continuous rolled or folded sheet with the same original dimensions or even greater due to the additional edge surface around the mesh perforations. A mesh carrier may have the further advantage that if the mesh is inserted into the liquid (e.g. water) sample, a high capillarity of the liquid, which would deactivate the catalyst, may be prevented. According to an optional embodiment, it may be provided that the mesh is woven, knitted or felted. Here, the same effects and advantages apply.

[0072] The invention may further comprise that the sheet or mesh surface has superhydrophobic properties. This has the technical effect that the catalytic reaction is not inactivated by contact with water of a sample.

[0073] According to a further optional embodiment, it is provided that the catalyst material comprises platinum, preferably sputtered from an Pt or PtAu target and / or an additional adhesive metal surface pre-treatment. Meaning that platinum is deposited via sputtering from a target which may be preferably Pt or a PtAu alloy target, resulting in a Pt-rich layer.

[0074] In other embodiments, the catalyst material comprises another platinum group metal (PGM) or an alloy thereof, for example palladium or an alloy, such as PtAu, similarly sputtered from an Pd or alloy target. The catalyst material may comprise a platinum group metal alloyed with a noble metal, such as Au, as in PtAu. As discussed above, for samples containing hydroxyl organic compounds, the sputter target may be a different platinum alloy (in particular not PtAu) and the catalyst carrier material may further optionally comprise P260996WO00 - [TP388706WO1]

[0075] - 14 - titanium or a titanium alloy, which also contributes to the reduction of the above-discussed C-C bond cleavage.

[0076] A sputtered coating provides a highly controlled and uniform layer of material on a substrate, such as the catalyst carrier, regardless of its shape (rod, or sheet, continuous or mesh), which contributes to the mechanical robustness and consistency of the coating. The sputtering process involves bombarding a target material, which is preferably pure Pt or PtAu with high-energy particles, causing atoms to be ejected and deposited onto the substrate. This method allows for precise control over the thickness and composition of the coating, resulting in a consistent and homogeneous layer with excellent adhesion to the underlying material. The uniformity of the sputtered coating reduces the likelihood of weak points or variations, enhancing the durability and maintaining consistent performance.

[0077] Furthermore, the sputtered coating exhibits good mechanical robustness due to the dense and compact structure formed during the deposition process. The strong bond between the coating and the substrate helps to resist wear, corrosion, and other forms of degradation that could compromise the component’s integrity.

[0078] In an advantageous embodiment, the catalyst material is substantially pure platinum, optionally with a adhesive coating or bonding layer comprising another metal. That is, the catalyst material may be platinum having a purity of at least 98%, preferably at least 99%, more preferably at least 99.9%, still more preferably at least 99.99%. In addition, the catalyst material preferably forms a continuous, substantially uninterrupted platinum layer. Such embodiments are particularly suitable for the measurement of isotopes of hydrogen in water in alcoholic beverages, such as beer and wine. The optional bonding layer or adhesive coating between the sputtered coating and the carrier may comprise titanium or mixtures of, for example, WTi10, titanium, tantalum (Ta) and / or chromium. Instead of a sputtered coating of platinum, a sputtered coating of palladium may be used.

[0079] In a further development of the invention, it is provided that the catalyst material comprises platinum electrodeposited on the surface of the carrier and / or an additional adhesive metal surface pre-treatment. Electrodeposition forms a strong adhesion between the catalyst material and the catalyst carrier and prevents issues like delamination, ensuring that the catalyst remains intact under mechanical stress. P260996WO00 - [TP388706WO1]

[0080] - 15 -

[0081] According to an optional embodiment, it may be provided that the catalyst material comprises palladium or any other metal of the Platinum Group Metals (PGM) or Platinum Group Elements (PGE). Such catalyst materials (or their alloys, e.g. PtAu) may be used for specific hydrogen isotope analysis.

[0082] Another aspect of the invention pertains to a sample vessel for hydrogen isotope exchange analysis, wherein the sample vessel contains one or more catalyst devices according to any of the above features, wherein a maximum outer diameter of the catalyst device is smaller than a minimum inner diameter of an opening of the sample vessel or of the sample vessel itself. In a further development of the invention, it is provided that the sample vessel is a sample vial. The invention can be embodied in that the sample vessel has a bottom portion extending partly over a height of the sample vessel from its bottom towards an opening opposite to the bottom of the vessel, configured to receive a volume of a liquid sample. The invention may further comprise that the catalyst device is offset from the bottom of the sample vessel by one or more distance elements, which can act as spacers.

[0083] For advantages and technical effects for the embodiment of the catalyst device, it is referred to the preceding paragraphs. The maximum outer diameter of the catalyst device being smaller than the minimum inner diameter of the vessel does allow for an unobstructed insertion of the catalyst device in the sample vessel. The catalyst carrier is preferably enclosed or fixed in the vessel, such that the catalyst can be transported and handled without moving it out of the reaction vessel. The user can optionally clean the embodiment without removing the catalyst carrier from the vessel.

