CN105473218B

CN105473218B - Surface catalysis thermal diode

Info

Publication number: CN105473218B
Application number: CN201480038411.8A
Authority: CN
Inventors: D·P·希恩
Original assignee: Individual
Current assignee: Individual
Priority date: 2013-05-29
Filing date: 2014-05-29
Publication date: 2018-05-22
Anticipated expiration: 2034-05-29
Also published as: EP3003547A1; CN105473218A; KR20160034856A; WO2014194138A1; EP3003547A4; AU2014274104A1

Abstract

Surface catalysis thermal diode (ETD) includes one or more ETD units.Each unit includes first surface and second surface, has cavity between first surface and second surface, which includes the gas for compared with this to surface being superficial catalytic activation.The surface and the mutual chemical action of gas so that gas is close to first surface with than being dissociated close to the faster rate of second surface.Thus, the steady state temperature difference between first surface and second surface is generated and maintains.In the respective applications, multiple ETD units are connected and/or are connected in parallel.

Description

Surface catalysis thermal diode

Cross reference to related applications

This application claims submitted on May 29th, 2013, the U.S. of entitled " Epicatalytic Thermal Diode " The rights and interests of Provisional Patent Application No. 61/828,419；It is submitted on May 29th, 2013, entitled " Epicatalytic Thermal The rights and interests of the U.S. Provisional Patent Application No. 61/828,421 of Diode "；And it is submitted on May 28th, 2014, is entitled The rights and interests of the U.S. Patent Application No. 14/289,322 of " Epicatalytic Thermal Diode ", it is all these all by drawing With and make its be integrally incorporated herein.

Technical field

Theme described herein is usually directed to management hot-fluid more particularly to a kind of equipment generated and maintain steady state temperature difference.

Background technology

Heat mitigates temperature gradient so that isolated system is finally reached by single uniform temperature usually from hot-fluid to cold The thermodynamical equilibrium of characterization.Currently, in order to make, equipment generates and temperature gradients must do work.Temperature gradients are all As heated, freezing, environmental Kuznets Curves, power generation and mechanical movement etc broad range technical field on it is with practical value.

Acting also generates waste heat with the existing equipment of temperature gradients.Some equipment attempt using the waste heat (for example, by The waste heat of vehicle motor generation can in winter during month the inside of guided vehicle with heat supply) but such system it is usual Efficiency is low and cannot solve to provide the initial requirement of work(by combustion of fossil fuels (for example, gasoline, coal, oil etc.).

The content of the invention

Above and other problems are solved by surface catalysis thermal diode (ETD) and corresponding method.ETD is naturally i) Generate and maintain the temperature difference between two independent surfaces of ETD；And ii) on the direction of temperature gradient (that is, on) across ETD.Efficient stable state hot-fluid is mediated in one aspect, and the structure of ETD is thermomechanical and chemically optimizes temperature gradient and hot-fluid Generation and maintain both.

In various embodiments, ETD equipment includes series connection and/or the one or more ETD units being connected in parallel.Specific In embodiment, adjacent ETD units shared one or more components are for increase operating efficiency and/or reduce production cost.

In one aspect, ETD units include first surface and second surface, have be configured to keep gas between them The cavity of body.When gas is present in cavity, surface and the mutual chemical action of gas so that gas close to first surface with Than close to second surface faster rate dissociation.Thus, compared with close at second surface, a greater amount of heats is close It is absorbed in first surface or discharges and (depend on whether dissociation reaction is individually neither endothermic nor exothermic).Therefore, first surface Steady state temperature difference between second surface is generated and maintains.

On the other hand, ETD units further comprise the first heat transfer surface and the second heat transfer surface, which passes It passs surface and the second heat transfer surface is correspondingly connected to first surface and second surface and substantially parallel.Heat transfer surface It is connected to the corresponding surface one side opposite with cavity.Heat transfer surface is configured to guide heat to corresponding surface And/or guide heat from corresponding surface.

Description of the drawings

Figure 1A is the schematic diagram for showing the surface-catalyzed reactions for causing the temperature difference between two surfaces according to one embodiment.

Figure 1B is the side view for the single ETD units that may be occurred according to the reaction of Figure 1A wherein of one embodiment.

Fig. 2 is the equidistant diagram according to the system configuration including parallel multiple ETD units of one embodiment.

Fig. 3 is represented according to the side view of the system configuration of the ETD units for combining three layers in series of one embodiment.

Fig. 4 is to show according to the combination for test material and gas of one embodiment to determine them in ETD units The schematic diagram of the device of the middle applicability used.

Fig. 5 is to show the applicability that the definite specific gas according to one embodiment-surface combination uses in ETD units Illustrative methods flow chart.

Fig. 6 is shown according to one embodiment for determining that it is suitable that specific gas-surface combination uses in ETD units With the flow chart of the alternative of property.

Specific embodiment

Attached drawing and description below only describe particular implementation in an illustrative manner.Those skilled in the art are readily able to It is recognized from description below and the alternate embodiments of structures and methods shown in this article may be employed without departing from retouching herein The principle stated.Reference will be carried out to multiple embodiments now, example illustrates in appended accompanying drawing.If it should be noted that feasible, Similar or identical reference numeral can be used in the accompanying drawings, and can indicate similar or identical function.

PROCESS OVERVIEW

The embodiment of ETD utilizes the process for including separated surface (at least) in two spaces, two surfaces compared with Gas is chemically active, which is subjected to general dissociation reactionFigure 1A illustrates parallel using two The embodiment of the process on surface 120 and 140.This two (or more) surface 120 and 140 illustrates traditional heterogeneous catalysis Most characteristic, but deviate catalysis a standard guidelines.Unlike the conventional catalyst that deflected gas-phase does not balance, since surface is imitated Should be compared with the ascendancy of the overall characteristic of the gas in the cavity 130 between surface, surface 120 and 140 changes gas phase and puts down Weighing apparatus.Thus, surface 120 and 140 is referred to herein as " surface catalyst (epicatalyst) " and based on such surface Process be referred to as " surface catalysis (epicatalysis) " and/or " surface catalysis process (epicatalytic process)”。

First surface 140 tends to dissociation (dissociation) half-reaction compared with second surface 120 and (means AB → A+ B).On the contrary, second surface 120 compares compared with first surface 140 tends to compound (recombination) half-reaction (meaning For A+B → AB).Thus, when gas dimer is close to first surface 140, the phase between dimer and first surface 140 Interaction causes its dissociation rate to be higher than the corresponding dissociation rate close to second surface 120.Term used herein approaches It is so as to meaning that the monomer of gas and/or dimer within 10 angstroms of surface, are included in surface compared with gas and surface On.

