CN111298813B - A kind of method of electrocatalytic nitrogen reduction catalyst - Google Patents
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Abstract
Description
技术领域technical field
本发明属于电催化产氨技术领域，尤其涉及一种电催化氮还原催化剂的方法。The invention belongs to the technical field of electrocatalytic ammonia production, and in particular relates to an electrocatalytic nitrogen reduction catalyst method.
背景技术Background technique
合成氨历来是最重要的工业过程之一，其产品氨既是一种用途广泛的工业产品，又是一种理想的清洁能源载体。传统的合成氨采用Haber-Bosch法通过高温高压等极端的苛刻条件促使高纯氢气和氮气反应生成氨气。该工艺耗能高，且排放大量温室气体。不利于现在绿色可持续发展战略举措。Ammonia synthesis has always been one of the most important industrial processes, and its product ammonia is not only a widely used industrial product, but also an ideal clean energy carrier. The traditional synthesis of ammonia uses the Haber-Bosch method to promote the reaction of high-purity hydrogen and nitrogen to form ammonia through extreme conditions such as high temperature and high pressure. The process is energy-intensive and emits large amounts of greenhouse gases. It is not conducive to the current green and sustainable development strategy.
因此，开发绿色可持续的替代方案尤为重要。目前产氨的方法有光催化氮还原，电催化氮还原，固氮酶催化。在这些方法中，电催化氮还原可在温和条件下实现高效率、低能耗、零排放合成氨，近年来受到广泛关注。Therefore, it is particularly important to develop green and sustainable alternatives. The current methods of producing ammonia include photocatalytic nitrogen reduction, electrocatalytic nitrogen reduction, and nitrogenase catalysis. Among these methods, electrocatalytic nitrogen reduction can achieve high-efficiency, low-energy consumption, and zero-emission ammonia synthesis under mild conditions, and has attracted extensive attention in recent years.
目前设计了各种电催化剂，如合金(PdCu，Angew.Chem.Int.Ed.，2019DOI:10.1002/anie.201913122)，硫化物(MoS2，Adv.Energy Mater.2019，9，1803935，Fe3S4，Chem.Commun.2018，54，13010-13013)，氧化物(CeO2，Chem.Commun.2019，55，2952-2955，BiVO4，Small Methods 2018，3，1800333)，磷化物(CoP，Small Methods 2018，2，1800204)，氮化物(W2N3，Adv.Mater.2019，31，1902709，Mo2N，ACS Energy Lett.2019，4，1053-1054)，单原子催化剂(FeSA-N-C，Nat.Commun.2019，10，341)等等。但是，催化效果主要集中在高电压下，造成的严重的电能耗损。因此如何解决高电位问题，实现在低电位下高产氨量是电化学氮还原的一大重要挑战。Various electrocatalysts have been designed, such as alloys (PdCu, Angew.Chem.Int.Ed., 2019DOI:10.1002/anie.201913122), sulfides (MoS 2 , Adv.Energy Mater.2019, 9, 1803935, Fe 3 S 4 , Chem.Commun.2018, 54, 13010-13013), oxides (CeO 2 , Chem.Commun.2019, 55, 2952-2955, BiVO 4 ,
在氮还原中难以实现低电压下高产氨量的原因主要体现在一方面较低的氮气溶解度严重限制了其传质过程，一方面强烈的析氢竞争反应使其选择性和活性在低电位下非常低，另一方面氮还原中氮气加氢还原要克服的能垒高，速度慢。因此设计发展一种新的催化剂来促进氮气吸附，抑制竞争反应，降低加氢能垒，实现低电压下高产氨量显得尤为重要。The reason why it is difficult to achieve high ammonia production at low voltage in nitrogen reduction is mainly reflected in the fact that on the one hand, the low solubility of nitrogen severely limits its mass transfer process, and on the other hand, the strong hydrogen evolution competition reaction makes its selectivity and activity extremely low at low potential. On the other hand, in nitrogen reduction, the energy barrier to be overcome by nitrogen hydrogenation reduction is high and the speed is slow. Therefore, it is particularly important to design and develop a new catalyst to promote nitrogen adsorption, inhibit competing reactions, lower the hydrogenation energy barrier, and achieve high ammonia production at low voltage.
碲化物纳米材料在日益蓬勃发展的无机功能材料和器件中扮演着重要角色。这些材料具有较好的光学，电学及催化等性质，可广泛应用于重要的研究和生产领域。但是作为一种极具应用前景的催化剂，在氮还原产氨方面的贡献尚未被研究。Telluride nanomaterials play an important role in the increasingly vigorous development of inorganic functional materials and devices. These materials have good optical, electrical and catalytic properties, and can be widely used in important research and production fields. However, as a promising catalyst, its contribution in nitrogen reduction to ammonia has not been investigated.
综上所述，现有技术存在的问题是：In summary, the problems in the prior art are:
(1)现有技术中，大多数催化剂难以在较低电压下实现高产氨量。(1) In the prior art, it is difficult for most catalysts to achieve high ammonia production at low voltage.
(2)现阶段一些催化剂能实现低电压下产氨，但是都是贵金属，价格昂贵，储量稀少，在工业生产中具有一定局限性。(2) At present, some catalysts can produce ammonia under low voltage, but they are all precious metals, which are expensive and have scarce reserves, which have certain limitations in industrial production.
(3)碲化物纳米材料在日益蓬勃发展的无机功能材料和器件中扮演着重要角色。这些材料具有较好的光学，电学及催化等性质，可广泛应用于重要的研究和生产领域。但是作为一种极具应用前景的催化剂，在氮还原产氨方面的贡献尚未被研究。(3) Telluride nanomaterials play an important role in the increasingly vigorous development of inorganic functional materials and devices. These materials have good optical, electrical and catalytic properties, and can be widely used in important research and production fields. However, as a promising catalyst, its contribution in nitrogen reduction to ammonia has not been studied.
