CN103866343B - Method and device for synthesizing ammonia through carrying out efficient electrocatalytic reduction on nitrogen gas at low temperature and normal pressure - Google Patents
Method and device for synthesizing ammonia through carrying out efficient electrocatalytic reduction on nitrogen gas at low temperature and normal pressure Download PDFInfo
- Publication number
- CN103866343B CN103866343B CN201410111975.1A CN201410111975A CN103866343B CN 103866343 B CN103866343 B CN 103866343B CN 201410111975 A CN201410111975 A CN 201410111975A CN 103866343 B CN103866343 B CN 103866343B
- Authority
- CN
- China
- Prior art keywords
- cathode
- anode
- chamber
- catalyst
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a method and device for synthesizing ammonia through carrying out efficient electrocatalytic reduction on nitrogen gas at low temperature and normal pressure. The method comprises the steps of constructing an electrocatalytic electrolytic tank with an anode chamber and a cathode chamber which are partitioned by using a proton exchange membrane, taking carbon cloth coated with a Pt catalyst as an anode electrode, taking carbon cloth coated with a sulfur-bridged di(multi)nuclear iron cluster compound catalyst as a cathode electrode, and respectively connecting an anode and a cathode with high-potential and low-potential ends of a stabilized-voltage supply through leads; oxidizing water saturated H2 on the surface of the anode electrode to generate H<+> and electrons, respectively migrating the generated H<+> and electrons to the surface of the cathode electrode through the proton exchange membrane and an external circuit, and combining N2 provided by the cathode chamber with H<+> and the electrons on the surface of the cathode electrode under the action of an o-benzenedithiol-bridged dinuclear iron compound catalyst to generate NH3. According to the invention, an azotase model compound, namely an iron-sulfur cluster compound is used as the cathode catalyst of the electrolytic tank, thus solving the problem that the cathode catalyst is relatively low in catalytic efficiency when ammonia is synthesized through electrocatalysis at high temperature, high pressure and high energy consumption in the traditional ammonia synthesis process.
Description
Technical field
The invention belongs to electro-catalysis synthesis technical field, be specifically related to the method that efficient electric under low-temperature atmosphere-pressure catalyzes and synthesizes ammonia
And device.
Background technology
Since Haber (Harber) ammonia synthesis in 1909 is born, the method has continued and has developed century more than one.
Researcher constantly reforms its technological process, develops new catalyst and catalyst aid, it is intended to reduce synthesis ammonia temperature and conjunction
Become ammonia pressure and improve the conversion ratio of nitrogen, but innovation the method still cannot break through thermodynamic (al) restriction in any case.Along with
Ammonia demand is continuously increased and the becoming increasingly conspicuous, to high efficiency, mental retardation of energy problem and problem of environmental pollution by the whole world
The exploration of consumption and eco-friendly synthesis ammonia new method becomes the inevitable requirement ensureing Global Sustainable Development.Many synthesis ammonia
New method is arisen at the historic moment, such as normal temperature and pressure streamer-discahrge method, microwave method, supercritical ultrasonics technology and electrocatalytic method etc., and wherein electro-catalysis
The synthesis of ammonia is wherein to study one more, that mechanism is more ripe.Electric energy is introduced synthesis ammonia, on the one hand can make some thermodynamics
Cells with non-spontaneous reactions occurs under the promotion of electric energy, thus expands the research field of ammonia synthesis mode；On the other hand synthesis can also be made
Ammonia reaction is not affected or less affected by the thermodynamical equilibrium restriction to conversion ratio.Use electro-catalytic process also can achieve the normal temperature and pressure of ammonia
Synthesis.
In electro-catalysis synthesis ammonia, first pass through the eelctro-catalyst modified at electrode surface and nitrogen molecular is carried out preliminary suction
Attached activation, then provides extra electronics to promote it to occur supplied for electronic to activate also further by electrode to adsorbed nitrogen molecular
Electronics needed for reduction is provided, provides the H needed for protonation by electrolyte solution or solid electrolyte to nitrogen molecular simultaneously+。
Mutually cut with multiphase catalyst adsorption activation and the activation of dinitrogen coordination compound supplied for electronic activation existence, reduction, protonation process
The situation split is different, and electro-catalysis synthesis ammonia is conducive to founding the fixed nitrogen ring of the collaborative activation similar to azotase and reduction synthesis
Border, and electro-catalysis synthesis ammonia can efficiently control the activation degree of nitrogen molecular, by controlling nitrogen by controlling electrode potential
The transfer rate of gas and proton controls building-up process easily, this obviously research to reaction kinetics and mechanism highly beneficial.But by
The relatively low bottleneck becoming the method for catalytic efficiency in cathod catalyst.