Cavity 130 includes gas, can move freely in the cavity.Thus, from first surface 140 to second surface 120 have the gas of the A and B species of the bigger flux than flowing through cavity 130 in the opposite direction.On the contrary, from second surface 120 have the gas of the AB species of the bigger flux than flowing through cavity 130 in the opposite direction to first surface 140.Therefore, exist In cavity 130 there are chemical cycle, wherein the net flow of the gas of AB species 125 in one direction, and A and B species 135 The net flow of gas is in other direction.The flowing of gas between two surfaces 120 and 140 carries net thermal energy and chemistry Can, cause steady state temperature difference between two surfaces.

In one embodiment, dissociation reaction is heat absorption, and recombination reaction is exothermic.As a result, be conducive to The surface 140 of dissociation cools down and maintains to be conducive to compound 120 lower temperature of surface than opposite naturally.If excessive heat Amount is provided to colder surface 140, and heat is transported to another surface 120 by space 130 by thermal convection current and chemical advection, from And upward net hot-fluid in ETD thermal gradients is generated between the surfaces.Subsequent heat can be via standard heat transfer mechanism (i.e., Convection current, conduction, radiation) it is harvested from relatively warm surface 120.Net result, which constitutes, to be conducive in one direction rather than another The thermal diode of heat transfer on a direction, so that net transfer of heat can resist temperature gradient.Although dissociation reaction It is that the specific embodiment to absorb heat is being described below, it is noted that in some embodiments, dissociation reaction is exothermic. In such embodiments, the surface for being conducive to dissociation 140 will be warmer than being conducive to compound surface.

The structure of ETD units

Figure 1B is the excision side view for the half structure for illustrating the ETD units 100 according to one embodiment.Multiple ETD Unit 100 can in various ways be combined to reach desired effect, these some examples combined referring to Fig. 2 and Fig. 3 is discussed in further detail.In an illustrated embodiment, ETD units 100 include first surface 140 and second surface 120, it is each supported by corresponding heat transfer surface 110 and is aligned with being substantially parallel to one another.Between surface 120 and 140 Separation is maintained by multiple separators 160, and two of which separator is illustrated herein.Thus, cavity 130 is formed in 120 He of surface Between 140, cavity 130 includes gas.In other embodiments, maintain between the substantial constant between two or more surfaces Every other geometries be used for ETD units 100, nested cylinder, nested sphere, conveyor screw etc..In some implementations In example, one or both of surface 120 and 140 also serves as corresponding heat transfer surface 110.In another embodiment, surface 120 and 140 are not arranged to the interval with substantial constant, for example, with 45 degree of angle or causing relative to each other One surface is compared with another surface general curved.

It is as those gases existing for dimer AB for the useful gas of disclosed device, but also serves as independent list Body A and B exist.And then it is based on their phase interactions with particular surface 120 and 140 for the useful gas of disclosed device With and it is selected.As disclosed above, it is compared in two surfaces for 120 and 140 useful gas of particular surface Second surface at for tend at the first surface in two surfaces dissociation and compared with first in two surfaces Tend to gas compound at the second surface in two surfaces at surface.In one embodiment, gas be based on It is chosen down：The stability of independent monomer A and B, the intensity being bonded between the component in dimer AB and in ETD The vapour pressure of (for example, at room temperature) gas at the operation temperature of equipment.

In some embodiments, gas is chosen to the vapour pressure of the gas when gas is in the operation temperature of ETD It is sufficient for operating chemical Xun Huan.In other words, must have in cavity 130 the enough gas in vapour phase for Dissociation/combined-circulation, therefore the temperature difference is maintained.Thus, the gas with relatively low molecular weight (for example, less than about 200amu) Body can be used to be intended for operation at room temperature in some embodiments.Such gas has can be with environment thermal energy phase The net molecular separating force and energy of ratio, therefore, the dissociation of discernable amount occur at ambient conditions.In general, with higher molecular weight Gas, the molecule of notable ratio is intended to liquefy or cure in room temperature, cause cavity 130 do not include sufficient amount in vapour phase Gas for maintain reaction cycle.

In some embodiments, it is for the stability of independent monomer and the intensity of bonding of dimer of selected gas So that when ETD equipment is for operation temperature due at the skin effect caused by surface 120 and 140 is compared with gas-liquid equilibrium characteristic In ascendancy.In these embodiments, dimer AB is bonded by relatively weak key so that dimer can be or close to room Thermal dissociation at temperature causes the gas (such as 10%) for locating discernable amount at any given time to exist with the species of dissociation.Each In kind embodiment, the gas dimer with hydrogen bond (HyB), halogen key (HaB) and Van der Waals key (vdWB) is used.In various realities It applies in example, two homodimers (gas identical with B monomer A) are used with heterodimer (gases different with B monomer A).

The dimer of hydrogen bond is the molecule using two monomers of one or more hydrogen bonds connection.Dissociation and compound speed Rate includes but not limited in the hydrogen bond dimer of the variation (thus can be used for surface catalysis during) close near surface： The carboxylic acid of low molecular weight, alcohol, aldehyde, ketone, ether, ester, acyl halide, amide and amine.In general, with being attached to electronegative element It is that hydrogen atom cooperates, by F, O, N, the lone pair electrons selected by S will cause to show when close near suitable surface sometimes The dimer of surface catalysis characteristic.It would be recognized by those skilled in the art that in various applications, based on considerations above, embodiment It may be employed following as gas：Formic acid, acetic acid, methanol, ethyl alcohol, formaldehyde, ammonia, dimethyl ketone, methylamine, dimethylamine, dimethyl ether, Water, acetamide, first sulphur, cyanogen, hydrogen cyanide, hydrogen fluoride, hydrogen sulfide, cyanogen methane, formamide, amino azomethine, hydrogen chloride, cyanogen second The heterodimer combination of the monomer of alkane, carbon monoxide, carbon dioxide, sulfur dioxide and nitrogen oxides and these molecules.

The dimer of halogen key is the molecule using two monomers of one or more halogen key connections.In general, comprising fluorine, Chlorine, the low molecular weight halogen key molecule of bromine or iodine present surface catalysis characteristic.It would be recognized by those skilled in the art that it is answered various In, based on considerations above, embodiment may be employed following as gas：Single halomethane, methylene halide, haloform, four halogen Methane, the heterodimer combination of the monomer of the halogenated form and these molecules of halothane and Yi Shang hydrogenation material.

The dimer of Van der Waals key is the molecule using two monomers of one or more Van der Waals key connections.Unlike Above HyB and HaB dimers, the Van der Waals key dimer of many types present the discernable amount significantly below room temperature Dissociation.Those skilled in the art will appreciate that in various applications, based on above understanding, embodiment may be employed following As gas：Rare gas dimer (for example, argon gas, xenon), methane, ethane, propane and nitrogen.