解决上述技术问题的难度：The difficulty of solving the above technical problems:
(1)Haber-Bosch法通过高温高压等极端的苛刻条件促使高纯氢气和氮气反应生成氨气。该工艺耗能高，且排放大量温室气体。不利于现在绿色可持续发展战略举措。因此寻找一种绿色安全高效的方法来取代传统的Haber-Bosch法，显得尤为重要。(1) The Haber-Bosch method promotes the reaction of high-purity hydrogen and nitrogen to generate ammonia through extreme harsh conditions such as high temperature and high pressure. The process is energy-intensive and emits large amounts of greenhouse gases. It is not conducive to the current green and sustainable development strategy. Therefore, it is particularly important to find a green, safe and efficient method to replace the traditional Haber-Bosch method.
(2)由于氮气溶解度小，强烈的析氢竞争反应以及氮还原中氮气加氢还原要克服的能垒高，速度慢导致现在的催化剂催化效果主要集中在高电压下，因此设计一种催化剂增大氮气吸附，抑制析氢，加快还原，在低电压下实现高产氨量非常重要。(2) Due to the low solubility of nitrogen, the strong hydrogen evolution competition reaction and the high energy barrier to be overcome in the hydrogenation reduction of nitrogen reduction, the speed is slow, so the catalytic effect of the current catalyst is mainly concentrated at high voltage, so a catalyst is designed to increase Nitrogen adsorption, inhibition of hydrogen evolution, accelerated reduction, and high ammonia production at low voltage are very important.
(3)在众多催化剂中，设计一种非贵金属催化剂在低电压下实现高产氨量来解决贵金属储量少价格昂贵等问题显得非常有意义。(3) Among many catalysts, it is very meaningful to design a non-precious metal catalyst to achieve high ammonia production at low voltage to solve the problem of low precious metal reserves and high price.
(4)在众多催化剂中，碲化物纳米材料具有较好的光学，电学及催化等性质，可广泛应用于重要的研究和生产领域。但是作为一种极具应用前景的催化剂，在氮还原产氨方面的贡献尚未被研究。(4) Among many catalysts, telluride nanomaterials have good optical, electrical and catalytic properties, and can be widely used in important research and production fields. However, as a promising catalyst, its contribution in nitrogen reduction to ammonia has not been investigated.
解决上述技术问题的意义：The significance of solving the above technical problems:
(1)本发明中所用的常温下电催化氮还原绿色，高效，环境友好，可以更好地迎合国家提出的绿色环保以及节能减排的方针政策。(1) The electrocatalytic nitrogen reduction at room temperature used in the present invention is green, efficient, and environmentally friendly, and can better meet the national policies of green environmental protection, energy saving and emission reduction.
(2)本发明在低电压下实现高产氨量可以有效降低电能消耗，利用更少的电能实现大量产氨。(2) The present invention realizes high ammonia production under low voltage, can effectively reduce electric energy consumption, and utilizes less electric energy to realize large amount of ammonia production.
(3)本发明使用非贵金属催化剂，相比较贵金属催化剂其价格低廉，储量丰富，在工业生产方面具有更大的优势。(3) The present invention uses non-noble metal catalysts, which are cheaper and more abundant than noble metal catalysts, and have greater advantages in industrial production.
(4)本发明所调研的碲化物在0V下具有很高的产氨量，开启了碲化物在氮还原产氨中的应用，同时还为其他电催化氮还原催化剂的设计提供新思路。(4) The telluride investigated in this invention has a high ammonia yield at 0V, which opens up the application of telluride in the nitrogen reduction ammonia production, and also provides new ideas for the design of other electrocatalytic nitrogen reduction catalysts.
发明内容Contents of the invention
针对现有技术存在的问题，本发明选用对氮气具有较强吸附的元素(Co，Bi，Cd，Sb)，借助碲化物具有储氢性质，将碲化物引入电催化氮还原。提供了一种新的非贵金属电催化氮还原催化剂。该催化剂可以在0V下实现较高的产氨量。Aiming at the problems existing in the prior art, the present invention selects elements (Co, Bi, Cd, Sb) with strong adsorption to nitrogen, and introduces the telluride into the electrocatalytic nitrogen reduction with the help of the telluride having hydrogen storage properties. A new non-noble metal electrocatalytic nitrogen reduction catalyst is provided. The catalyst can achieve higher ammonia production at 0V.
本发明是这样实现的，一种电催化氮还原催化剂的方法，包括：其中将碲化物引入电催化氮还原。选用对氮气具有良好吸附作用元素(Co，Bi，Cd，Sb)，以及借助碲化物具有储氢性质在0V实现了较高的产氨量。The present invention is realized as follows, a method of electrocatalyzing nitrogen reduction catalyst, comprising: wherein tellurides are introduced into electrocatalytic nitrogen reduction. The selection of elements (Co, Bi, Cd, Sb) with good adsorption to nitrogen, and the use of tellurides with hydrogen storage properties achieve a higher ammonia production at 0V.
进一步，碲化物包括：Sb2Te3、Bi3Te4、CoTe2及CdTe。Further, tellurides include: Sb 2 Te 3 , Bi 3 Te 4 , CoTe 2 and CdTe.