Summary of the invention
The present invention provides a kind of method that under low-temperature atmosphere-pressure, efficient electric catalyzes and synthesizes ammonia, with azotase model compound ferrum sulfur
Cluster compound is cathod catalyst, during to avoid the tradition high temperature of ammonia synthesis process, high pressure and high energy consumption and electro-catalysis synthesis ammonia
The problem that cathod catalyst catalytic efficiency is relatively low.
For solving the problems referred to above, the present invention adopts the following technical scheme that
The present invention provides the method for a kind of low-temperature atmosphere-pressure efficient electric catalytic reduction of nitrogen gas synthesis ammonia, is characterised by: build one
The individual electro-catalysis electrolyzer including anode chamber and cathode chamber, anode chamber and cathode chamber PEM Nafion 117 separate,
Anode chamber places anode electrode, cathode chamber is placed cathode electrode, anode electrode and cathode electrode by wire respectively with surely
The hot end of voltage source is connected with cold end；Anode catalyst is Pt；Cathod catalyst is adjacent diphenyl disulfide phenol bridged binuclear
Iron complex；Water saturated H2H is produced by Pt catalyst at anode electrode surface+And electronics, the H of generation+With electronics respectively
Cathode electrode surface, and the N provided with cathode chamber is moved to by PEM and external circuit2Adjacent in cathode electrode surface
Diphenyl disulfide phenol bridged binuclear iron complex catalyst generates NH3。
As preferred technical scheme, described anode electrode material is the carbon cloth that Pt catalyst is modified.
As preferred technical scheme, described cathode electrode material is that double (many) core Iron cluster catalyst of sulphur bridge connection is modified
Carbon cloth.
It is serpentine configuration as preferred technical scheme, the anode chamber of described electro-catalysis electrolyzer and the chamber of cathode chamber,
Add the probability that reactant contacts with catalyst, thus improve the electrode reaction efficiency of cathode and anode.
As preferred technical scheme, the VD of described regulated power supply is-3.0V ~ 3.0V.
As preferred technical scheme, the method for described low-temperature atmosphere-pressure efficient electric catalytic reduction of nitrogen gas synthesis ammonia is continuously behaviour
Making, anode chamber is passed through water saturated pure H continuously2, cathode chamber is passed through pure N continuously2。
Present invention also offers the device of a kind of low-temperature atmosphere-pressure electro-catalysis reduction nitrogen synthesis ammonia, described device includes: lead
Trachea, anode copper collector plate, anode electrode, PEM, wire, regulated power supply, wire, cathode electrode, and tough cathode collection
Stream plate；
Have guiding gutter in anode copper collector plate, as the anode chamber of electro-catalysis electrolyzer, upper and lower airway respectively with lead
Chute connects；
Have guiding gutter in tough cathode collector plate, as the cathode chamber of electro-catalysis electrolyzer, upper and lower airway respectively with lead
Chute connects；
By screw, anode copper collector plate, anode electrode, PEM, cathode electrode and tough cathode collector plate are fixed
Together, anode chamber and cathode chamber PEM Nafion 117 separate；
Anode electrode is connected with the high potential of regulated power supply through wire；Cathode electrode is through the electronegative potential of wire Yu regulated power supply
It is connected；The VD of regulated power supply is-3.0V ~ 3.0V；
Anode electrode is the carbon cloth of coating Pt catalyst, with Nafion solution as binding agent；
Cathode electrode is the carbon cloth of the adjacent diphenyl disulfide phenol bridged binuclear iron complex catalyst of coating, is viscous with Nafion solution
Knot agent.
It is serpentine configuration as preferred technical scheme, the anode chamber of electro-catalysis electrolyzer and the chamber of cathode chamber, increases
The probability that reactant contacts with catalyst, thus improve the electrode reaction efficiency of cathode and anode.
As preferred technical scheme, described device coordinates with azotase model compound neighbour's diphenyl disulfide phenol bridging multinuclear ferrum
Thing is cathod catalyst.
