WO2013004882A1

WO2013004882A1 - Doped carbon material for the electrocatalytic conversion of co2 into hydrocarbons, uses of the material and conversion method using said material

Info

Publication number: WO2013004882A1
Application number: PCT/ES2012/070508
Authority: WO
Inventors: Agustín F. PÉREZ CADENAS; Carlos Moreno Castilla; Francisco CARRASCO MARÍN; Francisco MALDONADO HÓDAR; Sergio Morales Torres; Frederik Kapteijn; Cornelia Hester ROS
Original assignee: Universidad De Granada
Priority date: 2011-07-07
Filing date: 2012-07-06
Publication date: 2013-01-10
Also published as: ES2369269A1; ES2369269B8; ES2369269B2; WO2013004882A9

Abstract

The invention relates to a material for the electrocatalytic conversion of CO₂into hydrocarbons, comprising a carbonaceous substrate and a metal catalyst anchored in the carbonaceous substrate, in which the carbonaceous substrate is a carbon gel doped with the metal catalyst, comprising a carbonaceous matrix to which the metal catalyst is anchored. The material is characterised in that the metal catalyst is a transition metal or a mixture of different transition metals. Said material is suitable for use as an electrode or catalyst in methods for the electrocatalytic conversion of CO₂ into hydrocarbons.

Description

COATED MATERIAL FOR THE ELECTRO- CATALYTIC TRANSFORMATION OF C0 ₂ IN HYDROCARBONS, USES OF THE MATERIAL AND TRANSFORMATION PROCEDURE USING THE MATERIAL TECHNICAL FIELD OF THE INVENTION

The present invention falls within the technical field of atmospheric CO2 capture technologies, particularly in the sector of electro-catalytic reduction systems of CO2 to hydrocarbons in which electrodes are used. BACKGROUND OF THE INVENTION

The increase in atmospheric CO2 emissions is one of the most important environmental problems facing the sustainable development of our planet, this increase being one of the main responsible for global climate change. In particular, it is those emissions from the energy use of fossil fuels, which generate the greatest impact on this increase, since they constitute a net and continuous increase in the natural tropospheric carbon cycle. There are several strategies to try to address this problem, being the electro-catalytic reduction of CO2 to hydrocarbons, using renewable energy, one of the great challenges for research (AT Bell, BC Gates, D. Ray, Basic Research Needs: Catalysis for Energy, US Department of Energy Pub, Washington, DC, 2007). In this reaction, the electrodes studied have been mainly metallic sheets, materials with a very small surface area which together with the low Faradic efficiency of the process, makes it necessary to develop new electro-catalysts that give a new impulse to this attractive way of decrease in atmospheric levels of CO2.

The direct electrochemical reduction of CO2 in aqueous solution has been studied mainly on sheet metal electrodes, both at atmospheric pressure and at higher pressures. So far, copper electrodes have been the most studied, showing quite exclusive in the activation of CO2 although the Faradic efficiency is still small: that is, the result of the dissociation of H2O to

H2. Several studies have been carried out to elucidate the mechanism of electro-reduction of CO2 to hydrocarbons, which seem to point towards a Fischer-Tropsch chain propagation mechanism (H. Shibata, JA Moulijn, G. Muí, Enabling electrocatalytic Fischer-Tropsch synthesis from carbon dioxide over copper-based electrodes, Catal. Lett. 123: 186-192, 2008]. The products obtained in the direct electrochemical reduction of CO2 generally vary between hydrocarbons of one to six carbon atoms, and oxygenated products such as alcohols or carboxylic acids have also been obtained, with chain lengths of the same order mentioned above.

The pressure at which the process is carried out is a very important factor, since, at higher pressure the concentration of CO2 dissolved in water is also higher, and the amount of products obtained per unit time increases. However, processes carried out at pressures above atmospheric are more expensive and technically more complex.

Some carbon materials have been successfully applied in electrochemical energy storage processes, where the porous texture, specific surface and surface chemistry of these materials plays an important role in such processes. By extension, the application of carbon materials in CO2 electrocatalytic reduction processes is a plausible option, which has been tested with platinum catalysts supported on carbon nanotubes or using Pt catalysts supported on carbon or black fabrics. coal (G. Centi, S. Perathoner, G. Wine, M. Gangeri, Electrocatalytic conversion of CO2 to long carbon-chain hydrocarbons, Green Chemistry 9: 671-678, 2007) obtaining a wide product distribution of up to nine atoms of carbon. However, in all these cases, platinum, a very expensive metal, has been deposited on the carbonaceous support by impregnation, and the extent to which metal leaching occurs during the electro-catalytic process has not been described.

In view of the above, there was a need to devise an electro-catalytic system that would avoid the inconvenience of the systems described above to reduce atmospheric emissions of CO2 through its transformation into hydrocarbons.