[0084] The optional offset or spacing by distance elements and / or the provision of a bottom portion of the vessel as a liquid sample receptacle room has the technical effect that wetting of the catalyst carrier surface and in particular the active surface of the catalyst carrier can be prevented. Wetting reduces the active area of the catalyst and wetting may e.g. occur due to direct contact condensation due to change in the dew point or due to capillary effects. If the catalyst is wetted, the catalytic reaction is commonly immediately stopped in the wetted areas. The catalyst carrier may be overlapping with the bottom portion of the sample vial, wherein in a first embodiment, the overlapping area of the catalyst carrier is not coated with the catalyst and in another embodiment, the overlapping area also has the catalyst material. In the latter case, wetting of the catalyst with the liquid sample may occur under the sacrifice of the inactivation of the catalyst in that overlapping P260996WO00 - [TP388706WO1]

[0085] - 16 - area. Additionally, if a highly aggressive sample is used, the optional offset by distance elements and / or the provision of a bottom portion serves to create a distance to any contact of the sample with the catalyst device, and particularly the active area with the catalyst material, as the sample resides in the bottom portion by gravity and preferably separated from the catalyst device.

[0086] According to a further optional embodiment, it is provided that the one or more distance elements are glass beads, ceramic structures, metal fabric, or a solid block of material. The invention can be embodied in that the one or more distance elements are of a material inert to the sample and to hydrogen isotopes. In a further development of the invention, it is provided that the vial contains a cloth or mesh extending at least partly in the bottom portion and extending at least partly above the bottom portion. The invention may further comprise that the offset corresponds to the sample volume to be withheld in the bottom portion.

[0087] The provision of distance elements further contributes to the technical effects mentioned above in relation to the bottom portion, as the distance elements with their specific embodiments each contribute to the separation of the liquid sample from the catalyst device and in particular from the active surface of the catalyst device, where the catalyst carrier is coated with the catalyst.

[0088] The invention can be embodied in that the catalyst device has a removable outer sleeve around its outer circumference, for example in the form of a tube, sheet or fabric.

[0089] A removable sleeve around the catalyst device plays an important role in maintaining mechanical integrity (if the carrier is embodied as folded or rolled sheet or mesh) and providing protection during insertion into a sample vessel. Mechanically, the sleeve helps stabilize the catalyst device, preventing deformation or damage that might occur due to handling or installation stresses. For folded or rolled catalyst device structures, the sleeve acts as a protective barrier that maintains the device’s shape and ensures the uniformity of its surface area. This protection is essential for preserving the catalyst’s performance and longevity, as any deformation or misalignment could adversely affect its catalytic efficiency or lead to premature failure. The outer sleeve may be made of a water repellent material to prevent water from the sample rising to the catalyst and deactivating it. P260996WO00 - [TP388706WO1]

[0090] - 17 -

[0091] During insertion into a sample vessel, the removable outer sleeve provides a layer of cushioning that shields the catalyst device from physical damage. This is particularly important in applications where the catalyst is housed in tight or confined spaces such as sample vessels or vials, where contact with the sample vessel walls or the opening orifice could otherwise cause abrasion or other forms of mechanical stress. The sleeve facilitates smoother insertion by reducing friction and preventing direct contact with potentially abrasive surfaces. Once the catalyst device is securely in place within the sample vessel, the sleeve can be removed, leaving the catalyst device intact and ready for operation. This protective approach not only ensures the integrity of the catalyst but also simplifies the installation process, ultimately contributing to more efficient and reliable catalytic processes. In an alternative embodiment, where the abrasion resistance during insertion plays a subordinate role, but the mechanical integrity is still to be maintained, it may also be foreseen that the catalyst device is held together by one or more threads wound and secured, e.g. by a knot, around the lateral surface of the catalyst device.

[0092] According to an optional embodiment, it may be provided that the catalyst device is attached to the bottom of the sample vessel and the catalyst coating is not present on the surface of the catalyst carrier overlapping with the bottom portion. In a further development of the invention, it is provided that the catalyst device has no contact to the sample vessel apart from designated attachment sections. The invention may further comprise that the catalyst device is attached to the bottom of the sample vessel in an attachment section. According to a further optional embodiment, it is provided that the catalyst device is attached to the distance element in an attachment section. The invention can be embodied in that the distance element is attached to the bottom of the sample vessel in an attachment section. The invention can be embodied in that the catalyst device is attached to a side wall of the sample vessel in an attachment section. The invention can be embodied in that the catalyst device is attached to a cap of the sample vessel in an attachment section.

[0093] The different attachment positions all further contribute to the avoidance of wetting as above. The invention may further comprise that the catalyst device is attached to the sample vessel by means of an adhesive, e.g. by adhesive measures such as gluing, or may be semi-permanent or removably. P260996WO00 - [TP388706WO1]

[0094] - 18 -

[0095] The catalyst device is suitable as a hydrogen exchange catalyst and is reusable. The catalyst device enables analysis of the isotope ratio of hydrogen from water contained in a sample. The catalyst device enables analysis of the isotope ratio of hydrogen from other compounds than water, such as organic compounds, for example alcohols. The gas from the hydrogen exchange reaction catalysed by the catalyst device may be analysed by mass spectrometry.