进一步，Sb2Te3的合成方法包括：采用4mg SbCl3溶于7.5mL水中，后依次加入25mg酒石酸钠，25mL氨水，22mg亚碲酸钾，10mL肼搅拌5min后装入反应釜于180℃下反应5h。Further, the synthesis method of Sb 2 Te 3 includes: dissolving 4 mg of SbCl 3 in 7.5 mL of water, then adding 25 mg of sodium tartrate, 25 mL of ammonia water, 22 mg of potassium tellurite, and 10 mL of hydrazine, stirring for 5 minutes, and then putting it into a reaction vessel at 180°C Reaction 5h.
进一步，Sb2Te3为六边纳米片。Further, Sb 2 Te 3 is a hexagonal nanosheet.
进一步，Bi3Te4合成方法包括：0.243g Bi(NO3)3·5H2O溶于25mL去离子水中；搅拌一小时后，加入0.126g K2TeO3，再继续搅拌10分钟；再加入0.5g抗坏血酸，0.5g聚乙烯吡咯烷酮，和15mL乙二醇；将获得的均匀分散的悬浊液放入反应釜中200℃下维持24h后取出离心，水乙醇洗涤真空干燥。Further, the synthesis method of Bi 3 Te 4 includes: dissolving 0.243g Bi(NO 3 ) 3 ·5H 2 O in 25mL deionized water; after stirring for one hour, adding 0.126g K 2 TeO 3 , and continuing stirring for 10 minutes; adding 0.5g ascorbic acid, 0.5g polyvinylpyrrolidone, and 15mL ethylene glycol; put the obtained uniformly dispersed suspension into a reaction kettle at 200°C for 24 hours, take it out and centrifuge, wash with water and ethanol, and dry in vacuum.
进一步，Bi3Te4为纳米针。Further, Bi 3 Te 4 is a nanoneedle.
进一步，CoTe2合成方法包括：0.15g Co(NO3)2·6H2O溶于15mL去离子水中；搅拌一小时后，加入0.126g K2TeO3，再继续搅拌10分钟；再加入1g抗坏血酸，和15mL乙二醇。将获得的均匀分散的悬浊液放入反应釜中200℃下维持12h，后取出离心，水乙醇洗涤真空干燥。Further, the synthesis method of CoTe 2 includes: dissolving 0.15g Co(NO 3 ) 2 ·6H 2 O in 15mL deionized water; after stirring for one hour, adding 0.126g K 2 TeO 3 , and continuing to stir for 10 minutes; then adding 1g of ascorbic acid , and 15 mL of ethylene glycol. The obtained uniformly dispersed suspension was put into a reaction kettle at 200° C. for 12 hours, then taken out, centrifuged, washed with water and ethanol, and dried in vacuum.
进一步，CoTe2为梭形纳米棒。Further, CoTe 2 is a spindle-shaped nanorod.
进一步，CdTe合成方法包括：0.159g Cd(NO3)3·5H2O搅拌一小时后，加入0.126gK2TeO3，再继续搅拌10分钟；再加入0.5g抗坏血酸，0.5g聚乙烯吡咯烷酮，和15mL乙二醇；将获得的均匀分散的溶液放入反应釜中200℃下维持24h；取出离心，水乙醇洗涤真空干燥。Further, the synthesis method of CdTe includes: after stirring 0.159g Cd(NO 3 ) 3 5H 2 O for one hour, adding 0.126g K 2 TeO 3 , and continuing to stir for 10 minutes; then adding 0.5g ascorbic acid, 0.5g polyvinylpyrrolidone, and 15mL of ethylene glycol; put the obtained uniformly dispersed solution into a reaction kettle at 200°C for 24 hours; take it out and centrifuge, wash with water and ethanol and dry in vacuum.
进一步，CdTe为纳米棒。Further, CdTe is a nanorod.
进一步，Sb合成方法包括：将20mg Sb放入研钵研磨成粉，放入异丙醇中在氩气气氛中超声8小时后离心，用乙醇洗涤三次，60℃过夜干燥。Further, the Sb synthesis method includes: putting 20 mg of Sb into a mortar, grinding it into powder, putting it into isopropanol, ultrasonicating for 8 hours in an argon atmosphere, centrifuging, washing with ethanol three times, and drying at 60° C. overnight.
综上所述，本发明的优点及积极效果为：碲化物(Sb2Te3、Bi3Te4、CoTe2及CdTe)可以在低电压下实现较好的产氨量，其中以Sb2Te3在0V(相对于RHE)产氨效果最好(图23)。而且随着电压继续增大，产氨量在-0.2V(相对于RHE)可达最高(图13)。对比Sb发现碲化物在氮还原中具有较好的催化效应(图21)。为了排除其他污染源的影响，一些同位素实验，对比实验同样证明Sb2Te3的高产氨效果。与目前报道的催化剂比其产氨具有极大优势(表1)，开启了碲化物在氮还原产氨中的应用。通过对其催化过程进行理论模拟研究(图24-图29)，得出存在一种协同的双原子位点。以Sb2Te3为例，Sb位点上吸附氮气，Te位点吸附H*。二者之间不仅存在一种协同作用可以促进Sb对氮气的吸附，同时Te上吸附的H*还可以在还原过程中抑制竞争反应，快速的转移到N上实现还原。这为其他电催化氮还原催化剂的设计提供新思路。本发明以Sb2Te3为例，对比单纯的Sb产氨能力发现碲化物在低电压下的氮还原中具有很大的前景。In summary, the advantages and positive effects of the present invention are: tellurides (Sb 2 Te 3 , Bi 3 Te 4 , CoTe 2 and CdTe) can achieve better ammonia production at low voltage, among which Sb 2 Te 3 produced the best ammonia at 0V (relative to RHE) (Figure 23). And as the voltage continues to increase, the ammonia production can reach the highest at -0.2V (relative to RHE) (Figure 13). Compared with Sb, it is found that telluride has a better catalytic effect in nitrogen reduction (Figure 21). In order to exclude the influence of other pollution sources, some isotope experiments and comparative experiments also proved the high ammonia production effect of Sb 2 Te 3 . Compared with the currently reported catalysts, it has great advantages in ammonia production (Table 1), which opens the application of telluride in nitrogen reduction for ammonia production. Through the theoretical simulation study of its catalytic process (Figure 24-Figure 29), it is concluded that there is a cooperative diatomic site. Taking Sb 2 Te 3 as an example, nitrogen gas is adsorbed on the Sb site, and H* is adsorbed on the Te site. There is not only a synergistic effect between the two that can promote the adsorption of nitrogen by Sb, but also the H* adsorbed on Te can inhibit the competitive reaction during the reduction process and quickly transfer to N to achieve reduction. This provides a new idea for the design of other electrocatalytic nitrogen reduction catalysts. The present invention takes Sb 2 Te 3 as an example, compares the ammonia-producing ability of pure Sb, and finds that telluride has great prospects in nitrogen reduction at low voltage.