In various embodiments, depending on specific environment, using and surfacing selection, except listed above Those outside gas used.For example, the gas (such as diborane and dinitrogen tetroxide) of some covalent bondings has enough Weak key for gas notable ratio in room temperature or the state in dissociation during close at room temperature.Although gas is herein It is described as dimer for convenient, it is noted that in some embodiments, gas is tripolymer or more high order molecule, Including the multiple monomers combined by above-described one or more key types.

In some embodiments, when gas of the selection for cavity 130, additional factor is put into consideration, including gas The chemical property of body, availability/price of gas, toxicity of gas etc..

Heat transfer surface 110 provides mechanical stability and support to surface 120 and 140.Heat transfer surface 110 is for gas And it is impermeable, and form a part for the sealing container for keeping gas.In some embodiments, surface 120 and 140 One or both of also serve as corresponding heat transfer surface 110.In typical application, ETD systems include multiple ETD units 100, wherein unit through multiple connections cavity 130 and common gas.One such system referring to Fig. 2 with Further details describe.

In various embodiments, the outer surface of heat transfer surface 110 include surface characteristics (for example, fin, roughness etc.) with Convenient for increasing heat transfer via conduction and convection current.Additionally, in some embodiments, outer surface be coated (such as blacking) so as to It is maximized in causing the heat transfer via radiation.For example, outer surface can include one or more anodised aluminiums, carbon black, carbon Nanotube woods etc. is in order to providing in unit 100 or to the effective radiation heat transfer outside unit 100.

In some embodiments, heat transfer surface 110 is heat conduction (for example, with high thermal conductivity and physically very thin) It is and mechanically strong.The example of material with these characteristics includes polyester film, aramid fiber, aromatic polyamides, metal foil etc..It leads Heat allows heat to be easy to enter ETD units 100 by the first heat transfer surface 110A, and at the second heat transfer surface 110B It is harvested from ETD units.The good mechanical for mechanically heat transfer surface 110 being allowed to provide surface 120 and 140 by force supports, thus really The functional geometry for protecting ETD units 100 is substantially maintained under stress.Heat transfer surface 110 can be by with the phase The identical or different material construction of characteristic is hoped, depending on specific embodiment.For example, the material for each heat transfer surface 110 Material can be selected as ensuring to be effectively combined with corresponding surfacing.

In one embodiment, heat transfer surface 110 is macroscopically flexible, and is machine in shorter length dimension On tool by force.Therefore, a piece of ETD units can be manipulated to form cylinder, conveyor screw, coiling body and other such knots Structure, as desired for a particular application.

In another embodiment, heat transfer surface on inside surface (such as minute surface) there is low-E to reduce The colder surface 140 of radiant heating is returned by warmer surface 120.In another embodiment, on heat transfer surface 110 and surface Relation between 120 and 140 radiance (and absorptivity) is optimized to the radiation of returning that further reduction is only realized by reflection and adds The amount of heat.

Specific gas in cavity 130 is at least partially based on for the selection of the material on surface 120 and 140, and especially Ground based on by specific gas close to how being changed to the dissociation near the material selected by surface/recombination reaction rate.Such as with Described in upper reference Figure 1A, the material for being conducive to the dissociation of gas is selected for first surface 140.On the contrary, (it is opposite and Speech) the compound material that is conducive to gas is selected for second surface 120.In some embodiments, in surface 120 and 140 One of or both geometry be customized to the quantity that interacts between gas and surface of increase, therefore increase and correspond to Dissociation or recombination rate.For example, surface 120 or 140 can be ripple, groove, it is coarse, dendritic or by with Put the surface area that (for example, scribbling carbon nanotubes woods) can be used for the interaction of gas surface for increase.In implementation as one In example, geometry on surface 120 and 140 is customized to for this so that the ratio of the dimer of the entrance dissociated at dissociation surface Example is roughly equal with the ratio of monomer pair compound at composite surface.

In the embodiment for using HyB and/or HaB gases, for dissociating the material on surface 140 and the gas for attraction Monomer competition, thus reduce the quantity close to compound monomer near dissociation surface and therefore increase total dissociation rate.So And if dissociation surface 140 excessively consumingly interacts with monomer, they may adhere to surface.If this occurs, monomer becomes It must be not useable for participating in chemical cycle, may prevent the foundation of steady state temperature difference.Thus, for dissociating the material on surface 140 Material should be the material for removing adsorption activity with perceptible dissociation compared with the specific dimer used, it is meant that incide into table Leave the region close to surface in the discernable part of the discernable partial dissociation of dimer on face and the monomer generated.Reason Think ground, incide into dissociation surface 140 on all dimers be subjected to dissociation go to adsorb.However, the system used is usually with small Dissociation in 100% goes adsorption rate (monomer that incident dimer dissociation occurs and generates is left close to dissociation surface 140 The percentage in neighbouring region).In one embodiment, dissociation goes adsorption rate between 0.01% and 90%.In another reality It applies in example, dissociation goes adsorption rate between 0.1% and 90%.In another embodiment, dissociation go adsorption rate between 0.1% with Between 50%.In a further embodiment, dissociation goes adsorption rate between 0.1% and 10%.In other embodiments, Its dissociation goes adsorption rate, depending on the specific gas and material and ETD operation temperatures and pressure that use.

The examples material class for showing the characteristic includes but is not limited to：Metal, ceramics, metal oxide, nitride and halogen The molecule of compound and functionalized organic polymer and other high molecule masses for showing functionalized surface.This field skill Art personnel will be appreciated that in various applications, based on considerations above, embodiment may be employed following as dissociation surface 140：Noble metal (for example, gold, silver), transition metal (for example, iron, nickel, copper), refractory metal (for example, tungsten, rhenium, molybdenum), aluminium oxide (Al₂O₃), magnesia (MgO), titanium dioxide (TiO₂), silica, nitrocellulose, aromatic polyamides, nylon, artificial silk, Or polymethyl methacrylate (PMMA).

In the embodiment used in vdWB gases, dissociation surface 140 also interacts with gas so that gas is close In dissociation surface near with than its close to composite surface 120 nearby bigger rate dissociate.Those skilled in the art will recognize Know, in various applications, based on above understanding, embodiment may be employed following as gas：Surface chlorination polyethylene, The chlorinated polypropylene or teflon on surface.

The use of the another kind of material for being used as dissociating surface 140 of vdWB, HaB or HyB is in some embodiments doping Semiconductor.By using negative electrical charge or positive charge species doped semiconductor, the strong phase of monomer with forming dimer is created The position of interaction increases absorption rate, thus increases the rate of absorption.The example bag of the semiconductor of such doping Include the silicon and germanium doped with item below one or more：Chlorine, fluorine, nitrogen, oxygen, barium and caesium.