As preferred technical scheme, described anode chamber is passed through water saturated pure H continuously2, described cathode chamber is passed through continuously
Pure N2。
As preferred technical scheme, described H2And N2Purity is 99.99%, and its flow velocity is 30 mL/min.
As preferred technical scheme, the Pt catalyst of described anode electrode coating is relative carbon cloth area 0.5 mg/
cm2, the adjacent diphenyl disulfide phenol bridged binuclear iron complex of described cathode electrode coating is relative carbon cloth area catalyst 0.5 mg/
cm2。
As preferred technical scheme, the VD of described regulated power supply is 2 V.
The method of low-temperature atmosphere-pressure efficient electric catalytic reduction of nitrogen gas provided by the present invention synthesis ammonia, it is with azotase modelling
Double (many) the core iron complexes of compound neighbour's diphenyl disulfide phenol bridging are cathod catalyst, synthesize at optimum conditions ammonia speed reach 2.18 ×
10-8 mol•cm-2•s-1, for 2 ~ 5 times of the electro-catalysis ammonia synthesis rate of prior art, to some extent solve existing
The problem that technology electro-catalysis synthesis ammonia speed is low.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram of low-temperature atmosphere-pressure electro-catalysis of the present invention reduction nitrogen synthesis ammonia.
Fig. 2 is the electrolytic cell anode copper collector plate structural representation of the embodiment of the present invention.
Fig. 3 is the cathode of electrolytic tank copper collector plate structural representation of the embodiment of the present invention.
Detailed description of the invention
Below by way of specific embodiment, in conjunction with accompanying drawing, the present invention is described in further details.
Fig. 1 is the device schematic diagram of low-temperature atmosphere-pressure electro-catalysis of the present invention reduction nitrogen synthesis ammonia.The present embodiment low-temperature atmosphere-pressure
The method of efficient electric catalytic reduction of nitrogen gas synthesis ammonia, operates with step the most in the following order:
(1) structure of electrolyzer
Electrolyzer includes: airway 1, anode copper collector plate 2, airway 3, anode electrode 4, PEM 5, wire 6,
Regulated power supply 7, wire 8, cathode electrode 9, tough cathode collector plate 10, airway 11 and airway 12；Open in anode copper collector plate 2
Having guiding gutter, as the anode chamber of electrolyzer, airway 1 connects with guiding gutter respectively with airway 3；In tough cathode collector plate 10
Having guiding gutter, as the cathode chamber of electrolyzer, airway 11 connects with guiding gutter respectively with airway 12；By screw by sun
Pole copper collector plate 2, anode electrode 4, PEM 5, cathode electrode 9 and tough cathode collector plate 10 are fixed together；Anode electricity
Pole 4 is connected through the high potential of wire 6 with regulated power supply 7；Cathode electrode 9 is connected through the electronegative potential of wire 8 with regulated power supply 7；Sun
Pole electrode 4 is coating Pt catalyst (0.5 mg/cm2, relative carbon cloth area) carbon cloth, with Nafion solution as binding agent；Cloudy
Pole electrode 9 is adjacent diphenyl disulfide phenol bridged binuclear iron complex catalyst (0.5 mg/cm of coating2, relative carbon cloth area) carbon cloth,
With Nafion solution as binding agent.
(2) the electro-catalysis synthesis of ammonia
Moistening H it is passed through continuously to the anode chamber of electrolyzer by airway 12G () (hydrogen purity 99.99%, by 25 DEG C
Enter after distilled water), it is passed through drying nitrogen (nitrogen gas purity 99.99%) by airway 12 continuously to the cathode chamber of electrolyzer, stream
Speed is 30 mL/min, and the power supply of regulated power supply is set to 2 V.H2First at the oxidized generation in anode electrode 4 surface H+And electronics,
The H produced+Migrate through PEM 5 and external circuit (anode electrode 4, wire 6, regulated power supply 7 and wire 8) respectively with electronics
To cathode electrode 9 surface, N under electricity assists2、H+On cathode electrode 9 surface, combination generates NH with electronics3, concrete chemical reaction side
Formula is as follows:
Anode electrode
Cathode electrode
And produced NH3Collect through conductive gas pipe 3, utilize airway 11 to unreacted H2Reclaim.