DESCRIPTION OF THE INVENTION

The present invention aims to overcome the drawbacks of the state of the art detailed above, by means of a doped carbon material for the electro-catalytic transformation of CO2 in hydrocarbons, uses of the material in the electro-catalytic transformation of CO2 in hydrocarbons, and electrocatalytic transformation process of CO2 into hydrocarbons using the material.

The material for the electro-catalytic transformation of CO2 into hydrocarbons comprising a carbonaceous support and a metallic catalyst supported on the carbonaceous support, is characterized in that the carbonaceous support is a carbon gel doped with the metal catalyst, which comprises a carbonaceous matrix to which the metal catalyst is anchored; and because the metal catalyst is a transition metal or mixture of several, preferably Ni, Cu, or Fe

One of the great advantages of these materials with respect to the rest of carbon materials is that, due to their preparation procedure, they can be obtained directly as sheets, that is, the optimum and suitable form for use as an electrode in a system of Two phases.

The sheets of carbon gels can be ground to obtain a powder, with which gas diffusion layers can be manufactured, which would also function as catalysts for the electro-reduction of CO2 in three-phase catalytic systems: gas-solid-liquid. All these gels are characterized by the possibility of being manufactured with a high surface area and porosity, which facilitates a high dispersion of the metal cations through the gel, as well as the adsorption of reagents improving the electro-catalytic efficiency against the metallic sheets . Finally, and also due to the gels preparation process, most of the metal cations will be anchored to the gel structure, which minimizes their leaching, and in this respect, these materials are advantageous compared to those electro-catalysts prepared by impregnating the corresponding metal phase.

The materials according to the present invention which. they comprise carbon gels, such as aerogels and carbon xerogels, doped with transition metals can be used as electrocatalysts for the transformation of CO2 into hydrocarbons, at atmospheric pressure and by electro-catalytic pathway in two phases: solid (electrodes ) and liquid (electrolyte).

The carbon gels used can be obtained in a conventional manner by mixing, for example, the appropriate proportions of a compound containing the metal, resorcinol, formaldehyde and water. This homogeneous mixture is introduced into glass molds and undergoes a healing process. Subsequently, the solid obtained (organic gel doped with the metal) is thermally dried in an air atmosphere to obtain a xerogel, or with supercritical CO2 to obtain an airgel, and finally, it is treated in an inert atmosphere at high temperature in a carbonization process , thus obtaining a carbon gel doped with the metal. When the organic gels doped with the metal are dried with supercritical CO2, instead of thermally, the process results in aerogels and favors the presence of a larger volume of mesopores and macropores in them. Likewise, organic gels doped with transition metals can be activated by chemical activation processes with alkaline hydroxides or phosphoric acid increasing the volume of pores and / or their surface area, or physical activation processes with CO2, water vapor, air or diluted oxygen, increasing the volume of pores and / or their surface area.

Depending on the preparation conditions, and especially the method of drying, thermal or using supercritical CO2, the porosity and surface values that can be achieved by coal gels, doped or undoped, are the following:

• Micropore volume up to 0.800 cm ³ / g determined by applying the Dubinin Radushkevich equation to the adsorption data of N ₂ at -196 ° C.

• Micropore volume up to 0.600 cm ³ / g determined by applying the Dubinin Radushkevich equation to the adsorption data of C0 ₂ at 0 ° C.

• Total pore volume of up to 2,000 cm ³ / g determined by mercury porosimetry.

• Volume of mesopores up to 1,500 cm ³ / g determined by mercury porosimetry.

• Volume of macropores up to 1,900 cm ³ / g determined by mercury porosimetry.

• Apparent surface area of up to 2000 m ² / g determined by applying the BET equation to the adsorption data of N ₂ at -196 ° C.

Depending on the metal precursor used, and the degree of final activation of the material, metal contents, expressed in percentage by weight with respect to the total weight of doped carbon gel, of up to 25% can be obtained.

As can be seen, the present invention makes use of carbon gels doped with transition metals as new electro-catalysts, and is focused on the elimination of carbon dioxide dissolved in water by its transformation into hydrocarbons, a process by which not only It helps reduce net CO2 emissions to the atmosphere, but also to obtain hydrocarbons that can serve as fuels.

In accordance with the foregoing, the present invention makes it possible to transform C0 ₂ into hydrocarbons, at atmospheric pressure, by electrocatalytic use using doped carbon gels as electrodes and process catalysts. In addition, taking advantage of the high surface area and porosity of the carbon gels, electrocatalysts can be obtained where the dispersion of the metal is very high across the porous surface of the gel, significantly increasing the catalytically active surface of the electrode. The synthesis technique of the proposed doped carbon gels makes possible a significant minimization of the leaching process of the doping metal, a process that is inherent and inevitable in these catalytic systems.