[0096] The invention thus provides use of the catalyst device in a method of hydrogen isotope analysis.

[0097] The invention also provides a method of hydrogen isotope analysis of a water-containing sample, comprising the steps of: providing the sample in a closed vessel; providing a catalyst device according to the invention in the closed vessel; introducing hydrogen gas into the closed vessel; causing exchange of hydrogen isotopes to occur in the closed vessel between hydrogen isotopes in the water and hydrogen isotopes in the hydrogen gas and allowing the exchange of hydrogen isotopes to equilibrate for an equilibration period; and after the equilibration period analysing the hydrogen gas using a mass spectrometer to determine an isotopic composition of the gas.

[0098] A precise volume of the sample may be injected into the vessel, which may be a vial or container. The catalyst device may be added in the vessel before or after the sample. The vessel is closed after addition of the catalyst and sample. The catalyst device preferably comprises platinum as described herein and facilitates the hydrogen isotope exchange reaction within the closed vessel. The hydrogen gas concentration is selected to fit the analytical range of the mass spectrometer.

[0099] The closed vessel containing sample and catalyst may be located in a controlled environment, such as in the Thermo Scientific™ Gasbench™ system, typically a temperature-controlled environment, since the isotope exchange process of the hydrogen in water in the gaseous phase and the liquid phase is temperature dependent. The temperature range should preferably be in a range to prevent water freezing (at least 5 °C at atmospheric pressure) and prevent condensation of water on the Pt catalyst to preclude deactivation (not greater than 80 °C). The closed vessel is allowed to equilibrate for a P260996WO00 - [TP388706WO1]

[0100] - 19 - specific equilibration period, during which the hydrogen isotopes within the water containing sample exchange with the isotopes of the hydrogen gas. This process ensures that the isotopic composition of the water sample is accurately represented in the same fraction as for standards and samples or control standards (“Principle of identical treatment”). After the equilibration period, a small portion of the hydrogen gas within the closed vessel is extracted and introduced into an isotope ratio mass spectrometer (I RMS) for analysis by a measurement needle. The IRMS measures the isotopic composition of the extracted gas, providing information about the hydrogen isotopic composition of the original water containing sample.

[0101] The closed vessel process enables precise control over the hydrogen isotope exchange reaction, ensuring accurate and reproducible measurements of the isotopic composition of samples containing water. It allows for the analysis of stable isotopes, such as deuterium and hydrogen, providing valuable insights into the origin, authenticity, and other parameters of the analyzed samples.

[0102] In the course of hydrogen isotope analysis, the catalyst device may become deactivated, reducing its efficiency for the hydrogen isotope exchange reaction. Deactivation can occur when the catalyst material, typically Pt or a PtAu alloy, becomes coated with inorganic or organic components from the sample. This coating can occur through evaporation and subsequent condensation or via capillary effects if the device comes into contact with the liquid sample. Furthermore, deactivation may result from chemical processes such as the hydrogenation or oxidation of the catalytic surface by the sample matrix, or the formation of a chemical layer that inhibits the catalyst's interaction with the equilibration reagent, e.g. hydrogen gas.

[0103] To restore the performance of the catalyst device and to enhance its reusability, a regeneration process may be performed. An embodiment of the method may thus comprise the step of regenerating the catalyst device for hydrogen isotope exchange analysis. If the catalyst device has been deactivated through use, the deactivated catalyst device may be subjected to a regeneration treatment. The regeneration treatment may be selected from at least one of a physical treatment, a chemical treatment, or a combination thereof. The physical treatment may comprise an abrasive action, a sonic treatment, or surface blasting (spraying abrasive particles). P260996WO00 - [TP388706WO1]

[0104] - 20 -

[0105] The chemical treatment may comprise contacting the catalyst device with a chemical cleaning agent selected from the group consisting of soaps, acids, alkaline reagents, alcohols, peroxides, organic solvents, and mixtures thereof. The regeneration treatment has the technical effect that deactivating substances are effectively removed, whether they are organic or inorganic components from a sample deposited the catalyst material or chemical alterations such as oxidized or hydrogenated platinum. The benefit of this regeneration is the restoration of the catalyst's activity. This extends the operational lifetime and enhances the re-usability of the catalyst device. By enabling effective in-situ or ex-situ cleaning, the method reduces the need for frequent replacement of the catalyst device, thereby lowering operational costs and waste.

[0106] Physical treatments may involve the mechanical removal of contaminants. In one embodiment, this involves an abrasive action, for instance, by gently rubbing the surface of the catalyst carrier with a fine-grade abrasive media such as sandpaper, preferably having a particle size between approximately 120 and 12000, or steel wool or abrasive materials such as inorganic oxides, abrasive crystals, or other abrasive substances and / or sonic treatment and / or blasting.