It is last that it is noted that obviously above-described embodiment is only for clearly demonstrating example of the present invention, and also
The non-restriction to embodiment.For those of ordinary skill in the field, can also do on the basis of the above description
Go out change or the variation of other multi-form.Here without also cannot all of embodiment be given exhaustive.And thus drawn
What Shen went out obviously changes or changes among still in protection scope of the present invention.
Claims (3)
1. a method for low-temperature atmosphere-pressure electro-catalysis reduction nitrogen synthesis ammonia, is characterised by: build one and include anode chamber and the moon
The electro-catalysis electrolyzer of room, pole, anode chamber and cathode chamber PEM Nafion 117 separate, and place anode in anode chamber
Electrode, places cathode electrode in cathode chamber, anode electrode and cathode electrode by wire respectively with the hot end of regulated power supply
It is connected with cold end；Anode catalyst is Pt；Cathod catalyst is adjacent diphenyl disulfide phenol bridging multinuclear iron complex；Water saturated
H2H is produced by Pt catalyst at anode electrode surface+And electronics, the H of generation+With electronics respectively by PEM and
External circuit moves to cathode electrode surface, and the N provided with cathode chamber2In cathode electrode surface by adjacent diphenyl disulfide phenol bridging multinuclear
Iron complex catalyst generates NH3；
The anode chamber of electro-catalysis electrolyzer and the chamber of cathode chamber are serpentine configuration；
Described method is with azotase model compound neighbour's diphenyl disulfide phenol bridging multinuclear iron complex as cathod catalyst.
2. a device for low-temperature atmosphere-pressure electro-catalysis reduction nitrogen synthesis ammonia, is characterised by: described device includes: airway, sun
Pole copper collector plate, anode electrode, PEM, wire, regulated power supply, wire, cathode electrode, and tough cathode collector plate；
Have guiding gutter in anode copper collector plate, as the anode chamber of electro-catalysis electrolyzer, upper and lower airway respectively with guiding gutter
Connection；
Have guiding gutter in tough cathode collector plate, as the cathode chamber of electro-catalysis electrolyzer, upper and lower airway respectively with guiding gutter
Connection；
By screw, anode copper collector plate, anode electrode, PEM, cathode electrode and tough cathode collector plate are fixed on one
Rising, anode chamber and cathode chamber PEM Nafion 117 separate；
Anode electrode is connected with the high potential of regulated power supply through wire；Cathode electrode is through the electronegative potential phase of wire with regulated power supply
Even；The VD of regulated power supply is-3.0V ~ 3.0V；
Anode electrode is the carbon cloth of coating Pt catalyst；
Cathode electrode is the carbon cloth of the adjacent diphenyl disulfide phenol bridging multinuclear iron complex catalyst of coating；
The anode chamber of described electro-catalysis electrolyzer and the chamber of cathode chamber are serpentine configuration；
Described device is with azotase model compound neighbour's diphenyl disulfide phenol bridging multinuclear iron complex as cathod catalyst；
Described anode chamber is passed through water saturated pure H continuously2, described cathode chamber is passed through pure N continuously2；Described H2And N2Purity is
99.99%, its flow velocity is 30 mL/min；
The Pt catalyst of described anode electrode coating is relative carbon cloth area 0.5 mg/cm2, the adjacent benzene of described cathode electrode coating
Dithiol bridging multinuclear iron complex is relative carbon cloth area catalyst 0.5 mg/cm2。
The device of a kind of low-temperature atmosphere-pressure electro-catalysis the most according to claim 2 reduction nitrogen synthesis ammonia, it is characterised in that: institute