BRIEF DESCRIPTION OF THE FIGURES

Figure 1.- Graph showing an example using the carbon xerogel XNi5 of the molar production, PM, of different hydrocarbons detected in the reactor in the gas phase, expressed in μπιοΐ, as a function of time, T, expressed in minutes.

Figure 2.- Graph showing an example using the XCul carbon xerogel of the molar production, PM, of different hydrocarbons detected in the reactor in the gas phase, expressed in pmol, as a function of time, T, expressed in minutes.

Figure 3.- Graph showing an example using the XFel carbon xerogel of the molar production, PM, of different hydrocarbons detected in the reactor in the gas phase, expressed in μη οΐ, as a function of time, T, expressed in minutes.

EMBODIMENTS OF THE INVENTION

Example 1:

The preparation of the gels is carried out using resorcinol (R), formaldehyde (F), water (W) and a water soluble compound containing the transition metal, hereinafter precursor compound. The amount of precursor compound to be used is calculated based on the different percentages of metal, by weight, that it is desired to achieve with respect to the initial mixture. The maximum theoretical metal content in these materials is limited, by the amount of water used in the synthesis, and the solubility in it of the selected precursor compound.

The precursor compound and resorcinol are dissolved in the appropriate amount of water, under stirring and at room temperature. On the above aqueous solution, and maintaining the stirring, formaldehyde is slowly added in the form of a 37% aqueous solution. The polymer mixture is kept under stirring and at room temperature until complete homogenization, at which time it is poured into glass molds, on which it will remain 24 hours at room temperature followed by 5 days at 80 ° C, during which time the gel Organic doped with metal solidifies completely. During this synthesis procedure, the metal, which also acts as a polymerization catalyst for R and F, is occluded and strongly adhered to the polymer matrix. Finally, the sheets of doped organic gels are separated from the glass molds and carbonized at 900 ° C under a nitrogen atmosphere for 5 hours. Example 2:

Following the synthesis procedure described in example 1, and specifically, when the amounts of reagents used were 12.35 grams of R, 18.16 grams of F, 16.70 grams of water, and 2.11 grams of the precursor compound nickel acetate tetrahydrate (Ni (AcO) 2 »4H20], a nickel doped carbon xerogel was obtained, hereinafter referred to as" XNi5 ", which has an apparent surface area value of 300 m ² / g obtained by applying the equation of BET to the nitrogen adsorption data at -196 ° C; a micropore volume of 0.155 cm ³ / g obtained by applying the Dubinin-Radushkevich equation to the CO2 adsorption data at 0 ° C; a volume of mesoporos of 0.160 cm ³ / g obtained by mercury porosimetry; a macropore volume of 0.050 cm ³ / g obtained by mercury porosimetry; and a total nickel content of 5.0% by weight. Example 3:

Following the synthesis procedure described in example 1, and specifically, when the amounts of reagents used were 12.35 grams of R, 18.16 grams of F, 33.4 grams of water, and 2.15 grams of the precursor compound copper acetate monohydrate (Cu (AcO) 2 »H203, a carbon-doped xerogel with copper considered non-porous was obtained, hereinafter referred to as" XCul ", which has an apparent surface area value of 4 m ² / g obtained by applying the BET equation to nitrogen adsorption data at -196 ° C; and a total copper content of 7.1% by weight Example 4:

Following the synthesis procedure described in example 1, and specifically, when the amounts of reagents used were 12.35 grams of R, 18.16 grams of F, 16.70 grams of water, and 2.30 grams of the precursor compound iron acetate (Fe (AcO) 2), an iron-doped carbon xerogel was obtained, hereinafter referred to as "XFel", which has an apparent surface area value of 275 m ² / g obtained by applying the BET equation to nitrogen adsorption data at -196 ° C; a micropore volume of 0.070 cm ³ / g obtained by applying the Dubinin-Radushkevich equation to the CO2 adsorption data at 0 ° C; a total pore volume of 0.450 cm ³ / g obtained by adsorption of nitrogen at -196 ° C and 0.995 relative pressure; and a total iron content of 6.5% by weight. Example 5:

As an experimental system, a glass electrochemical cell equipped with three electrodes is used, using as a electrolyte a 0.1 M solution of KHCO3 saturated with CO2 gas, for which, before the reaction, a stream of CO2 bubbles into the solution. The cell is connected to a potentiostat / galvanostat. This type of device, tightly closed, will work as a discontinuous, heterogeneous and non-agitated reactor, which has worked in a potentiostatic mode, with potentials between -1.40 and -2.15 V with respect to the reference electrode (Ag / AgCl) . The nickel-doped carbon gel acts as a working electrode and as a cathode. A platinum electrode is used as a counter electrode acting as an anode. To monitor the evolution of the reaction, the gas phase of the reactor is analyzed as a function of time, using a gas chromatograph equipped with a Poraplot Q column, for the separation of the different products, and an ionic flame detector (FID) for its detection The electrochemical reactor / cell can be modified to work in semi-continuous or continuous mode.