In various embodiments, depending on specific environment, using and gas selection, except it is above listed that Material outside a little be used to dissociate surface 140.

Composite surface 120 contributes to monomer is compound to return to dimer, thus, is selected for the material and list of composite surface Body by be conducive to it is compound in a manner of interact, for example, the distribution of the charge by influencing monomer.In some embodiments, it is multiple It closes surface 120 and slightly combines monomer, such as pass through weak HyB, HaB or VdWB.Therefore, in gaseous monomer and composite surface 120 Between interaction compared with the formation being bonded between monomer and without ascendancy, so as to generate dimer.With Dissociate surface 140 similarly, in idealized system, 100% monomer incided on composite surface 120 is combined with generation pair Aggressiveness is subsequently departed from close to the region near review surface.It is answered however, the system that uses is typically below 100% Adsorption rate is gone in conjunction, and (the compound dimer for occurring and generating of incident monomer is left close to the region near composite surface 120 Percentage).In one embodiment, it is compound to go adsorption rate between 0.01% and 90%.In another embodiment, it is compound Adsorption rate is gone between 0.1% and 90%.In another embodiment, it is compound to go adsorption rate between 0.1% and 50%. It is compound to go adsorption rate between 0.1% and 10% in further embodiment.In other embodiments, others are compound goes Adsorption rate occurs, depending on the specific gas and material and ETD operation temperatures and pressure that use.

The usual classification for showing the material of these characteristics includes but is not limited to：Nonpolar, organic surface is such as high The hydrocarbon of molecular weight, organosilan, chlorine polymer and unfunctionalized polymer.Those skilled in the art will appreciate that In various applications, based on above understanding, embodiment may be employed following as composite surface 120：Polyethylene, polypropylene, paraffin, Natural rubber or polyethers.

In addition, many fluoropolymers are presented for the proper characteristics as composite surface 120, including from following item system The homopolymer and copolymer of work：Ethylene, propylene, vinyl fluoride, vinylidene fluoride, tetrafluoroethene, hexafluoropropene, perfluoro propyl vinyl Ether, perfluoromethylvinyl base and chlorotrifluoroethylene.Those skilled in the art will appreciate that in various applications, based on Upper understanding, embodiment may be employed following as composite surface 120：Polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), entirely Fluoroalkyloxy polymer, polyethylene chlorotrifluoroethylene, fluorubber, perfluoropolyether or perfluorinated sulfonic acid.And then graphene is same with it Plain obform body (for example, graphite, carbon nanotubes) also shows these characteristics and can be used for composite surface 120, and combines suitable When gas be used together.

The use of the another kind of material for being used as composite surface 120 of vdWB, HaB or HyB is in some embodiments doping Semiconductor.By using negative electrical charge or positive charge species doped semiconductor, by encourage it is compound in a manner of interact with monomer Position be created.The example of the semiconductor of such doping includes the silicon and germanium doped with item below one or more：Chlorine, Fluorine, nitrogen, oxygen, barium and caesium.

In various embodiments, depending on specific environment, using and gas selection, except it is above listed that Material outside a little is used for composite surface 120.

In one embodiment, the separation between surface 120 and 140 is less than for gas phase dissociation-recombination reactionCollision or reflection mean free path (or its grade).It is for example, big for about 0.01 to 10 The air pressure of gas can use the corresponding separation in about 10-0.01 micron ranges.In other embodiments, down to 0.001 and Up to the air pressure of 40 air is used, corresponding to the separation in about 100 to 0.0025 micron ranges.

In addition, surface 120 and 140 has high thermal conductivity and is physically thin (for example, 1 to 10nm) in order to aid in Heat transfer disengaging ETD units 100.In some embodiments, surface 120 and 140 have high surface area (for example, it is coarse or It is dendritic) chemical reaction to maximize per cellar area, and be optically thin (for example, less than infrared wavelength) so that The radiation for the inside that the optical signature branch for obtaining heat transfer surface 110 fits over ETD units 100 is transferred.

Multiple separators 160 maintain the expectation between active surface 120 and 140 to separate.The material and structure of separator 160 It is selected as keeping low as much as possible via the amount of the heat transfer across cavity 130 of separator.Shown embodiment in fig. ib In, this is done by using separator 160, which is the thin column for having fillet tip, so as to heat transfer table The area that face 110 contacts is minimized.In other embodiments, separator 160 of different shapes is used, such as spherical micro- Grain.Although separator 160 is against heat transfer surface 110 in an illustrated embodiment, separator is against table in other embodiments Face 120 and 140 and/or it is embedded into surface 120 and 140 (such as shown in figure 3).

Separator 160 is mechanically sufficiently strong and is appropriately spaced to tie up when ETD units 100 are applied in stress The separation held between surface 120 and 140 is in close to desired value.Distance piece 160, which also has, to be used for minimizing from colder surface The thermal conductivity that the 120 heat passback to relatively warm surface 140 is led.In addition, distance piece 160 has low-E (for example, similar minute surface) In order to not absorb internal radiation.

In one exemplary embodiment, the gas in cavity 130 is acetic acid, and dissociation surface 140 is polymethyl Sour methyl esters, and it is polyethylene to be combined in complex surface 120.In a further exemplary embodiment, gas is formamide, dissociates surface 140 are the haloflex of part surface and composite surface 120 is polypropylene.In still further illustrative embodiments, gas Body is ammonia, and dissociation surface 140 is aluminium oxide ceramics, and composite surface 120 is polystyrene.In another exemplary embodiment In, gas is formic acid, and dissociation surface 140 is polymethyl methacrylate, and composite surface 120 is polyethylene.

Determine the combination of gas-surface

Fig. 4 illustrates according to the combination for test material and gas of one embodiment to determine them in ETD units The device 400 of the middle applicability used.Device 400 is included in the black matrix cylinder 420 inside vacuum tank 410.In a reality It applies in example, the main body of vacuum tank 410 is the stainless steel with the diameter of about 30 centimetres (cm) and the length of about 40cm Cylinder, and black matrix cylinder 420 be by tungsten or rhenium paper tinsel (thickness with about 26 microns) structure, with about The cylinder of the length of the diameter of 0.64cm and about 10cm.Vacuum tank is by diffusion pump to about 10^-6The reference pressure of support. It is closed by a pair of of aluminum pan the inside 524 (for example, part of centre 2.5cm) of black matrix cylinder 420.