The VD stating regulated power supply is 2 V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410111975.1A CN103866343B (en) | 2014-03-25 | 2014-03-25 | Method and device for synthesizing ammonia through carrying out efficient electrocatalytic reduction on nitrogen gas at low temperature and normal pressure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410111975.1A CN103866343B (en) | 2014-03-25 | 2014-03-25 | Method and device for synthesizing ammonia through carrying out efficient electrocatalytic reduction on nitrogen gas at low temperature and normal pressure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103866343A CN103866343A (en) | 2014-06-18 |
| CN103866343B true CN103866343B (en) | 2017-01-11 |
Family
ID=50905338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410111975.1A Expired - Fee Related CN103866343B (en) | 2014-03-25 | 2014-03-25 | Method and device for synthesizing ammonia through carrying out efficient electrocatalytic reduction on nitrogen gas at low temperature and normal pressure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103866343B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10058819B2 (en) | 2015-11-06 | 2018-08-28 | Paccar Inc | Thermally integrated compact aftertreatment system |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104630811B (en) * | 2015-02-13 | 2017-03-08 | 王海斌 | A kind of electrolysis ammonia-preparing device |
| US10188986B2 (en) * | 2015-11-06 | 2019-01-29 | Paccar Inc | Electrochemical reductant generation while dosing DEF |
| CN106480469A (en) * | 2016-07-14 | 2017-03-08 | 张国权 | The manufacture method of small-sized ammonia machine processed |
| GB2552526A (en) * | 2016-07-28 | 2018-01-31 | Siemens Ag | Electrochemical method of ammonia generation |
| US10675586B2 (en) | 2017-06-02 | 2020-06-09 | Paccar Inc | Hybrid binary catalysts, methods and uses thereof |
| US10835866B2 (en) | 2017-06-02 | 2020-11-17 | Paccar Inc | 4-way hybrid binary catalysts, methods and uses thereof |
| GB2572354B (en) * | 2018-03-27 | 2022-10-26 | The Univ Of Oxford | Novel electrochemical set-up for ammonia production |
| CN111304689B (en) * | 2018-12-11 | 2022-04-12 | 深圳先进技术研究院 | Titanium diboride/boron carbide composite electrode and preparation method and application thereof |
| US11007514B2 (en) | 2019-04-05 | 2021-05-18 | Paccar Inc | Ammonia facilitated cation loading of zeolite catalysts |
| US10906031B2 (en) | 2019-04-05 | 2021-02-02 | Paccar Inc | Intra-crystalline binary catalysts and uses thereof |
| CN110055558B (en) * | 2019-06-04 | 2021-03-16 | 宁夏回族自治区环境监测中心站 | Normal-temperature nitrogen fixing electrocatalyst, preparation method of electrocatalytic electrode and nitrogen fixing method |
| JPWO2021045206A1 (en) * | 2019-09-05 | 2021-03-11 | ||
| US10934918B1 (en) | 2019-10-14 | 2021-03-02 | Paccar Inc | Combined urea hydrolysis and selective catalytic reduction for emissions control |
| CN110983356B (en) * | 2019-10-22 | 2021-04-20 | 浙江大学 | Nitrogen fixation device and method based on low-temperature jet plasma coupled monatomic catalysis |
| CN111058054B (en) * | 2020-01-03 | 2022-01-18 | 大连理工大学 | Device and method for synthesizing ammonia by electrocatalytic nitrogen reduction by using salt bridge to replace Nafion membrane |
| WO2023081323A1 (en) * | 2021-11-04 | 2023-05-11 | Lawrence Livermore National Security, Llc | Direct conversion of air to ammonia and nitric acid via advanced manufactured electrochemical reactors |
| CN115142079B (en) * | 2022-07-06 | 2024-04-02 | 中国华能集团清洁能源技术研究院有限公司 | Dual-functional electrolysis method and system for producing ammonia and hydrogen |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0254790A (en) * | 1988-08-18 | 1990-02-23 | Choichi Furuya | Method and apparatus for electrolytically synthesizing ammonia |
| CN101589176A (en) * | 2006-12-21 | 2009-11-25 | 代理并代表亚利桑那州立大学的亚利桑那董事会 | Method and apparatus for ammonia (NH3) generation |
| JP2013209685A (en) * | 2012-03-30 | 2013-10-10 | Nippon Shokubai Co Ltd | Electrochemical cell for ammonia production and ammonia synthesis method using the same |
| CN203741430U (en) * | 2014-03-25 | 2014-07-30 | 内蒙古科技大学 | Device for synthesizing ammonia by electro-catalytically reducing nitrogen at low-temperature and under normal pressure |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6881308B2 (en) * | 2002-03-04 | 2005-04-19 | Lynntech, Inc. | Electrochemical synthesis of ammonia |
-
2014
- 2014-03-25 CN CN201410111975.1A patent/CN103866343B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0254790A (en) * | 1988-08-18 | 1990-02-23 | Choichi Furuya | Method and apparatus for electrolytically synthesizing ammonia |