附图说明Description of drawings
图1是本发明实施例提供的Sb2Te3合成流程图。Fig. 1 is a flow chart of the synthesis of Sb 2 Te 3 provided by the embodiment of the present invention.
图2是本发明实施例提供的Sb合成流程图。Fig. 2 is a flow chart of Sb synthesis provided by the embodiment of the present invention.
图3是本发明实施例提供的Bi3Te4合成流程图。Fig. 3 is a flow chart of the synthesis of Bi 3 Te 4 provided by the embodiment of the present invention.
图4是本发明实施例提供的CoTe2合成流程图。Fig. 4 is a flowchart of the synthesis of CoTe 2 provided by the embodiment of the present invention.
图5是本发明实施例提供的CdTe合成流程图。Fig. 5 is a flow chart of CdTe synthesis provided by the embodiment of the present invention.
图6为Sb2Te3化合物的XRD图Figure 6 is the XRD pattern of Sb 2 Te 3 compound
图7为Sb2Te3化合物的扫描电镜图(a)和透射电镜图(b)。Fig. 7 is a scanning electron micrograph (a) and a transmission electron micrograph (b) of the Sb 2 Te 3 compound.
图8为Bi3Te4化合物的XRD图(a)和透射电镜图(b)。Figure 8 is the XRD pattern (a) and transmission electron microscope pattern (b) of the Bi 3 Te 4 compound.
图9为CdTe化合物的XRD图(a)和透射电镜图(b)。Figure 9 is the XRD pattern (a) and transmission electron microscope pattern (b) of the CdTe compound.
图10为CoTe2化合物的XRD图(a)和透射电镜图(b)。Figure 10 is the XRD pattern (a) and transmission electron microscope pattern (b) of the CoTe 2 compound.
图11为Sb的XRD图(a)和透射电镜图(b)。Figure 11 is the XRD pattern (a) and transmission electron microscope pattern (b) of Sb.
图12为在室温下静置2小时后，一系列NH4 +浓度的UV-Vis吸收光谱(a)。和相关的计算NH4 +浓度的校准曲线(b)。Fig. 12 is the UV-Vis absorption spectrum (a) of a series of NH 4 + concentrations after standing at room temperature for 2 hours. and the associated calibration curve (b) for calculating the NH 4 + concentration.
图13为本发明实施例提供的Sb2Te3的电催化氮还原性质测试图：不同电压下时间-电流曲线(a)，不同电压下紫外可见光吸收谱图(b)，不同电压下的产氨量(c)，Sb2Te3和CP的产氨对比图(d)。Figure 13 is a test diagram of the electrocatalytic nitrogen reduction properties of Sb 2 Te 3 provided by the embodiment of the present invention: time-current curves (a) at different voltages, ultraviolet-visible light absorption spectra (b) at different voltages, and output at different voltages Ammonia amount (c), comparison of ammonia production between Sb 2 Te 3 and CP (d).
图14为一系列NH4 +离子浓度的离子色谱图(a)和用于计算NH4Cl浓度的校准曲线(b)。Figure 14 is a series of ion chromatograms of NH 4 + ion concentrations (a) and a calibration curve (b) used to calculate the concentration of NH 4 Cl.
图15为电解质中NH4 +离子的离子色谱图(a)和通过吲哚酚蓝法和离子色谱法检测到0V(相对于RHE)下Sb2Te3/CP的NH3收率图(b)。Figure 15 is the ion chromatogram (a) of NH 4 + ions in the electrolyte and the NH 3 yield diagram (b) of Sb 2 Te 3 /CP at 0V (relative to RHE) detected by indoxyl blue method and ion chromatography ).
图16为在室温下静置2小时后，一系列N2H4浓度的UV-Vis吸收光谱图(a)。和相关的计算N2H4浓度的校准曲线图(b)。Fig. 16 is a UV-Vis absorption spectrum diagram (a) of a series of N 2 H 4 concentrations after standing at room temperature for 2 hours. and the associated calibration curve plot (b ) for calculating the N2H4 concentration.
图17为电解液在0V(相对于RHE)进行电解前后的UV-Vis光谱图。Fig. 17 is a UV-Vis spectrum diagram before and after electrolysis of the electrolyte at 0V (relative to RHE).
图18为在开路电位下进行电解后的和在电解之前的电解液的UV-Vis光谱图。Fig. 18 is a UV-Vis spectrum diagram of the electrolyte solution after electrolysis and before electrolysis at open circuit potential.
图19在N2和Ar气氛中，Sb2Te3/CP在0V(相对于RHE)电位下的NH3产率图。Fig. 19 is a diagram of the NH 3 yield of Sb 2 Te 3 /CP at a potential of 0 V (vs. RHE) in N 2 and Ar atmospheres.