[0107] For a catalyst device where the carrier is a rolled sheet material, the sheet may be unrolled to provide better access to its surfaces for abrasion. Care should be taken to treat the entire catalysed surface, as some areas may remain occluded if the sheet material does not lie perfectly flat. Other physical treatments include sonic treatment (sonication) in a fluid or blasting the surface with a suitable abrasive medium.

[0108] Chemical treatments utilise cleaning agents to dissolve or dislodge contaminants, wherein the selection of the agent depends on the nature of the deactivating substance. Suitable chemical agents include, but are not limited to, methanol (MeOH), a mixture of isopropanol and water, a (preferably) 1 :1 mixture of isopropanol and water, n-hexane at a volume range of preferably 60-99%, or an aqueous solution of nitric acid at a volume range of 1 to 30%, preferably approximately 5 to 10%. Other agents such as soaps, preferably with acids, alkaline reagents (e.g., NaOH) at a volume range of preferably 5-20%, peroxides at a volume range of preferably 5-20%, or other organic solvents can also be used. P260996WO00 - [TP388706WO1]

[0109] - 21 -

[0110] The method may comprise one or more chemical and / or physical treatment steps as exemplarily outlined below, not necessarily in the order as presented below. It will be understood that not all steps are required.

[0111] Placing a deactivated catalyst device in a suitable vessel, such as a reaction tube, and submerging the catalyst device in a selected chemical cleaning agent

[0112] - Sonicating of the catalyst device preferably up to 10 minutes, to dislodge the deactivating substances from the catalyst surface, wherein the sonicating frequency is preferably ultrasonic

[0113] Draining the chemical cleaning agent from the vessel

[0114] Rinsing the catalyst device to ensure that all contaminants and residual cleaning agents are removed

[0115] - Adding deionised water to the vessel and preferably sonicating again for a preferable period of up to 5 minutes

[0116] Removing the catalyst device from the vessel

[0117] Rinsing the catalyst device under a continuous stream of water, preferably deionised water

[0118] Drying the regenerated catalyst device before use in a hydrogen isotope analysis.

[0119] The invention further provides the use of the catalyst device according to the above or the sample vessel according to the above, in a method of hydrogen isotope analysis. The method may preferably be embodied as the foregoing method.

[0120] Listing of Figures

[0121] The present disclosure will now be described by way of example, with reference to the accompanying drawings, in which:

[0122] Figures 1 A-D show four embodiments of the catalyst device,

[0123] Figures 2A-D show different embodiments of the rolling-folding of the sheet material;

[0124] Figures 3A-C show a sample vessel for hydrogen isotope exchange analysis;

[0125] Figures 4A-C show embodiments of a distancing concept for the catalyst device within the sample vessel; and P260996WO00 - [TP388706WO1]

[0126] - 22 -

[0127] Figures 4D-E show embodiments of possible attachment or support strategies for the catalyst device within the sample vessel.

[0128] Figures 5A-B schematically show sectional views of catalyst materials arranged on a catalyst carrier.

[0129] Detailed Description

[0130] Unless otherwise indicated, the reference signs are used uniformly in the drawings, i.e. a reference sign always refers to the same feature for all embodiments.

[0131] Figure 1 A-D show four embodiments of the catalyst device 1 , wherein Fig. 1 A shows a catalyst device 1 with a bar-shaped catalyst carrier 10, wherein the catalyst carrier 10 is a solid rod having ends 5, 6, which in the embodiment of Fig. 1 A are frustoconical ends. The surface area of the rod, and in particular on the circumferential lateral surface between the ends may be increased by roughening or by application of a thread (not shown in the figures). Fig. 1 B shows a catalyst device 1 , wherein the catalyst carrier 10 is made of a rolled sheet material 13. The sheet material is a continuous sheet 15, i.e. without any perforations. Fig. 1 C shows a catalyst device 1 , wherein the catalyst carrier 10 is made of a rolled sheet material 13. The sheet material is a mesh 16. The sheet material of Fig 1 B,C is rolled. Viewed perpendicular to the rolling direction R, the rolled sheet material 13 may have a spiral-like cross-section. In an alternate variant of this embodiment, the spiral crosssection may involve vertical creases which run substantially parallel to the rolling direction R. Those vertical creases may deviate from the pure geometric form of a spiral. Fig. 1 D shows an embodiment of the catalyst device 1 , wherein the catalyst carrier 10 is a folded sheet material. As with the embodiments shown in Fig. 1 B and Fig. 1 C, the sheet material can be embodied as a sheet material, as a continuous sheet or as a mesh 16. The mesh 16 may be woven, knitted or felted. The folding may be a zig-zag folding or a leporello folding. All embodiments of the catalyst device 1 feature a respective maximum outer diameter D.