For the electro-catalytic reduction of CO2 dissolved in water to hydrocarbons, at atmospheric pressure, and catalyzed by a nickel-doped carbon gel electrode, the electrochemical experimental system described above has been used as a discontinuous reactor, working in potentiostatic mode at - 1.65V, and at 23 ° C temperature. As a cathode, a sheet of the product XNi5 of Example 2 has been used. The dimensions of the sheet of XNi5 have been approximately 20 x 25 x 1 mm, which corresponds to an exact weight of 0.8643 g.

For comparison purposes, a commercial nickel foil from the Alfa Aesar® house, a nickel foam from the Metpore® house, a graphite sheet from Alfa Aesar® house, and a non-doped carbon gel sheet were also tested as cathodes, all of them similar in size to the carbon gel sheet doped with nickel.

With XNi5 as a cathode, no reaction products were detected until 18 hours after the electro-catalytic process, due to the simultaneous existence of an adsorption process of the products on the porous structure of the gel.

From the detection of the first reaction product, considered as zero time in Figure 1, an increase in electro-catalytic activity directly proportional to the reaction time is detected. Figure 1 shows the molar production in the reactor, as a function of time, of the following detected hydrocarbons of 1, 2, 3 and 4 carbon atoms: methane [CH4), ethane (C2H6), propene (C3H6), ethyne and ethene (C2H2 / C2H4), tip (C3H4), and butane (C4H10).

With the use of a graphite sheet, or a non-doped carbon gel sheet as cathodes, no reaction products are detected.

With the use of a dissolved CO2-free electrolyte, and XNi5 as a cathode, no reaction products are detected.

If XNi5 is used as a cathode, and during the period in which reaction products are being detected, the in situ removal of dissolved CO2 from the electrolyte is carried out, the detection of reaction products ceases; The reaction products are detected again when CO2 is bubbled back into the electrolyte, almost immediately, and the necessary 18 hours of reaction / adsorption time necessary for any new sheet of doped carbon gel with nickel.

Both the sheet and the commercial metallic nickel foam used as cathodes give a distribution of reaction products similar to that obtained with XNi5. Table 1 shows a comparison of the general electro-catalytic behavior of all these materials, where it is clearly observed, that having obtained a total molar production of the same order, and a thorough quantitative comparison of the catalytic activity being difficult since they are very different materials , it is evident that with the nickel-doped carbon gel, XNi5, a much smaller amount of catalyst was used. Example 6:

Using the same experimental system, and experimental conditions, described in example 5, a sheet of the product XCul of example 3 of dimensions 20 x 19 x 0.8 mm, approximately, corresponding to an exact weight of 0, was used as cathode. 6332 g

With XCul as a cathode reaction products were detected a few minutes after starting the electro-catalytic process. From the detection of the first reaction product, considered as zero time in Figure 2, an increase in electro-catalytic activity directly proportional to the reaction time is detected. Figure 2 shows the molar production in the reactor, as a function of time, of the following detected hydrocarbons of 1, 2 and 3 carbon atoms: methane (CH4), ethane (C2H6), propene (C3H6), ethene ( C2H4), and propane (C3H8).

Total molar hydrocarbon production in the reactor at 270 minutes of product detection time was 0.181 micromoles. The amount of copper in the XCul cathode was 0.036g. Example 7:

Using the same experimental system, and experimental conditions, described in example 5, a sheet of the product XFel of example 4 of dimensions 20 x 12 x 1 mm mm, approximately, corresponding to an exact weight of 0.3965 was used as cathode g.

With XFel as a cathode reaction products were detected a few minutes after starting the electro-catalytic process. From the detection of the first reaction product, considered as zero time in Figure 3, an increase in electro-catalytic activity directly proportional to the reaction time is detected. Figure 3 shows the molar production in the reactor, as a function of time, of the following detected hydrocarbons of 1, 2 and 3 carbon atoms: methane (CH4), ethane (C2H6), ethene (C2H4), and propane (C3H8].

Total molar hydrocarbon production in the reactor at 270 minutes of product detection time was 0.178 micromoles. The amount of iron in the XFel cathode was 0.02 lg.

Table 1.- Total molar production at 270 minutes of product detection time.

Total micromoles Amount of Ni

Cathode / Electro-catalyst

of hydrocarbons detected in the cathode (g)

XNi5 0.512 0.043

XNi5 (2 »cycle) 0.503

Ni Aesar® 0.735 1.450 Ni foil

Ni Foam Metpore® 0.645 0.620 Table 1 also shows how, with a second use of the same XNi5 sheet, virtually the same catalytic result is repeated.

Table 2 shows the leaching results analyzed by atomic absorption spectroscopy. The amount of total nickel leached from XNi5 is quite acceptable if we compare it with that leached from commercial nickel materials. Table 2.- Ni concentration detected in the liquid phase of the reactor / electrolytic cell.