图20为在-0.2V(相对于RHE)下在14N2饱和条件下进行电解的电解质的1H-NMR谱图(a)和在-0.2V(相对于RHE)下在15N2饱和条件下电解的电解质的1H-NMR谱图(b)。Figure 20 is the 1 H-NMR spectrum (a) of the electrolyte electrolyzed under 14 N 2 saturation at -0.2 V (relative to RHE) and saturated in 15 N 2 at -0.2 V (relative to RHE). The 1 H-NMR spectrum (b) of the electrolyte electrolyzed under the conditions.
图21是本发明实施例提供的Sb2Te3和Sb的电催化氮还原性质测试图：极化曲线(a)，紫外可见光吸收谱图(b)，在-0.2V(相对于RHE)下的产氨量(c)，0V(相对于RHE)下的产氨对比图(d)，Sb2Te3在0V(相对于RHE)下循环产氨图(e)，Sb2Te3在0V(相对于RHE)下50个小时时间电流曲线图(f)。Figure 21 is a test diagram of the electrocatalytic nitrogen reduction properties of Sb 2 Te 3 and Sb provided by the embodiment of the present invention: polarization curve (a), ultraviolet-visible light absorption spectrum (b), at -0.2V (relative to RHE) Ammonia production at 0V (relative to RHE) (c), comparison chart of ammonia production at 0V (relative to RHE) (d), cycle ammonia production chart of Sb 2 Te 3 at 0V (relative to RHE) (e), Sb 2 Te 3 at 0V (relative to RHE) time-current curves (f) for 50 hours.
图22是本发明实施例提供的N2程序升温脱附测量图。所得Sb2Te3和Sb的N2程序升温脱附测量图。Fig. 22 is a N 2 temperature programmed desorption measurement diagram provided by an embodiment of the present invention. The resulting N2 temperature - programmed desorption measurements of Sb2Te3 and Sb.
图23是本发明实施例提供的CoTe2，Bi3Te4，CdTe在0V(相对于RHE)下紫外可见光吸收谱图(a)和CoTe2，Bi3Te4，CdTe在0V(相对于RHE)下的产氨量图(b)。Figure 23 is the UV-visible absorption spectrum (a) of CoTe 2 , Bi 3 Te 4 , CdTe at 0V (relative to RHE) and CoTe 2 , Bi 3 Te 4 , CdTe at 0V (relative to RHE) provided by the embodiment of the present invention ) Ammonia production diagram (b) under.
图24是吸附在催化剂上的N2的电荷差图：Sb(a)和Sb2Te3(b)。Figure 24 is a charge difference diagram of N2 adsorbed on catalyst: Sb (a) and Sb2Te3 (b).
图25是催化剂的DOS图：Sb2Te3总图(a)和Sb2Te3拆分图(b)。Figure 25 is the DOS diagram of the catalyst: the general diagram of Sb 2 Te 3 (a) and the split diagram of Sb 2 Te 3 (b).
图26是在表面氢化的Sb2Te3进行的N2吸附(a)和*NNH(b)图。Figure 26 is a graph of N 2 adsorption (a) and *NNH (b) on surface hydrogenated Sb 2 Te 3 .
图27是本发明实施例提供的Sb2Te3吸附氢计算图。Fig. 27 is a calculation diagram of hydrogen adsorption by Sb 2 Te 3 provided by an example of the present invention.
图28是本发明实施例提供的Sb2Te3-H*和Sb的氮还原加氢自由能计算图。Fig. 28 is a diagram for calculating the free energy of nitrogen reduction and hydrogenation of Sb 2 Te 3 -H* and Sb provided by the examples of the present invention.
图29是本发明实施例提供的Sb2Te3双原子位点助力电催化NH3还原的方法的机理示意图。Fig. 29 is a schematic diagram of the mechanism of the Sb 2 Te 3 diatomic site-assisted electrocatalytic NH 3 reduction method provided by the embodiment of the present invention.
表1为现阶段报道低电压下催化剂的催化性能。如表所示，碲化物在低电压下催化氮气还原具有较好的前景。Table 1 is the catalytic performance of the catalysts reported at this stage under low voltage. As shown in the table, tellurides are promising for catalyzing nitrogen reduction at low voltages.
具体实施方式detailed description
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the object, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the examples. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.
现有技术中没有利用碲化物具引入电催化氮还原，不能对氮气良好吸附，以及不能借助碲化物具有储氢的性质，造成在0V不能实现较高的产氨量。In the prior art, tellurides are not used to introduce electrocatalytic nitrogen reduction, can not absorb nitrogen well, and cannot use tellurides to have the property of hydrogen storage, resulting in the inability to achieve high ammonia production at 0V.
针对现有技术存在的问题，本发明提供了一种电催化氮还原催化剂的方法，下面结合附图对本发明作详细的描述。Aiming at the problems existing in the prior art, the present invention provides a method for electrocatalyzing a nitrogen reduction catalyst. The present invention will be described in detail below with reference to the accompanying drawings.
本发明实施例提供的电催化氮还原催化剂的方法，包括：利用碲化物具有储氢能力，将碲化物引入电催化氮还原，其中选用对氮气具有良好吸附作用的元素，以及借助碲化物具有储氢性质，在0V实现了较高的产氨量。发现碲化物在氮还原中具有很大的前景。The method of the electrocatalytic nitrogen reduction catalyst provided by the embodiment of the present invention includes: utilizing the hydrogen storage capacity of the telluride, introducing the telluride into the electrocatalytic nitrogen reduction, wherein the element with good adsorption effect on nitrogen is selected, and the telluride has the hydrogen storage capacity Hydrogen properties, a higher ammonia production was achieved at 0V. Tellurides were found to hold great promise in nitrogen reduction.