In the embodiment illustrated in figure 4, cylindrical electrode 442 (for example, tantalum electrode) is attached to black matrix cylinder 420 Every one end interior surface.Electrode 442 is attached to variable power supply 440 via a pair of of electric wire 445.By using variable power supply 440 apply electric current to black matrix cylinder 420, and black matrix cylinder and its content can be by Ohmic heatings.420 He of black matrix cylinder The equalization temperature (without any surface catalysis effect) of its content thus the variation power that can be supplied by variable power supply 440 And it is controlled.It is designed to be used in the other embodiments for finding the combination of room temperature surface catalysis in device 400, variable power supply 440th, some or all of electric wire 445 and electrode 442 are omitted.In another embodiment, for cooling down black matrix cylinder 420 Mechanism be provided to enable can test material low-temperature surface catalysis characteristics.

A pair of of thermocouple 430 is positioned within black matrix cylinder 420 and is presented by the hole in aluminum pan 422 It send so that the central part of each thermocouple 430 is positioned within inside 425.It is tendency that first thermocouple 430A, which is coated with, In the material of the candidate to specific gas dissociation half-reaction, and the second thermocouple 430B is coated with and is intended to same gas The material of the candidate of compound half-reaction (compared with the first material).Each thermocouple is connected to corresponding heat via electric wire 435 Galvanic couple meter 450.Thus, the thermocouple needle 450A for being connected to the first thermocouple monitors the temperature of the first thermocouple, and second Thermocouple needle 450B monitors the temperature of the second thermocouple.For example, thermocouple needle 450 may be by once per second to monitor and remembering Record a pair of channels in the data logger of the temperature of thermocouple.

Within black matrix cavity 420, thermocouple 430 is subjected to four heat transfer channels：1) along the heat transfer of electric wire 435, 2) thermal convection current of gas present in cavity and 4) gaseous dissociation/recombination reaction (that is, surface catalysis black body radiation, 3) are passed through Effect).Thus, in order to determine the temperature difference sensed between thermocouple whether be caused by (at least partly by) surface catalysis, System should be tested for any difference as caused by other three channels.

Fig. 5 illustrates the applicability that the definite specific gas according to one embodiment-surface combination uses in ETD units Illustrative methods 500.In the following paragraphs, method 500 performs this method from the device 400 used shown in Fig. 4 Aspect is described.However, different test devices can be used in other embodiments.In various embodiments, method 500 Some in step with different order and/or are performed in parallel.Some embodiments of method 500 include additional and/or different The step of.

510, this is placed within black matrix cylinder 420 thermocouple 430.It is described above with reference to Fig. 4, the One thermocouple 430A is coated with the first candidate material and the second thermocouple 430B is coated with the second candidate material.

520, vacuum tank 410 is evacuated (such as to 10^-6The pressure of support) and this temperature of thermocouple 430 is supervised Control is until reaching balance.For example, temperature can be monitored, all do not observed until in a set period of time (such as one minute) More than the variation of threshold value (such as 0.1%).If material-gas combination is not for being that the target operating temperature of room temperature is tested Examination, power are provided to variable power supply 440 in order to the Ohmic heating system.Because thermocouple 430 is positioned in the black of vacuum In body cavity body, any variation in temperature must be due to the heat transfer along electric wire 435 either due to black body radiation or Due to the two.Theoretical and experiment is determined under these conditions at this to not having the temperature difference to be observed between thermocouple 430.

530, surface catalysis inert gas (is not subjected to the dissociation of significant quantity when meaning in target temperature everywhere in balance With the gas of recombination reaction) it is input into vacuum tank 410.Inert gas preferably has and candidate surface to be tested The gas of catalyzed gas similar characteristic in order to minimize non-surface catalysis effect be it is any sense the temperature difference the reason for can It can property.For example, if tested candidate surface catalyzed gas is hydrogen, then helium can be used in the stage of method 500.It is false If inert gas does not show surface catalysis characteristic in the presence of candidate material, it is sensed compared with step 520 It is (and any other that any variation in the temperature of thermocouple 430 will be due to the inert gas present in black matrix cylinder 420 Search gas) thermal convection current caused by.Theoretical and experiment is determined under these conditions at this to no temperature between thermocouple 430 Difference is observed.

540, the inert gas in vacuum tank 410 is substituted by candidate surface catalyzed gas.If candidate surface Catalyzed gas preferably compared with the second thermocouple 430B closer near the first thermocouple 430A (or vice versa) dissociation, It will cause steady state temperature difference, as previously described.Thus, it will being not present before between the thermocouple 430 (in step 520 and 530) Observe the temperature difference.Theoretical and experiment has confirmed the characteristic.For example, when tungsten and rhenium thermocouple 430 high temperature and low pressure (for example, At the temperature of 1900 Kelvins (K) and the pressure of 1 support) when being exposed to hydrogen, tungsten thermocouple 430A is sighted relatively It is heated naturally in rhenium thermocouple 430B, and the temperature difference observed is thermodynamic stable.

550, the feasibilities of ETD units is constructed based on observing using candidate surface catalyzed gas and candidate material Temperature and be determined.Do not show in step 540 but in step 520 and 530 that any combinations of the big temperature difference can be used to structure The effective ETD units of part.In general, the combination with the big temperature difference by cause the special properties by material applied it is other about There is the more efficient ETD units of more high power density within beam.For example, if candidate material is strong with especially low tension Degree, this can limit the size of ETD units and possible geometry.Such as another example, if specific combination requirement is heated to Raised temperature is to operate, this will reduce the net efficiency of ETD units, because power must be consumed to heating system.Its result It is that the combination showed compared with Low Temperature Difference can cause more efficiently or overall convenient ETD units.

Application method 500, for surface catalysis characteristic, material and combination of gases can be tested easily.In some realities It applies in example, more than two candidate material can utilize given gas by including additional thermocouple 430 in black matrix cylinder It is tested concurrently within 420.Additionally, by including scribbling one or more thermocouples 430 of such inert material, wait Material selection can similarly be known as be the inert material of surface catalysis compared with given gas compared with.

Fig. 6 is illustrated according to one embodiment for determining the gas used in ETD units 100, dissociation table The alternative of the applicability of the given combination of plane materiel material and composite surface material.In various embodiments, method 600 The step of in some with different order and/or be performed in parallel.Some embodiments of method 600 include additional and/or not Same step.

610, Candidate gaseous stream is directed on the first candidate material.In one embodiment, this is in supervacuum chamber It is done, wherein the pure samples of the first candidate material are subjected to Candidate gaseous stream, which includes the dimer and list of Candidate gaseous Body substance.As used in this article, pure samples are cleaned as far as possible.In other embodiments, impure sample It is used.

Air-flow is impinged upon on the sample of the first candidate material, is absorbed on sample, with sample chemical and/or physically anti- Should, and leave and (go to adsorb).620, the monomer/dimer ratio for leaving the flux for going absorption of the first candidate material is tested It measures.In one embodiment, the flux of absorption is gone to be analyzed by mass spectrograph.In other embodiments, suitable for quantitative knowledge Other diagnostic tools of the substance of absorption is not gone also to be used.