Reaction time Ni leachate

Cathode / Electro-catalyst

(min) (mg / L)

XNiS 1480 1.27

Ni Aesar® 400 1.96 Ni sheet

Metpore® Ni Foam 370 1.54

METHOD AND SYSTEM OF COORDINATION OF SOFTWARE SYSTEMS BASED ON MULTIPARADIGM ARCHITECTURES

OBJECT OF THE INVENTION

The present invention, as expressed in the statement of this specification, refers to a coordination method for software systems based on multiparadigma architectures, which makes use of events with dynamically alterable semantics, and which aims to simplify the coordination between entities of software system, facilitating the addition of new entities to coordinate in the system without the need for them to be designed so that they can exchange information in an instant of time or must be synchronized, that is, interrupt their execution flow until another entity has reached a specific point in its own flow.

It is another object of the invention to ensure a correct execution order, when two or more entities are executed concurrently and, therefore, to provide a final state of the system that meets the objectives with which the entities were originally designed. It is also the object of the invention to improve the efficiency of coordination between entities by eliminating the need for state surveys from one entity to others by using events with a formal and dynamically alterable semantics. This allows the state changes to be informed only to those entities that previously express the need to receive the status information automatically each time it is modified.

The invention is applicable to entities that present a service-oriented, agent, multi-agent, event-driven architecture, operating system processes, or any combination of the foregoing. BACKGROUND OF THE INVENTION

The development of complex distributed software systems poses a great difficulty in terms of proper coordination between the different entities that make them up and cooperate with each other to achieve certain objectives, since the coordination methods proposed so far are rigid in terms of need to specify which entities will be coordinated. Therefore, when it is desired to incorporate a new entity into the system, it is necessary to redevelop / modify a large part of the rest of the entities so that the coordination requirements that are desired at each moment or particular case are met.

In addition, existing coordination methods involve blocking in the execution flow of at least one of the entities of the system, since coordination, to date, is resolved through a synchronization operation.

In addition the introduction of different types of entities

(services, agents, event emitters or event receivers, operating system processes, etc.), in a distributed software system adds greater complexity, since it makes it difficult to apply coordination methods under a single common method that provides uniformity and the adequate integration that is needed in our systems to enable the various entities to cooperate with each other. The lack of proposals in this regard leads to the use and application of ad-hoc solutions for coordination between entities, with the inconvenience that this entails.

DESCRIPTION OF THE INVENTION

In order to achieve the objectives and solve the aforementioned drawbacks, the invention provides a new method for software systems based on multi-paradigm architectures, based on events with dynamically alterable semantics, comprising the following phases:

a) generate at a specific point of execution where a coordination with at least one source entity associated with a specific type of event is required, a requirement event indicative of the need to receive notifications every time At least one source entity generates the specific type of event to which it is associated.

b) Receive the requirement event in a coordinating entity, associated with all types of events, to receive any of the events that may occur in the system.

c) Process and infer, in the coordinating entity, events related to the information required in the requirement event received, based on previously established rules that semantically associate the types of events with each other.

d) Next, the coordinating entity notifies each of the origin entities of the system the specific types of events that must be notified to said coordinating entity.

e) Next, the coordinating entity receives the notifications of the specific events produced in the different source entities.

f) Finally, the coordinating entity transmits, to the destination entity, inferred events and notifications received from the source entities. In addition, the method of the invention optionally comprises a phase in which, if the structure of an event is modified in phases d-f, it is passed to phase c).

Furthermore, optionally, the method of the invention comprises a phase in which when a new event is defined in phases df, it is also passed to phase c). Also, optionally, the method comprises a phase in which, if the destination entity changes needs in the df phases, it goes back to phase c).

When the requirement event indicates the need to receive coordinated notifications from more than one source entity, the notification transmitted from the coordinating entity to the destination entity is constituted by a new notification event resulting from a composition of the information contained in the notification of each origin entity, so that the coordinating entity composes the information that each of the events contains to produce new events of other types than the notifications generated by the origin entities, resulting from the combination of the events it received. In the event that in this task of composition an event of a certain type is obtained to which any of the entities of the system (destination entity) expressed its prior interest in receiving it automatically, a transmission of these events is made to these latter entities.

Based on the description made, it is easily deduced that a destination entity may be waiting for a type of event that can only originate due to the composition of the information provided by one or more entities with which it is desired to coordinate. This prevents the execution flow of an entity from advancing until other entities of the system have reached a specific point in the execution flow of each of them. Consequently, coordination between entities of a system is possible. In addition, thanks to the fact that the coordinating entity is responsible for the composition of event information and for receiving and transmitting the new events generated, each source and destination entity only needs to know about the existence of this single coordinating entity. Therefore, the origin and destination entities remain decoupled from each other, which favors obtaining quality properties of a software system, such as maintainability and reusability. Finally, the Using an event model in the coordination method allows entities to coordinate origin and destination to maintain the execution of part of their execution flow at all times, even if they are waiting for a particular event to perform an operation specifically, since entities are notified when an event is received asynchronously.