如图1是Sb2Te3的合成步骤流程图，具体为采用4mg SbCl3溶于7.5mL水中，后依次加入25mg酒石酸钠，25mL氨水，22mg亚碲酸钾，10mL肼搅拌5min后装入反应釜于180℃下反应5h。Figure 1 is a flow chart of the synthesis steps of Sb 2 Te 3 , specifically, 4 mg of SbCl 3 was dissolved in 7.5 mL of water, and then 25 mg of sodium tartrate, 25 mL of ammonia water, 22 mg of potassium tellurite, and 10 mL of hydrazine were added to the reaction after being stirred for 5 minutes. The kettle was reacted at 180°C for 5h.
图2是Sb合成步骤流程图，具体为20mg Sb放入研钵研磨成粉，后放入异丙醇中在氩气气氛中超声8小时后离心，用乙醇洗涤三次，60℃过夜干燥。Figure 2 is a flowchart of the synthesis steps of Sb. Specifically, 20 mg of Sb was put into a mortar and ground into powder, then put into isopropanol, ultrasonicated in an argon atmosphere for 8 hours, centrifuged, washed with ethanol three times, and dried overnight at 60°C.
图3是Bi3Te4合成步骤流程图，具体为0.243g Bi(NO3)3·5H2O溶于25mL去离子水中。搅拌一个小时后，加入0.126g K2TeO3，再继续搅拌10分钟。后加入0.5g抗坏血酸，0.5g聚乙烯吡咯烷酮，和15mL乙二醇。将获得的均匀分散的悬浊液放入反应釜中200℃下维持24h后取出离心，水乙醇洗涤真空干燥。Fig. 3 is a flowchart of the synthesis steps of Bi 3 Te 4 , specifically, 0.243g of Bi(NO 3 ) 3 ·5H 2 O is dissolved in 25mL of deionized water. After stirring for one hour, 0.126 g of K 2 TeO 3 was added and stirring was continued for another 10 minutes. Then 0.5 g of ascorbic acid, 0.5 g of polyvinylpyrrolidone, and 15 mL of ethylene glycol were added. The obtained uniformly dispersed suspension was put into a reaction kettle at 200° C. for 24 hours, then taken out and centrifuged, washed with water and ethanol, and dried in vacuum.
图4是CoTe2合成步骤流程图，具体为0.15g Co(NO3)2·6H2O溶于15mL去离子水中。搅拌一个小时后，加入0.126g K2TeO3，再继续搅拌10分钟。后加入1g抗坏血酸，和15mL乙二醇。将获得的均匀分散的悬浊液放入反应釜中200℃下维持12h.后取出离心，水乙醇洗涤真空干燥。Fig. 4 is a flowchart of the synthesis steps of CoTe 2 , specifically, 0.15g of Co(NO 3 ) 2 ·6H 2 O is dissolved in 15mL of deionized water. After stirring for one hour, 0.126 g of K 2 TeO 3 was added and stirring was continued for another 10 minutes. Then add 1 g of ascorbic acid, and 15 mL of ethylene glycol. Put the obtained homogeneously dispersed suspension into a reaction kettle at 200° C. for 12 hours. After that, take it out and centrifuge, wash with water and ethanol, and dry in vacuum.
图5是CdTe合成步骤流程图，具体为0.159g Cd(NO3)3·5H2O搅拌一个小时后，加入0.126g K2TeO3，再继续搅拌10分钟。后加入0.5g抗坏血酸，0.5g聚乙烯吡咯烷酮，和15mL乙二醇。将获得的均匀分散的溶液放入反应釜中200℃下维持24h.后取出离心，水乙醇洗涤真空干燥。Fig. 5 is a flowchart of CdTe synthesis steps, specifically, 0.159g Cd(NO 3 ) 3 ·5H 2 O was stirred for one hour, then 0.126g K 2 TeO 3 was added, and stirring was continued for 10 minutes. Then 0.5 g of ascorbic acid, 0.5 g of polyvinylpyrrolidone, and 15 mL of ethylene glycol were added. The obtained uniformly dispersed solution was put into a reaction kettle at 200° C. for 24 hours. After that, it was taken out and centrifuged, washed with water and ethanol, and dried in vacuum.
图6为Sb2Te3化合物的XRD图Figure 6 is the XRD pattern of Sb 2 Te 3 compound
图7为Sb2Te3化合物的扫描电镜图(a)和透射电镜图(b)。如图所示得到的Sb2Te3是六边纳米片。Fig. 7 is a scanning electron micrograph (a) and a transmission electron micrograph (b) of the Sb 2 Te 3 compound. The obtained Sb 2 Te 3 is hexagonal nanosheets as shown in the figure.
图8为Bi3Te4化合物的XRD图(a)和透射电镜图(b)。如图所示Bi3Te4成功制备得到。Figure 8 is the XRD pattern (a) and transmission electron microscope pattern (b) of the Bi 3 Te 4 compound. As shown in the figure, Bi 3 Te 4 was successfully prepared.
图9为CdTe化合物的XRD图(a)和透射电镜图(b)。如图所示CdTe成功制备得到。Figure 9 is the XRD pattern (a) and transmission electron microscope pattern (b) of the CdTe compound. As shown in the figure, CdTe was successfully prepared.
图10为CoTe2化合物的XRD图(a)和透射电镜图(b)。如图所示CoTe2成功制备得到。Figure 10 is the XRD pattern (a) and transmission electron microscope pattern (b) of the CoTe 2 compound. As shown in the figure, CoTe 2 was successfully prepared.