630, Candidate gaseous stream is knocked on the second candidate material.In one embodiment, this is in supervacuum chamber In be done, wherein the pure samples of the second candidate material are subjected to Candidate gaseous stream, the stream include Candidate gaseous dimer and Monomeric substance.In other embodiments, impure sample is used.

Air-flow is impinged upon on the sample of the second candidate material, is absorbed on sample, with sample chemical and/or physically anti- Should, and leave and (go to adsorb).640, the monomer/dimer ratio for leaving the flux for going absorption of the second candidate material is tested It measures.In one embodiment, the flux of absorption is gone to be analyzed by mass spectrograph.In other embodiments, suitable for quantitative knowledge Other diagnostic tools of the substance of absorption is not gone also to be used.

650, the monomer measured/dimer ratio is compared to determine gas and whether the particular combination of material is applicable in It is used in the structure in ETD units 100.Displaying removes the flux of absorption for specific more than the monomer component of gas-liquid equilibrium value Gas generates good dissociation surface 140.On the contrary, displaying goes to adsorb less than or equal to the monomer component of gas-liquid equilibrium value Flux generate good composite surface 120 for specific gas.In various embodiments, if for each surface institute Difference between the monomer component of measurement is more than threshold quantity, and the combination of specific gas and candidate material pair is deemed applicable in ETD It is used in the structure of unit 100.The threshold value used based on the desired minimum temperature difference between the surface for the embodiment and by Selection, the wherein difference of the temperature difference requirement bigger of bigger, therefore the threshold value of bigger.In some such embodiments, upper threshold value Also it is used to set the poor upper limit in monomer component, the sufficiently large temperature difference is generated to cause to ETD units 100 in order to filter out And/or the combination of the pyrolytic damage of surrounding objects.

Above method 600 can be directed to multiple combinations of gas and material pair and be repeated to determine that ETD can be being constructed In unit 100 by using those combination (consideration for the use of casting aside such as structure and economic feasibility etc).

Exemplary test data

Using shown in Fig. 5 method 500, the experiment implemented using the device of Fig. 4 determine that steady state temperature difference can deposited It is established between a pair of of surface of superficial catalytic activation gas.Temperature of the hydrogen dimer H2 in the range of 300K to 1950K Place tests the thermocouple for scribbling tungsten (W) and rhenium (Re) simultaneously, wherein air pressure up to about 10 supports.For the temperature more than 1700K Degree, the different steady state temperature differences developed between thermocouples of the W from Re is scribbled provide evidence for ETD effects.Measured The maximum steady state ETD temperature difference is 126K, is observed at the mean temperature of 1950K and the pressure of 1 support.

Based on energy scale parameter, it can speculate that steady state temperature difference can be established and maintain in room temperature.All standardization It learns the chemical equilibrium constant (Keq) that reaction is based on and depends on temperature and reaction Gibbs free energy (Keq=exp [- G/RT]), It is typically the combination energy for reaction to its main contributions.In this case, for the characteristic energy of chemical balance Scale (φ) is provided by being bonded energy to the ratio of thermal energy, i.e. φ=Δ G/RT.Thus, weaker key needs rather low Similar level of the temperature to realize dissociation and go absorption.

Hydrogen bond (about 0.5eV) is typically the order of magnitude more weaker than covalent bond (about 5eV), and Van der Waals key is typically more The weak order of magnitude (about 0.05eV).Thus, because the covalent surface of H2 is catalyzed the operational excellence at about 2000K, follow Be the dimer of hydrogen bonding and Van der Waals bonding surface catalysis dissociation should be happened at room temperature or less than room temperature.For example, because Wherein 4.5eV is that ratio φ (4.5eV/2000K) and the wherein 220K at the appropriate bond strength of hydrogen dimer is far below room Temperature at ratio φ (0.5eV/220K) it is roughly equal, can with it is conjectured that in the presence of appropriate surface pair hydrogen bond two Aggressiveness may be easy to show surface catalysis characteristic at room temperature.

Additional experiment and theoretical details on the steady state temperature difference between a pair of of surface catalysis surface can be following It finds in delivering, is incorporated herein herein with its entirety.

Sheehan, D.P., D.J.Mallin, J.T.Garamella and W.F.Sheehan, Experimental test of a thermodynamic paradox,Found.Phys.44235(2014).

Sheehan,D.P.,Nonequilibrium heterogeneous catalysis in the long mean- free-path regime,Phys.Rev.E 88032125(2013).

Sheehan, D.P., J.T.Garamella, D.J.Mallin and W.F.Sheehan, Steady-state nonequilibrium temperature gradients in hydrogen gas-metal systems； Challenging the second law of thermodynamics,Phys.Scr.T151014030(2012).

It should be noted that the phenomenon that similar, it has also been found that be present in certain type of plasma, is referred to as surface Ionic plasma.Such plasma can establish steady state pressure gradient under the conditions of black matrix.As its name implies, surface The plasma of ionization is generated by the surface via strong gas-surface interactions ionized gas.Many surface ionizations Plasma present strong nonlinearity feature, the speed of such as non-Maxwell's pencil ion can then cause stable state pressure Power and the temperature difference.Thus, ETD units can also be constructed, and wherein energy is ionizing surface and compared with plasma electric from less living Cavity is transmitted between the surface of property.

Additional experiment and theoretical details on the steady state pressure difference in the plasma of surface ionization can with Under deliver in find, be incorporated herein herein with its entirety.

Sheehan, D.P. and T.Seideman, Intrinsically biased electrocapacitive catalysis；J.Chem.Physics 122204713(2005).

Sheehan, D.P. and J.D.Means, Minimum requirement for second law violation: A paradox revisited；Phys.Plasmas 52469(1998).

Sheehan,D.P.,Another paradox involving the second law of thermodynamics；Phys.Plasmas 3104(1996).

Sheehan,D.P.,A paradox involving the second law of thermodynamics； Phys.Plasmas 21893(1995).

Use the exemplary system of multiple ETD units

Fig. 2 is the equidistant diagram according to the system configuration 200 including parallel multiple ETD units 100 of one embodiment. Merely for the purpose of diagram, Fig. 2 shows one section of the ETD plates that three ETD units 100 are wide and two ETD units 100 are deep.It is real In trampling, ETD plates will include more (for example, into hundred, thousands of or even millions of) ETD units 100.When ETD units 100 are put down When arranging capablely, the heat flux increase of cross-system 200, but the temperature difference between the both sides of unit remains unchanged.It is similarly to simultaneously By unit arrangement in circuit, electric current increases wherein and voltage is constant on row ground.