Consequently, the method of the invention allows the coordination to be carried out asynchronously, although obviously it can also be carried out synchronously, and it is avoided that the entities must have an explicit knowledge of the existence of other entities, allowing the possibility of adding new entities to a system without redesigning or restarting the rest of the entities to be executed or already running in the system.

Finally, it should be noted that the method of coordination of the invention is unique to the software system and common to different types of entities, providing the uniformity and integration required in these systems to enable the various entities to cooperate with each other. This avoids the need to use ad-hoc methods that are conventionally used in entity coordination.

On the other hand, it should be noted that the configuration described allows the invention to be applicable in architectural-based software systems for distributed software systems in which entities can be conceptually distinct, allowing the invention to apply to entities with a service-oriented architecture , agent, multi-agent, event driven, operating system processes, or any combination of the above.

In an additional embodiment of the invention it is envisioned that the method comprises mechanisms for storing the information exchanged between the entities, which contributes to improving the process of analysis, verification and maintenance of a software system. For this it makes use of a knowledge base where meta-information about the information exchanged between entities is stored.

Additionally, if the method of the invention is incorporated as part of a software system that is responsible for solving communication tasks between entities, synchronous and asynchronous communication and coordination methods can be combined that contribute to meet the coordination requirements in each instant and for each specific software system and that provide greater ease of development of distributed software systems.

Finally, when coordination is carried out by means of an asynchronous notification of information, it is possible to continue with part of the execution flow of the entities, thus not introducing as many downtimes in the execution flow as other existing coordination methods , which involve involving synchronization between execution flows.

Furthermore, the invention relates to a software system coordination system based on multi-paradigm architectures in accordance with the method described above.

The specific implementation of the origin and destination entities to be coordinated, of the coordinating entity and of the concrete distributed software system on which the described method is applied, as well as the accessory details that may arise, are provided, independent of the object of the invention. It does not affect its essential characteristics.

Next, in order to facilitate a better understanding of this specification and forming an integral part thereof, a series of figures are attached in which the object of the invention has been shown as an illustrative and non-limiting nature. BRIEF DESCRIPTION OF THE FIGURES

Figure 1. - Shows a schematic representation of a software system based on multi iparadigm architectures to which the method of coordination of the invention is applied.

Figure 2.— Shows the software system of the previous figure in which the source entities are determined by a humidity sensor and a noise sensor, while the destination entity is determined by a temperature sensor.

DESCRIPTION OF THE PREFERRED EMBODIMENT

Below is a description of the invention based on the figures mentioned above.

In the exemplary embodiment of Figure 1, "n" source entities 1 have been represented, each associated with a specific type of event T ₁ -T _n respectively, so that through a coordinating entity 2 that is associated with all type of events, that is, it is configured so that it can receive any type of event, the operation of the source entities 1 is coordinated with a destination entity 3, in accordance with the method of the invention.

Previously it is necessary to define the events T ₁ -T _n with a normal semantics, with a set of information associated with each type of event and equipped with a structure that relates some types to others.

In order to achieve the aforementioned coordination, the method of the invention comprises a phase a) in which the destination entity 3 generates, at a specific point of execution in which it is required to perform coordination with at least one of the origin entities 1, a requirement event indicative of the need to receive notifications every time one or more of the origin entities 1 generates the type of specific event to which it is associated.

Following is a phase b) in which the coordinating entity 2 receives the request event, following a phase c) in which it processes and infers events related to the information required in said requirement event received, by means of a set of pre-established rules that semantically associate the types of events with each other. A phase d) follows, in which the coordinating entity 2 notifies each of the origin entities 1 the types of events that must be notified to the coordinating entity; following a phase e) in which the coordinating entity 2 receives the notifications of the specific events T ₁ -T _n produced in the different origin entities 1, so that the procedure ends according to a phase f) in which the coordinating entity 2 performs various compositions of the information contained in the T ₁ -T _{n events} received and inferred, composing new events Τ _± -Ί \ so that said coordinating entity 2 transmits the inferred events and the notifications received from the origin 1 entities according to the new T _± -T events towards the source entity 3. In this way, the coordinating entity 2 when a composition with which a T.-T. event is obtained is obtained, the new event will be notified to the destination entity 3. When it If you receive notification of this event, you can continue with the part of your execution flow that required the coordination method described, to enable the various entities to cooperate with each other.

Figure 2 shows a particularization of an embodiment of the previous figure in which the origin entities 1 are constituted by a humidity sensor and a noise sensor Ib, while the destination entity is constituted by a temperature sensor 3. This example requires a coordination in which the temperature sensor 3 can only notify a measurement if measurements have been previously reported by the humidity sensor la and the noise sensor Ib.