[0132] All the catalyst carriers 10 shown in Figs. 1 A-D have a catalyst material 20 applied to a surface 12 of the catalyst carrier 10. The catalyst carrier surface 12 consists of an inorganic material, which is preferably a metal or a metal alloy, which may be one of, but not limited to: PGM, preferably platinum, and alloys containing at least one PGM. The catalyst material P260996WO00 - [TP388706WO1]

[0133] - 23 -

[0134] 20 is coated at least partly to the surface 12 and the catalyst material 20 coating may be applied by a sputtering or electrodeposition process. The catalyst material coating can be applied to the carrier surface before or after rolling or folding the sheet material. The coating may be applied before rolling or folding in the case of sputtering because if the sheet is rolled or folded before sputtering, the surfaces to be coated may become at least partly shaded to the sputtering by the rolling or folding. The sputtering with platinum or a platinum alloy may be done from a Pt or PtAu target. It may as well - for certain applications involving hydrogen exchange analysis for hydrogen isotopes - that the catalyst material 20 contains or consists of palladium. The catalyst material 20 has preferably a thickness between 25 and 150 pm.

[0135] Figure 2A-C show different embodiments of the rolling or folding of the sheet material. Fig. 2A shows from top to bottom a simple rolling and a simple folding of the sheet material and from left to right the evolution of the rolling and folding outer dimensions over time, as the sheet material tends to unroll or unfold due to internal mechanical stresses. This is unproblematic, as soon as the outer dimensions of the rolled sheet material 13 or folded sheet material 14 are within the constraints of a maximum diameter D for which a corresponding circumference is shown in the Figs. 2A-C. The diameter D should be less than the minimum inner diameter of a sample vessel in which the rolled or folded sheet will be placed.

[0136] Figure 2B shows an embodiment of the sheet material with stabilizing features 17 which run substantively parallel to the rolling direction R or folding direction F. Those stabilizing features 17 may be thickened portions of the sheet material or hardened units 17 such creases, pleats or added material on the surface 12 of the sheet material. The stabilizing features 17 do not need to cover the whole extent of the sheet material in the rolling direction R or folding direction F. These features might as well cover only a part of the extent or may be foreseen intermittently. The reinforcement does compensate for the internal mechanical stresses, which are introduced to the sheet material during rolling and folding, so that the outer dimensions of the rolled sheet material 13 or folded sheet material 14 remain constant over time, as illustrated in Fig. 2B from left to right for the rolled sheet material 13 with stabilizing features 17 above the folded sheet material 14 with stabilizing features 17. P260996WO00 - [TP388706WO1]

[0137] - 24 -

[0138] Figure 2C shows an embodiment, where an outer sleeve 2 is confining the rolled sheet material 13 or folded sheet material 14, so that any unrolling or unfolding is restricted or prevented and that the rolled sheet material 13 or folded sheet material 14 remains within a required maximum diameter D for the corresponding circumference is shown. The outer sleeve 2 may be a water-repellent tube or sheet or fabric. The outer sleeve 2 may be unreinforced (as discussed with reference to Fig. 2A) or may also be combined with the sheet material comprising stabilizing features 17 as discussed above with reference to Fig. 2B.

[0139] Figure 2D shows a the rolled sheet material 13 or folded sheet material 14 according to the embodiments according to Figs. 2A-C, wherein only the embodiment without outer sleeve 2 is shown in Fig. 2D. It is however possible to foresee the embodiment discussed here with reference to Fig. 2D also with the outer sleeve 2 according to Fig. 2C. Figure 2D shows embodiments of the rolled sheet material 13 or folded sheet material 14, wherein the catalyst device 1 features an inlay 3 of a protective sheet 4 which is intercalated within the rolling or the folding of the sheet material. The inlay 3 material may be inert to the material of the catalyst carrier 10 and / or the catalyst material 20 itself. An alternative embodiment to the intercalated inlay 3 may be distance pieces or spacers, which may be of the same material as the inlay 3 or of a material with similar properties, and those distance pieces may serve as well to avoid self-contact between the pleats of the folding or self-contact of the rolling windings.

[0140] Figure 3A-C shows a sample vessel 100 for hydrogen isotope exchange analysis, wherein the sample vessel 100 contains one or more catalyst devices 1 according to the embodiments discussed above, wherein a maximum outer diameter D of the catalyst device 1 is smaller than a minimum inner diameter 101 of an opening of the sample vessel 100 or of the sample vessel 100 itself. The sample vessel 100 may be of any form and representative of this, the sample vessel is illustrated as a sample vial 102 in the Figs. 3A- C and 4 A-F. The sample vessel 100 completely houses the catalyst device 1 , wherein the overall height of the catalyst device 1 is smaller than a usable inner height of the sample vessel 100. The sample vessel 100, in use, is a closed vessel and can be sealed with a cap 109. In that way, a bottom portion 103 of the sample vessel 100 may be cleared of the catalyst device 1 (as described below with reference to Figs. 4A-E) and / or a headspace 104 of the sample vessel 100 may be free for the insertion of e.g. a probing embodiment such as a probing needle. The catalyst device 1 may be unattached (according to Figs. 3A- P260996WO00 - [TP388706WO1]

[0141] - 25 -

[0142] C) or attached to the sample vessel 100 (see Figs. 4 D-F). In case of an unattached catalyst device 1 , it may be foreseen that the catalyst coating is not present on the surface 12 of the catalyst carrier 10 overlapping with the bottom portion 103 of the sample vessel 100.