In an illustrated embodiment, surface 120 and 140 and heat transfer surface 100 are expanded across multiple ETD units 100.This Be conducive to produce, because ETD plates can layer by layer be built using method well known in the prior art.It is in addition, adjacent Units shared separator 160 (thus, each separator is the logical gate of four ETD units 100).As previously mentioned, with reference to figure 1B, single cavity 130 are shared by owning the ETD units 100 of (or at least some) in plate.Heat transfer surface 110 uses airtight close It seals and is connected in the edge of plate with end wall 280.Thus, the combination of heat transfer surface 110 and end wall 280 generates the appearance of sealing Device prevents gas from leaving cavity 130.In one embodiment, valve is set (not between the outside of cavity 130 and ETD equipment Show) with the insertion and/or replacement of enabled gas.

Separator 160 maintains the separation 230 of substantial constant throughout the plate between surface 120 and 140.In each implementation In example, depending on environment and concrete application, separate 230 and be chosen in about 0.01 micron to about 100 microns of scope. In shown embodiment, separator 160 is equally spaced a distance 260.The number for reducing separator 160 increases surface 120 and 140 useable surface area, with the less regularity of surface separation 260 for cost.Therefore, distance 260 is based on specifically should Demand and for surface 120 and 140 material rigidity and heat transfer surface 110 and make choice.In each reality It applies in example, distance 260 is chosen in about 0.1 micron to about 1000 microns of scope.In other embodiments, distance 260 can different from other direction in one direction and/or non-rectilinear configuration (for example, hexagonal cells) used. In another embodiment, particle (for example, ball shaped nano pearl) be normally used as separator 160 and they by random or semi-randomly It is dispersed in cavity 130.This has the advantages that need smaller accurate control during production process.

Fig. 3 is the side view according to the system configuration 300 of the ETD units 100 for combining three layers in series of one embodiment It represents.Although every layer is illustrated as being single ETD units 100, in practice, every layer can include many (examples being arranged in parallel Such as, it is hundreds of, thousands of or even millions of) ETD units, it is described as described above with Fig. 2.Display three layers selection for purely The purpose of diagram.Principles described herein can be used to be stacked any number of layer.Independent layer is in good with adjacent layer Good thermo-contact.When ETD units 100 are by arranged in series, the temperature difference of unit is increased, but the heat flux of cross-system 200 is not Become.It is similarly to that unit being arranged, in circuit, voltage increases wherein and electric current is constant in series.

In an illustrated embodiment, adjacent layer shares heat transfer surface 110 so that one layer of top heat transfer surface is also used Make the bottom heat transfer surface of the layer on it, and vice versa.In an illustrated embodiment, there are two surfaces for the tool of bottom 301 350 and 360 and the cavity 355 comprising first gas.Thus, bottom 301 causes the first temperature difference T1 across it.For surface 350 and 360 material and first gas be selected as when input heat transfer surface 110A be in desired operation temperature when it is excellent The operation of change system.

Interlayer 302 also has there are two surface 330 and 340 and the cavity 335 comprising second gas.Thus, interlayer 302 cause the second temperature difference T2 across it.In one embodiment, for the material and gas in interlayer 302 and in bottom 301 Those middle used are identical.In other embodiments, the material and second gas for surface 330 and 340 are based on input heat It transfers the desired operation temperature of surface 110A and Δ T1 is selected as being in desired as the first internal heat transfer surface 110B The operation of optimization system during operation temperature.

Top layer 303 also has there are two surface 310 and 320 and the cavity 315 comprising third gas.Thus, top layer 303 is led It causes across its 3rd temperature difference T3.In one embodiment, for top layer 303 material and gas with bottom 301 and/or in Those used in interbed 302 are identical.In other embodiments, it is based on for the material and third gas on surface 310 and 320 The desired operation temperature and Δ T1 and Δ T2 of input heat transfer surface 110A is selected as when the second internal heat transfer surface The operation of optimization system when 110C is in desired operation temperature.

Therefore, system configuration 300 as a whole provides input heat transfer surface 110A and output heat transfer surface Temperature difference T1+ Δ T2+ Δ T3 between 110D, this can be noticeably greater than by any one temperature obtained in layer 301-303 Difference.

Additional consideration

As used herein, term "comprising", " comprising ", " having ", " having " or any other variant are intended to cover non-exclusive Property includes.E.g., including the process of a series of elements, method, article or device are not necessarily limited to those elements, but can It is not expressly listed or inherently in other elements of these processes, method, article or device to include.In addition, removing non-clearly has phase Anti- explanation, "or" refer to inclusive or, rather than exclusiveness or.For example, condition A or B be satisfied with it is following in any one：A It is true (or presence) and B is false (or there is no), A is false (or there is no) and B is that true (or presence) and A and B are true (or presence).

In addition, the use of "a" or "an" is used to describe the element and component of embodiment described herein.This be only for Convenience simultaneously gives in general sense completing for the disclosure.This description should be read to include one or at least one, and And odd number further includes plural number, unless clearly it refers to odd number.

When reading present disclosure, those skilled in the art will be appreciated that the another alternative structure and work(for ETD It can design, which create steady state temperature difference.Thus, although specific embodiment and application have been illustrated and have described, but it is to be understood that Described theme is not limited to precision architecture disclosed herein and component, to those skilled in the art obviously Various modifications, change and variation can in method and device disclosed herein arrangement, make in operation and details.

Claims

1. a kind of surface catalysis thermal diode equipment, including multiple surface catalysis thermal diode units being connected in parallel, Mei Gebiao Surface catalysis thermal diode unit includes：

First surface, the first surface and the mutual chemical action of gas so that the gas is close to the first surface Sentence first rate dissociation；

Second surface, the second surface and the mutual chemical action of the gas so that the gas is close to described second The second rate dissociation is sentenced on surface, and the second surface is arranged essentially parallel to the first surface, and second rate is low In the first rate；And

Multiple distance pieces between the first surface and the second surface, the multiple distance piece is by first table Distance maintaining between face and the second surface is in the distance of substantial constant；

Wherein：

The first surface and the second surface define the cavity for being configured to include the gas；

Difference between the first rate and second rate causes across the cavity in the first surface and described second Steady state temperature difference between surface；

The cavity of the multiple surface catalysis thermal diode unit being connected in parallel is interconnected；And

Adjacent at least one distance piece of surface catalysis thermal diode units shared.

2. surface catalysis thermal diode equipment according to claim 1, wherein the first surface is by being selected from the following At least one of group formed material is made：Magnesium, aluminium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, molybdenum, Ruthenium, rhodium, palladium, silver, tin, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, hafnium, the silicon of doping, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, lead, oxidation Aluminium, magnesia, titanium dioxide, silica, nitrocellulose, aromatic polyamides, nylon, staple fibre and polymethyl Sour methyl esters.