According to phase a) of the indicated coordination method, given that there is more than one origin unit 1, it must be expressed from the temperature sensor 3, by means of an event of requirement, that automatic reception of those events whose associated information is the result of the composition of the information extracted from the events notified by the noise and humidity sensors Ib is desired. Upon receipt of the requirement event in the coordinating entity 3, and as described in phase c), the coordinating entity 3 processes and infers that the events required for the combination are those that are notified by the humidity sensor and the noise sensor Ib. Likewise, as explained in phase d), the humidity and noise sensors 1 will be notified so that the coordination method is applied by initiating the notification of events generated by said sensors.

After notification of events by the humidity and noise sensors Ib, the coordinating entity 2 composes the information associated with each event, resulting in the construction of a new event semantically associated with both "humidity" and "noise", the which will be notified accordingly, as described in phase d) of the method. Having previously expressed from the temperature sensor 3 the need to automatically receive the new event generated, this sensor will automatically receive the new event resulting from the composition. As a result of the receipt of the notification of one of those events, a notification of an event is made by the temperature sensor 3 including information about the quantified value thereof. In this way, each time a new event semantically associated with both "humidity" and "noise" is received, the temperature sensor 3 makes the relevant notification and, consequently, the required coordination for the system is met: Temperature sensor 3 can only notify a measurement if measurements have been previously notified by the humidity sensor la and the noise sensor Ib. Finally, it should be noted that phase c) should be returned when in one of the d) af) phases the following circumstances occur: the internal structure of any of the events changes, new events are defined as a consequence, for example, of the incorporation of new entities to the system, and / or the needs of the origin entity 3 change, for example, if the coordination rule imposed is only valid for a limited time or after a predetermined number of events received.

The origin 1 and destination 3 entities can be designed as required: agents, services, multi-agent, events, operating system processes, etc. The coordinating entity 2 can also be considered a service as an agent or an event issuer / consumer. The coordinating entity 2 must have, at least, a public interface that allows communication with the rest of entities 1 and 3 to allow the association between an entity 1 and 3 and an event type, the notification of an event to an entity interested destination 3 and, finally, the sending of an event from any source entity 1 to the coordinating entity 2.

The coordinating entity 2 must be able to access a knowledge base 4 where you can check the type of each of the events received, so that the composition of information is efficient in time, it is also necessary to consult this knowledge base 4 and only perform the compositions that are collected in it.

The knowledge base 4 can be any type of software system that allows storing and retrieving information, properties about this information (meta-information) and the relationships between different kinds of information. For example, a knowledge base may be a relational database, an ontology and its instances, etc.

The coordination method can be integrated into a software system responsible for solving the various communication mechanisms between entities of a distributed software system.

In addition, the invention also relates to a system comprising the means necessary to carry out the described method, presenting the advantages that were indicated in the description section of the invention.

Claims

1. Material for the electro-catalytic transformation of CO2 into hydrocarbons comprising a carbonaceous support and a metallic catalyst anchored in the carbonaceous support, in which the carbonaceous support is a carbon gel doped with the metallic catalyst, which comprises a carbonaceous matrix to which the metal catalyst is anchored, characterized in that the metal catalyst is a transition metal or mixture of several transition metals and contains between 5% and 25% by weight of said metal with respect to the total weight of the doped carbon gel.

2. Material according to claim 1, characterized in that the transition metal used as a catalyst is nickel.

3. Material according to claim 1, characterized in that the transition metal used as a catalyst is copper.

4. Material according to claim 1, characterized in that the transition metal used as a catalyst is iron.

5. Material according to any one of claims 1 to 4, characterized in that the doped carbon gel is a carbon gel activated by a physical activation process with diluted oxygen.

6. Material according to any of claims 1 to 4, characterized in that the doped carbon gel is a carbon gel activated by a chemical activation process with an alkali hydroxide.

7. Material according to any of claims 1 to 4, characterized in that the doped carbon gel is a carbon gel activated by a chemical activation process with phosphoric acid.

8. Material according to any one of claims 1 to 7, characterized in that the doped carbon gel is a carbonized airgel.

9. Material according to any of claims 1 to 7, characterized in that the doped carbon gel is a carbonized xerogel.

10. Material according to any one of the preceding claims, characterized in that it is a sheet comprising the carbonized doped carbon gel.

11. Material according to claim 10 comprising at least one gas diffusion layer prepared from a powder obtained by grinding a sheet obtained from the carbonized doped carbon gel.

12. Electrode for the electro-catalytic transformation of CO2 to hydrocarbons, characterized in that it comprises the material defined in any one of claims 1 to 11.

13. Electrode according to claim 12, characterized in that it is a cathode at least partially formed by said material.

14. Electrode according to claim 12, characterized in that it comprises a cathode at least partially coated with said material.