| CN101589176A (en) * | 2006-12-21 | 2009-11-25 | 代理并代表亚利桑那州立大学的亚利桑那董事会 | Method and apparatus for ammonia (NH3) generation |
| JP2013209685A (en) * | 2012-03-30 | 2013-10-10 | Nippon Shokubai Co Ltd | Electrochemical cell for ammonia production and ammonia synthesis method using the same |
| CN203741430U (en) * | 2014-03-25 | 2014-07-30 | 内蒙古科技大学 | Device for synthesizing ammonia by electro-catalytically reducing nitrogen at low-temperature and under normal pressure |
Non-Patent Citations (4)
| Title |
|---|
| Ammonia formation by a thiolate-bridged diiron amide complex as a nitrogenase mimic;Yang Li等;《Nature Chemistry》;20130317;第5卷;第320-326页 * |
| SmCo_(0.8)Fe_(0.2-x)Ni_xO_3(x=0,0.1,0.2)粉体在低温常压电化学合成氨中的阴极催化性能;韩慧等;《化学通报》;20091115(第11期);第998-1002页 * |
| 全氟磺酸型质子交换膜在低温常压电化学合成氨中的应用;刘玉星等;《科技信息》;20090815(第23期);第442-443、458页 * |
| 利用Nafion膜和SFCN在低温常压下电化学合成氨;徐高超等;《中国科学(B辑:化学)》;20090515;第39卷(第05期);第447-451页 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10058819B2 (en) | 2015-11-06 | 2018-08-28 | Paccar Inc | Thermally integrated compact aftertreatment system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103866343A (en) | 2014-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103866343B (en) | Method and device for synthesizing ammonia through carrying out efficient electrocatalytic reduction on nitrogen gas at low temperature and normal pressure | |
| CN203741430U (en) | Device for synthesizing ammonia by electro-catalytically reducing nitrogen at low-temperature and under normal pressure | |
| McHugh et al. | Decoupled electrochemical water splitting: from fundamentals to applications | |
| Wu et al. | Non-noble metal-based bifunctional electrocatalysts for hydrogen production | |
| Shen et al. | Heterogeneous Ni-MoN nanosheet-assembled microspheres for urea-assisted hydrogen production | |
| Nam et al. | Optimization of catholyte concentration and anolyte pHs in two chamber microbial electrolysis cells | |
| TWI414636B (en) | Membrane reactor | |
| Jiang et al. | Periodic polarity reversal for stabilizing the pH in two-chamber microbial electrolysis cells | |
| Zhang et al. | Stable multifunctional single-atom catalysts adsorbed on pyrazine-modified graphyne | |
| Luo et al. | Realizing efficient oxygen evolution at low overpotential via dopant-induced interfacial coupling enhancement effect | |
| Nelabhotla et al. | Electrochemically mediated CO2 reduction for bio-methane production: a review | |
| BR112012000046B1 (en) | method to produce methane | |
| CN113908870B (en) | Controllable preparation of double-function non-noble metal nitride catalyst and high-current electrolytic urea hydrogen production application | |
| CN109954503A (en) | A kind of nickelous selenide and ternary selenizing ferronickel composite electrocatalyst and preparation method and application | |
| Sun et al. | Interface catalysts of Ni/Co2N for hydrogen electrochemistry | |
| Wu et al. | Recent advances and strategies of electrocatalysts for large current density industrial hydrogen evolution reaction | |
| Ma et al. | Solid‐state redox mediators for decoupled H2 production: principle and challenges | |
| Kadier et al. | Microbial electrolysis cells (MECs) as innovative technology for sustainable hydrogen production: fundamentals and perspective applications | |
| Liu et al. | Energy-efficient monosaccharides electrooxidation coupled with green hydrogen production by bifunctional Co9S8/Ni3S2 electrode | |
| CN109022495A (en) | A kind of method of micro-reduction carbon dioxide methane phase | |
| Yang et al. | PdAgCu alloy nanoparticles integrated on three-dimensional nanoporous CuO for efficient electrocatalytic nitrogen reduction under ambient conditions | |
| CN104762635A (en) | Method and device for co-production of methane by electrically assisted conversion of ethanol into acetic acid | |
| CN112958116A (en) | Bi2O2.33-CdS composite photocatalyst and preparation process thereof | |
| Zhou et al. | Decoupled water electrolysis: Flexible strategy for pure hydrogen production with small voltage inputs | |
| Yin et al. | Co3O4/C derived from ZIF-67 cathode enhances the microbial electrosynthesis of acetate from CO2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170111 Termination date: 20180325 |