[0143] Figure 3A shows a rod-shaped catalyst device 1 with frustoconical ends according to the above description, which is contained in the sample vessel 100. In this embodiment, the catalyst device 1 is sputtered with platinum or a platinum alloy and is free to move within the sample vessel 100.

[0144] Figure 3B shows a rod-shaped catalyst device 1 made of a sheet material, which is a continuous sheet 15 sputtered with platinum or a platinum alloy and rolled to a bar-shape. The catalyst device 1 is free to move within the sample vessel 100. Figure 3C shows an embodiment with the sheet-material, wherein the sheet material is a platinum or platinum alloy coated mesh 16 according to the above and free to move within the sample vessel 100 (embodiment not shown in Figs. 3A-C).

[0145] It will be appreciated that alternative to a single catalyst device 1 in the sample vessel as shown, a plurality of catalyst devices 1 may be placed in the sample vessel 100 if there is sufficient room. Preferably, the plurality of catalyst devices 1 do not have contact with each other in the sample vessel.

[0146] Figure 4A-C shows embodiments of a distancing concept for the catalyst device 1 within the sample vessel 100. Figure 4D-E show embodiments of possible attachment strategies for the catalyst device 1 within the sample vessel 100 described in detail below. In all embodiments, it can be seen that the sample vessel 100 has a bottom portion 103 extending partly over a height of the sample vessel 100 from its bottom towards an opening opposite to the bottom of the vessel, configured to receive a volume of a liquid sample. The catalyst device 1 may be offset from the bottom of the sample vessel 100 by one or more distance elements 105 as shown in Fig. 4A-C. Another option is to offset the catalyst device 1 by means of an attachment to the sample vessel 100, wherein the attachment maintains the position of the catalyst device 1 above the bottom portion 103 as can be seen from Figs. 4D-E. P260996WO00 - [TP388706WO1]

[0147] - 26 -

[0148] The catalyst material 20 of the catalyst device 1 should preferably not have direct contact with the liquid sample in the vessel since water will deactivate the catalyst. The catalyst device 1 may thus be offset from the bottom of the sample vessel 100 by one or more distance elements 105 in certain embodiments. Some examples are shown in Figs. 4A-C, wherein Fig. 4A shows a tangled wire, Fig. 4B shows pieces of arbitrary shape to generate the distance and Fig. 4C shows a cuboid, which is to be regarded as representing any three-dimensional or two-dimensional shape for a distance element 105. Although some of the embodiments only show a single distance element 105, it should be understood that the catalyst device 1 may be offset from the bottom of the sample vessel 100 by one or more distance elements 105. The material of the distance elements 105 is preferably inert to the sample and / or the hydrogen exchange reaction and may, in special embodiments be a glass material, a ceramic material, or a metal material fabric. In addition to the shapes discussed above, the distance elements 105 may be embodied - but not limited to - beads, fabric or solid blocks of material.

[0149] In Figure 4D-E, two exemplary attachment or support strategies are shown for an attachment of the catalyst device 1 to the sample vessel 100, wherein the catalyst device 1 has no contact to the sample vessel 100 apart from designated attachment sections 110. Fig. 4D shows a catalyst device 1 which is held to the vessel in an attachment section 110 from a top end 5 of the catalyst device 1 , whereas the distance element(s) 105, as discussed with reference to Figs. 4A-C, separate the catalyst device 1 to the bottom 108 of the sample vessel 100 from the bottom end 6 of the catalyst device 1 . Fig. 4E shows a catalyst device 1 which is attached to a side wall of the sample vessel 100 in an attachment section 110. The embodiments are not limited to the attachments shown exemplarily in Figs. 4D and E, further non-limiting attachments may be that the catalyst device 1 is attached to the bottom of the sample vessel 100 in an attachment section 110, or that the catalyst device 1 is attached to the distance element 105 in an attachment section 110. It may as well be that the catalyst device 1 is attached to a cap 109 of the sample vessel 100 in an attachment section 110. The catalyst device 1 may be attached to the sample vessel 100 in the attachments section by means of an adhesive. The catalyst device 1 may be attached to the sample vessel 100 in a releasable manner or in a permanent manner, i.e. the catalyst device 1 may be releasably or non-releasably attached to the sample vessel 100. P260996WO00 - [TP388706WO1]