15. Catalyst for the electro-catalytic transformation of CO2 to hydrocarbons, characterized in that it comprises the material defined in any one of claims 1 to 11.

16. Use of the material defined in any one of claims 1 to 11 in the electro-catalytic transformation of CO2 in hydrocarbons, characterized in that the material is used as at least part of an electrode for said transformation.

17. Use according to claim 16, characterized in that the material is used as a cathode at least partially formed by said material.

18. Use according to claim 16, characterized in that the material is used to at least partially cover a cathode of another material.

19. Use of the material defined in any one of claims 1 to 11 in the electro-catalytic transformation of CO2 in hydrocarbons, characterized in that the material is used as a catalyst for said transformation.

20. Method for the electro-catalytic transformation of CO2 into hydrocarbons, characterized in that it comprises contacting the CO2 with an electrode comprising the material defined in any one of claims 1 to 11.

21. Method according to claim 20, characterized in that the electrode is a cathode at least partially formed by said material.

22. Method according to claim 20, characterized in that the electro-catalytic transformation of CO2 into hydrocarbons is carried out in a catalytic system comprising a solid and a liquid phase.

23. Method for the electro-catalytic transformation of CO2 into hydrocarbons, characterized in that it comprises contacting the CO2 with an electro-catalyst comprising the material defined in any one of claims 1 to 11.

24. Method according to claim 21, characterized in that the electro-catalytic transformation of CO2 into hydrocarbons is carried out in a gas-solid-liquid catalytic system.

1. - METHOD AND SYSTEM OF COORDINATION OF SOFTWARE SYSTEMS BASED ON MULTIPARADIGM ARCHITECTURES that uses events with dynamically altered semantics in the coordination between entities of a software system; characterized in that it comprises the following phases:

a) Generate in a specific entity of execution (3), at a specific point of execution where coordination with at least one source entity (1) associated with a specific type of event is required, a requirement event indicative of the need of receiving notifications every time the at least source entity (1) generates the specific type of event to which it is associated.

b) Receive the requirement event in a coordinating entity (2), associated with all types of events.

c) Process and infer, in the coordinating entity (2), events related to the information required in the requirement event received, based on previously established rules that semantically associate the types of events with each other.

d) Notify the coordinating entity (2), to each of the origin entities (1) of the system, the types of specific events that must be notified to said coordinating entity (2).

e) Receive in the coordinating entity (2) the notifications of the specific events produced in the different origin entities (1).

f) Transmit the coordinating entity (2) to the destination entity (3), the inferred events and the notifications received from the source entities (1).

2. - METHOD AND SYSTEM OF COORDINATION OF SOFTWARE SYSTEMS BASED ON MULTIPARADIGM ARCHITECTURES, according to claim 1, characterized in that it comprises a phase in which when the structure of a new event is modified in the df phases, it is passed to phase c.

3. - METHOD AND SYSTEM OF COORDINATION OF SOFTWARE SYSTEMS BASED ON MULTIPARADIGM ARCHITECTURES, according to claim 1, characterized in that it comprises a phase in which when a new event is defined in phases d-f, it is passed to phase c.

4. METHOD AND SYSTEM OF COORDINATION OF SOFTWARE SYSTEMS BASED ON MULTIPARADIGM ARCHITECTURES, according to claim 1, characterized in that it comprises a phase in which when the destination entity (3) changes needs in the df phases, it goes to phase c .

5. - METHOD AND SYSTEM OF COORDINATION OF SOFTWARE SYSTEMS BASED ON MULTIPARADIGM ARCHITECTURES, according to claim 1, characterized in that when the requirement element indicates the need to receive coordinate notifications from more than one source entity (1), the notification transmitted from the coordinating entity (2) to the destination entity (3) is constituted by a new notification event resulting from a composition of the information contained in the notification of each source entity.

6. - METHOD AND SYSTEM OF COORDINATION OF SOFTWARE SYSTEMS BASED ON MULTIPARADIGM ARCHITECTURES, according to claim 1, characterized in that the generation of a requirement event of the destination entity is carried out in a manner selected between synchronous and asynchronous.

7. - METHOD AND SYSTEM OF COORDINATION OF SOFTWARE SYSTEMS BASED ON MULTIPARADIGM ARCHITECTURES, according to claim 1, characterized in that it comprises storing the information exchanged between the different entities (1, 2 and 3).

8. - METHOD AND SYSTEM OF COORDINATION OF SOFTWARE SYSTEMS BASED ON MULTIPARADIGM ARCHITECTURES, according to claim 1, characterized in that the different entities (1, 2 and 3) have an architecture selected from a service-oriented, agent, multi-agent, event-driven architecture, operating system processes and a combination of any of the above.

9.- SOFTWARE SYSTEMS COORDINATION SYSTEM BASED ON MULTIPARADIGM ARCHITECTURES, characterized in that it comprises means for implementing the method of claims 1 to 8.