图11为Sb的XRD图(a)和透射电镜图(b)。如图所示得到了Sb纳米片。Figure 11 is the XRD pattern (a) and transmission electron microscope pattern (b) of Sb. Sb nanosheets were obtained as shown in the figure.
在CHI760工作站(中国上海晨华仪器有限公司)上进行了电化学测量。采用三电极***，使用一个用盐桥连接的两个电解池。为了制备工作电极，将含有5mg催化剂，0.9mL乙醇和0.1mL 5wt％Nafion的溶液超声处理30分钟以上，以形成均匀的墨水。然后在催化剂载量为0.2mg cm-2的情况下，将40μL准备好的墨水滴到碳纸(1cm2)上。在进行电化学测试之前，将所用的电池，电极用去离子水彻底冲洗3次以上，并将气体(纯度为99.999％，气速40sccm)通入0.1M KOH中超过30分钟。在CV曲线稳定后进行电化学测试，对极化曲线(扫描速率为5mV s-1)进行iR校正，并在搅拌(450rpm)下进行计时电流法测试。Electrochemical measurements were performed on a CHI760 workstation (Shanghai Chenhua Instrument Co., Ltd., China). A three-electrode system is employed, using two electrolytic cells connected by a salt bridge. To prepare the working electrode, a solution containing 5 mg of catalyst, 0.9 mL of ethanol, and 0.1 mL of 5 wt% Nafion was sonicated for more than 30 min to form a uniform ink. Then 40 μL of the prepared ink was dropped onto carbon paper (1 cm 2 ) with a catalyst loading of 0.2 mg cm −2 . Before the electrochemical test, the used cells and electrodes were thoroughly rinsed with deionized water for more than 3 times, and gas (purity 99.999%,
下面结合附图对本发明的技术效果作详细的描述。The technical effects of the present invention will be described in detail below in conjunction with the accompanying drawings.
图12为在室温下静置2小时后，一系列NH4 +浓度的UV-Vis吸收光谱(a)。和相关的计算NH4 +浓度的校准曲线图(b)。由此图可以计算产氨量。Fig. 12 is the UV-Vis absorption spectrum (a) of a series of NH 4 + concentrations after standing at room temperature for 2 hours. and the associated calibration curve for calculating the NH 4 + concentration (b). Ammonia production can be calculated from this figure.
图13为Sb2Te3的电催化氮还原性质测试图：不同电压下时间-电流曲线(a)，不同电压下紫外可见光吸收谱图(b)，不同电压下的产氨量(c)，Sb2Te3和CP的产氨对比图(d)。由图所知，图a显示了具有不同电势的i-t曲线。电解后，NH3的相应的紫外可见光吸收光谱(U-vis)显示在图b中。发现Sb2Te3在低过电势下表现出出色的NRR性能，N2还原能力始于0.1V(vs.RHE)，但NH3收率低。而NH3的产率和FE在0V时分别达到34.6μg h-1mg-1和27.7％(vs.RHE)(图c)，优于许多NRR电催化剂(表1)。而且在-0.2V时可达到最大。但是，由于施加的电势不断增加，FE和NH3的产率下降。FE和NH3收率的这种降低可归因于反应的HER，导致较低的FE和较低的速率将N2还原为NH3。从图d可以看出，Sb2Te3/CP的NH3产率比CP大，这表明检测到的NH3源自Sb2Te3的优异性能。Figure 13 is the test diagram of electrocatalytic nitrogen reduction properties of Sb 2 Te 3 : time-current curves at different voltages (a), UV-visible light absorption spectra at different voltages (b), ammonia production at different voltages (c), Comparison of ammonia production between Sb 2 Te 3 and CP (d). From the figure, panel a shows it curves with different potentials. After electrolysis, the corresponding ultraviolet-visible absorption spectrum (U-vis) of NH3 is shown in panel b. It is found that Sb 2 Te 3 exhibits excellent NRR performance at low overpotential, N 2 reducing ability starts at 0.1 V (vs. RHE), but NH 3 yield is low. While the yield of NH 3 and FE reached 34.6 μg h −1 mg −1 and 27.7% (vs. RHE) at 0 V, respectively (Fig. c), better than many NRR electrocatalysts (Table 1). And it can reach the maximum at -0.2V. However, the yields of FE and NH3 decreased due to the increasing applied potential. This decrease in FE and NH3 yields can be attributed to the HER of the reaction, resulting in lower FE and lower rate of reduction of N2 to NH3 . From panel d, it can be seen that the NH yield of Sb 2 Te 3 /CP is larger than that of CP, which indicates that the detected NH 3 originates from the excellent performance of Sb 2 Te 3 .
图14为一系列NH4 +离子的离子色谱图(a)和用于计算NH4Cl浓度的校准曲线(b)。可以进一步准确检测以及计算产生的氨。Figure 14 is a series of ion chromatograms of NH 4 + ions (a) and a calibration curve (b) used to calculate the concentration of NH 4 Cl. The ammonia produced can be further accurately detected and calculated.
图15为电解质中NH4 +离子的离子色谱图(a)和通过吲哚酚蓝法和离子色谱法检测到0V(vs。RHE)下Sb2Te3/CP的NH3收率图(b)。由图所知在0V(相对于RHE)时，离子色谱检测到的NH3产率与吲哚酚蓝法测定的结果相近，进一步证明实验测定的准确性。Figure 15 is the ion chromatogram (a) of NH 4 + ions in the electrolyte and the NH 3 yield diagram of Sb 2 Te 3 /CP under 0V (vs. RHE) detected by indoxyl blue method and ion chromatography (b ). As known from the figure, when 0V (relative to RHE), the NH3 productive rate detected by ion chromatography is close to the result determined by the indoxyl blue method, which further proves the accuracy of the experimental determination.