[0150] - 27 -

[0151] Fig. 5A schematically shows a schematical sectional view of a first embodiment of a catalyst device 1 with a catalyst carrier 10, an adhesive coating or bonding layer 22 and the catalyst material 20, wherein the adhesive coating or bonding layer 22 and the catalyst material 20 are superposed on each other and the adhesive coating or bonding layer 22 is intertwined between the catalyst carrier 10 and the catalyst coating 20. The adhesive coating or bonding layer 22 and the catalyst material 20 both constitute the catalyst of the catalyst device 1 . The catalyst carrier 10 may be a metal carrier. The adhesive coating or bonding layer 22 may comprise titanium or a mixture of e.g. WTi10, Ti, Ta and / or chromium. The catalyst material 20 may, not limited to the embodiment of Fig. 5A and B, consist of platinum or palladium. It is preferred that the platinum is substantially pure, e.g. at least 95% pure, at least 99% pure or at least 99.9% pure. Again, not limited to Fig. 5A and B, the catalyst carrier 10 may consist of any metal or metal alloy, including light or heavy metals, base metals or noble metals. The catalyst carrier 10 is suitable for deposition of the adhesive coating or bonding layer 22 if present, or the catalyst material 20 alone, if no adhesive coating or bonding layer 22 is present as shown in Fig. 5B, which schematically illustrates a sectional view of an embodiment of the catalyst device 1 wherein the catalyst material 20 is deposited directly on the catalyst carrier 10. With reference to Figure 5B, the above applies to the composition of the catalyst carrier 10 and the catalyst material 20, as well as to the coating of the catalyst carrier 10 with the catalyst material 20.

[0152] As used herein, including in the claims, unless the context indicates otherwise, singular forms of the terms herein are to be construed as including the plural form and, where the context allows, vice versa. For instance, unless the context indicates otherwise, a singular reference herein including in the claims, such as "a" or "an" (such as a sheet material or a distance element) means "one or more" (for instance, one or more sheet materials, or one or more distance element). Throughout the description and claims of this disclosure, the words "comprise", "including", "having" and "contain" and variations of the words, for example "comprising" and "comprises" or similar, mean that the described feature includes the additional features that follow, and are not intended to (and do not) exclude the presence of other components. Moreover, where a first feature is described as being “based on” a second feature, this may mean that the first feature is wholly based on the second feature, or that the first feature is based at least in part on the second feature.

[0153] The use of any and all examples, or exemplary language ("for instance", "such as", "for example" and like language) provided herein, is intended merely to better illustrate the P260996WO00 - [TP388706WO1]

[0154] - 28 - disclosure and does not indicate a limitation on the scope of the disclosure unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosure. Any steps described in this specification may be performed in any order or simultaneously unless stated or the context requires otherwise. Moreover, where a step is described as being performed after a step, this does not preclude intervening steps being performed.

[0155] All of the aspects and / or features disclosed in this specification may be combined in any combination, except combinations where at least some of such features and / or steps are mutually exclusive. In particular, the preferred features of the disclosure are applicable to all aspects and embodiments of the disclosure and may be used in any combination. Likewise, features described in non-essential combinations may be used separately (not in combination).

[0156] 16886380. AJG1.SLS P260996WO00 - [TP388706WO1]

[0157] - 29 -

[0158] Listing of reference signs

[0159] 1 catalyst device

[0160] 2 outer sleeve

[0161] 3 inlay

[0162] 4 protective sheet

[0163] 5 top end of the catalyst device

[0164] 6 bottom end of the catalyst device

[0165] 10 catalyst carrier

[0166] 12 surface

[0167] 13 rolled sheet material

[0168] 14 folded sheet material

[0169] 15 continuous sheet

[0170] 16 mesh

[0171] 17 stabilizing feature (hardened unit, crease, pleat)

[0172] 20 catalyst material

[0173] 22 adhesive coating or bonding layer

[0174] 100 sample vessel

[0175] 101 inner diameter of the sample vessel

[0176] 102 sample vial

[0177] 103 bottom portion

[0178] 104 headspace

[0179] 105 distance element

[0180] 107 top of the sample vessel

[0181] 108 bottom of the sample vessel

[0182] 109 cap

[0183] 110 attachment section

[0184] R rolling direction

[0185] F folding direction

[0186] D maximum outer diameter

Claims

P260996WO00 - [TP388706WO1]- 30 -CLAIMS:1 . Catalyst device (1 ) for hydrogen isotope exchange analysis, wherein the catalyst device (1) consists of a catalyst carrier (10) and a catalyst material (20) applied to a surface (12) of the carrier (10), characterized in that at least the carrier surface (12) consists of an inorganic material and in that the catalyst material is sputtered or electrodeposited on at least a part of the surface (12) of the carrier (10).

2. Catalyst device (1 ) according to claim 1 , wherein at least the carrier surface (12) consists of a metal or metal-alloy.