3. surface catalysis thermal diode equipment according to claim 1, wherein the second surface is by being selected from the following At least one of group formed material is made：Polyethylene, polypropylene, paraffin, natural rubber, the silicon of doping, polyethers, poly- fluorine Ethylene, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), perfluoroalkoxy, polyethylene chlorotrifluoroethylene, fluorubber, perfluor gather Ether, perfluorinated sulfonic acid, graphene, graphite and carbon nanotubes.

4. surface catalysis thermal diode equipment according to claim 1, wherein the gas is included selected from the following institute At least one of group of composition gas：Formic acid, acetic acid, methanol, ethyl alcohol, formaldehyde, ammonia, dimethyl ketone, methylamine, dimethylamine, two Methyl ether, water, acetamide, first sulphur, cyanogen, hydrogen cyanide, hydrogen fluoride, hydrogen sulfide, cyanogen methane, formamide, amino azomethine, hydrogen chloride, Ethyl cyanide, nitrogen, carbon monoxide, carbon dioxide, sulfur dioxide, nitrogen oxide, single halomethane, methylene halide, haloform, four halogen Methane, halothane, hydrogen, helium, neon, argon, krypton, xenon, radon, methane, ethane and propane.

5. surface catalysis thermal diode equipment according to claim 1, wherein the constant distance is micro- in 0.01 to 100 In the scope of rice.

6. surface catalysis thermal diode equipment according to claim 1, wherein the multiple surface catalysis thermal diode list At least one in member further comprises the first heat transfer surface, first heat transfer surface the first surface with it is described It is connected on the opposite side of cavity with the first surface and substantially parallel, first heat transfer surface is configured to from institute Heat is conducted to the first surface in the outside for stating surface catalysis thermal diode.

7. surface catalysis thermal diode equipment according to claim 6, wherein the multiple surface catalysis thermal diode list At least one in member further comprises the second heat transfer surface, second heat transfer surface the second surface with it is described It is connected on the opposite side of cavity with the second surface and substantially parallel, second heat transfer surface is configured to from institute It states second surface and conducts heat outside the surface catalysis thermal diode.

8. a kind of surface catalysis thermal diode system, including being urged with the multiple surfaces according to claim 1 being connected in series Change thermal diode equipment, wherein adjacent surface catalysis thermal diode equipment is separated by shared heat transfer surface, institute Shared heat transfer surface is stated to be configured to transfer heat between adjacent surface catalysis thermal diode equipment.

9. surface catalysis thermal diode equipment according to claim 1, wherein the gas on the first surface with The first rate dissociates and the gas is dissociated on the second surface with second rate.

10. surface catalysis thermal diode equipment according to claim 1, wherein the first surface and the second surface Cleaned.

11. surface catalysis thermal diode equipment according to claim 1 further comprises being located at one within the cavity The quantitative gas, the amount of the gas are chosen to the pressure that the gas is in 0.01 to 10 barometric pressure range Under.

12. surface catalysis thermal diode equipment according to claim 11, wherein the gas is purified.

13. a kind of method for generating and maintaining the temperature difference, including：

Surface catalysis thermal diode equipment is provided, the surface catalysis thermal diode equipment is urged including multiple surfaces being connected in parallel Change thermal diode unit, each surface catalysis thermal diode unit includes：

The second surface of the first surface, the second surface and the mutual chemical action of the gas are arranged essentially parallel to, is made The gas is dissociated close at the second surface with the second rate, second rate is less than the first rate, The first surface and the second surface define cavity；And

Wherein：

Adjacent at least one distance piece of surface catalysis thermal diode units shared

A certain amount of gas is provided in the cavity；

Difference between wherein described first rate and second rate causes across the cavity in the multiple surface catalysis heat The temperature difference between the first surface and the second surface of diode.

14. according to the method for claim 13, wherein the first surface is by the group that the following is formed At least one material is made：Ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold, scandium, cadmium, titanium, hafnium, the silicon of doping, vanadium, tantalum, chromium, tungsten, manganese, Rhenium, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, aluminium oxide, magnesia, titanium dioxide, silica, nitrocellulose, aromatics Polyamide, nylon, staple fibre and polymethyl methacrylate.

15. according to the method for claim 13, wherein the second surface is by the group that the following is formed At least one material is made：Polyethylene, polypropylene, paraffin, natural rubber, the silicon of doping, polyethers, polyvinyl fluoride gather inclined difluoro Ethylene, polytetrafluoroethylene (PTFE), perfluoroalkoxy, polyethylene chlorotrifluoroethylene, fluorubber, perfluoropolyether, perfluorinated sulfonic acid, stone Black alkene, graphite and carbon nanotubes.

16. according to the method for claim 13, wherein the gas is included in the group that the following is formed extremely A kind of few gas：Formic acid, acetic acid, methanol, ethyl alcohol, formaldehyde, ammonia, dimethyl ketone, methylamine, dimethylamine, dimethyl ether, water, acetamide, First sulphur, cyanogen, hydrogen cyanide, hydrogen fluoride, hydrogen sulfide, cyanogen methane, formamide, amino azomethine, hydrogen chloride, ethyl cyanide, nitrogen, an oxygen Change carbon, carbon dioxide, sulfur dioxide, nitrogen oxide, single halomethane, methylene halide, haloform, tetrahalomethanes, halothane, Hydrogen, helium, neon, argon, krypton, xenon, radon, methane, ethane and propane.

17. according to the method for claim 13, wherein at least one in the multiple surface catalysis thermal diode unit Further comprise：

First heat transfer surface, first heat transfer surface on opposite side of the first surface with the cavity with it is described First surface connect and it is substantially parallel, first heat transfer surface is configured to from the surface catalysis thermal diode Heat is conducted to the first surface in outside.

18. according to the method for claim 17, wherein at least one in the multiple surface catalysis thermal diode unit Further comprise：

Second heat transfer surface, second heat transfer surface on opposite side of the second surface with the cavity with it is described Second surface connect and it is substantially parallel, second heat transfer surface is configured to from the second surface to the surface Heat is conducted outside catalysis thermal diode.

19. according to the method for claim 13, wherein the gas on the first surface with the first rate from It solves and the gas is dissociated on the second surface with second rate.

20. according to the method for claim 13, further comprise cleaning the first surface before the gas is provided With the second surface.

21. according to the method for claim 13, wherein the amount of the gas within the cavity cause 0.01 to Pressure in the range of 10 atmospheric pressure.

22. according to the method for claim 13, further comprise purifying the gas before the gas is provided.