3. Catalyst device (1) according to any preceding claim, wherein the carrier is barshaped.

4. Catalyst device (1) according to claim 3, wherein the carrier is a solid rod.

5. Catalyst device (1) according to claim 3 or 4, wherein the rod-shaped carrier has cone-shaped ends (5, 6).

6. Catalyst device (1) according to any of claims 1 to 3, wherein the carrier consists at least partly of a sheet material.

7. Catalyst device (1) according to claim 6, wherein the sheet material has a surface of a metal or metal alloy.

8. Catalyst device (1) according to any of the claims 6 to 7, wherein the sheet material is rolled, preferably to form a bar-shaped carrier (10).

9. Catalyst device (1) according to any of the claims 6 to 8, wherein the sheet material is stapled.

10. Catalyst device (1 ) according to any of the claims 6 to 9, wherein the sheet material has stabilizing features (17) parallel to the rolling direction (R) or folding direction (F).P260996WO00 - [TP388706WO1]- 31 -11 . Catalyst device (1 ) according to any of the claims 6 to 10, wherein the surface of the sheet material has no self-contact.

12. Catalyst device (1 ) according to any of the claims 6 to 11 , wherein the sheet material is a continuous sheet (15).

13. Catalyst device (1 ) according to any of the claims 6 to 11 , wherein the sheet material is a mesh (16).

14. Catalyst device (1) according to claim 13, wherein the mesh (16) is woven, knitted or felted.

15. Catalyst device (1) according to any preceding claim, wherein the catalyst material (20) comprises platinum sputtered from a platinum-containing target, preferably a Pt or PtAu target and / or an additional adhesive metal surface pre-treatment.

16. Catalyst device (1) according to claim 15, wherein the catalyst material is substantially pure platinum, optionally with an adhesive coating or bonding layer (22) comprising another metal.

17. Catalyst device (1) according to any of the claims 1 to 17, wherein the catalyst material (20) comprises platinum electrodeposited on the surface 12 of the carrier (10) and / or an additional adhesive metal surface pre-treatment.

18. Catalyst device (1) according to any of the claims 1 to 17, wherein the catalyst material (20) comprises palladium.

19. Sample vessel (100) for hydrogen isotope exchange analysis, wherein the sample vessel (100) contains one or more catalyst devices (1) according to any of the preceding claims, wherein a maximum outer diameter (D) of the catalyst device (1 ) is smaller than a minimum inner diameter (101) of an opening of the sample vessel(100) or of the sample vessel (100) itself.

20. Sample vessel (100) according to claim 19, wherein the sample vessel (100) is a sample vial (102).P260996WO00 - [TP388706WO1]- 32 -21 . Sample vessel (100) according to claim 19 or 20, wherein the sample vessel (100) has a bottom portion (103) extending partly over a height of the sample vessel (100) from its bottom towards an opening opposite to the bottom (108) of the vessel, configured to receive a volume of a liquid sample.

22. Sample vessel (100) according to one of the claims 19 to 21 , wherein the catalyst device (1) is offset from the bottom (108) of the sample vessel (100) by one or more distance elements (105).

23. Sample vessel (100) according to claim 22, wherein the one or more distance element (105) are glass beads, ceramic structures, metal fabric, or a solid block of material.

24. Sample vessel (100) according to one of the claims 22 to 23, wherein the one or more distance elements (105) are of a material inert to the sample and to hydrogen isotopes.

25. Sample vessel (100) according to one of the claims 22 to 24, wherein the vial (102) contains a cloth or mesh (16) extending at least partly in the bottom portion (103) and extending at least partly above the bottom portion (103).

26. Sample vessel (100) according to one of the claims 21 to 25, wherein the catalyst device (1) is attached to the bottom of the sample vessel (100) and the catalyst material (20) is not present on the surface (12) of the catalyst carrier (10) overlapping with the bottom portion (103).

27. Sample vessel (100) according to one of the claims 21 to 26, wherein, wherein the catalyst device (1) has no contact to the sample vessel (100) apart from designated attachment sections (110).

28. Sample vessel (100) according to one of the claims 21 to 27, wherein the catalyst device (1) is attached to the bottom of the sample vessel (100) in an attachment section (110).P260996WO00 - [TP388706WO1]- 33 -29. Sample vessel (100) according to claim 28, wherein the catalyst device (1 ) is attached to the sample vessel (100) by means of an adhesive.

30. Method of hydrogen isotope analysis of a water-containing sample, comprising the steps of: providing the sample in a closed vessel; providing a catalyst device according to the invention in the closed vessel; introducing hydrogen gas into the closed vessel; causing exchange of hydrogen isotopes to occur in the closed vessel between hydrogen isotopes in the water and hydrogen isotopes in the hydrogen gas and allowing the exchange of hydrogen isotopes to equilibrate for an equilibration period; and after the equilibration period analysing the hydrogen gas using a mass spectrometer to determine an isotopic composition of the gas.31 . Use of the catalyst device (1 ) according to any of claims 1 to 18, or the sample vessel (100) according to any one of claims 19 to 29, in a method of hydrogen isotope analysis.16886380. AJG1.SLS

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