图16为在室温下静置2小时后，一系列N2H4浓度的UV-Vis吸收光谱图(a)。和相关的计算N2H4浓度的校准曲线图(b)。用于计算副产物N2H4的存在Fig. 16 is a UV-Vis absorption spectrum diagram (a) of a series of N 2 H 4 concentrations after standing at room temperature for 2 hours. and the associated calibration curve plot (b ) for calculating the N2H4 concentration. Used to calculate the presence of by - product N2H4
图17为电解液在0V进行电解前后的UV-Vis光谱图(相对于RHE)。由图所知，发现没有副产物N2H4产生，证明Sb2Te3具有较好的选择性Fig. 17 is the UV-Vis spectrogram (relative to RHE) of the electrolyte before and after electrolysis at 0V. As can be seen from the figure, it is found that no by-product N 2 H 4 is produced, which proves that Sb 2 Te 3 has better selectivity
图18为在开路电位下进行电解后的和在电解之前的电解液的UV-Vis光谱图。由图所知，没有氨的产生，去除了电解液里本身存在的污染源的影响，证明检测到的NH3产率完全来自与Sb2Te3的催化作用Fig. 18 is a UV-Vis spectrum diagram of the electrolyte solution after electrolysis and before electrolysis at open circuit potential. As can be seen from the figure, there is no ammonia production, and the influence of the pollution source in the electrolyte is removed, which proves that the detected NH 3 yield is entirely from the catalytic action with Sb 2 Te 3
图19在N2和Ar气氛中，Sb2Te3/CP在0V(相对于RHE)电位下的NH3产率图。由图所知，发现在Ar气氛下，没有氨的产生，去除了其他污染源的影响，证明溶液中产生的氨来源于氮气，进一步证明NH3产率完全来自与Sb2Te3的催化氮气还原作用Fig. 19 is a diagram of the NH 3 yield of Sb 2 Te 3 /CP at a potential of 0 V (vs. RHE) in N 2 and Ar atmospheres. As can be seen from the figure, it is found that under the Ar atmosphere, there is no ammonia production, and the influence of other pollution sources is removed, which proves that the ammonia produced in the solution comes from nitrogen, and further proves that the NH 3 yield is completely from the catalytic nitrogen reduction with Sb 2 Te 3 effect
图20为在-0.2V(相对于RHE)下在14N2饱和条件下进行电解的电解质的1H-NMR谱图(a)和在-0.2V(相对于RHE)下在15N2饱和条件下电解的电解质的1H-NMR谱图(b)。由图所知，15N2饱和条件下电解的电解质的1H-NMR谱图中有两个峰，不同于14N2饱和条件下进行电解的电解质的1H-NMR谱图，证明溶液中产生的氨来源于氮气，进一步去除其他影响，证明NH3产率完全来自与Sb2Te3的催化氮气还原作用Figure 20 is the 1 H-NMR spectrum (a) of the electrolyte electrolyzed under 14 N 2 saturation at -0.2 V (relative to RHE) and saturated in 15 N 2 at -0.2 V (relative to RHE). The 1 H-NMR spectrum (b) of the electrolyte electrolyzed under the conditions. It can be known from the figure that there are two peaks in the 1 H-NMR spectrum of the electrolyte electrolyzed under 15 N 2 saturated condition, which is different from the 1 H-NMR spectrum of the electrolyte electrolyzed under 14 N 2 saturated condition, which proves that in the solution The generated ammonia was derived from nitrogen, and other effects were further removed, proving that the NH3 yield was entirely from the catalytic nitrogen reduction with Sb2Te3
图21为Sb2Te3和Sb的电催化氮还原性质测试图：极化曲线(a)，紫外可见光吸收谱图(b)，-0.2V(相对于RHE)下的产氨量(c)，0V(相对于RHE)下的产氨对比图(d)，Sb2Te3在0V(相对于RHE)下的循环产氨图(e)，Sb2Te3在0V(相对于RHE)下50个小时时间-电流曲线图(f)。由图所知，在线性扫描伏安法(LSV)曲线图所示，在相同电势下Sb2Te3/CP的电流密度较高(图a)，表明Sb2Te3/CP的活性位点更多。在0.1M KOH中比Sb/CP有活性。同时，Sb/CP的NRR的U-vis吸收光谱，NH3产率和FE分别如图b-d所示。在0V(相对于RHE)和-0.2V(相对于RHE)下，Sb2Te3/CP的NH3产率比Sb/CP高，这意味着Sb2Te3在低过电位下可获得更高的NH3产率比Sb。由图e所知，循环6次氨产量基本保持不变，证明Sb2Te3具有较好的稳定性。图f，发现50小时后，电流密度基本保持不变，进一步证明其具有较高的稳定性。Figure 21 is the test diagram of electrocatalytic nitrogen reduction properties of Sb 2 Te 3 and Sb: polarization curve (a), UV-visible light absorption spectrum (b), ammonia production at -0.2V (relative to RHE) (c) , Comparison of ammonia production at 0V (relative to RHE) (d), cyclic ammonia production graph of Sb 2 Te 3 at 0V (relative to RHE) (e), Sb 2 Te 3 at 0V (relative to RHE) 50 hours time-current curve (f). As can be seen from the figure, as shown in the linear sweep voltammetry (LSV) curve, the current density of Sb 2 Te 3 /CP is higher at the same potential (figure a), indicating that the active site of Sb 2 Te 3 /CP More. It is more active than Sb/CP in 0.1M KOH. Meanwhile, the U-vis absorption spectra of NRR of Sb/CP, NH3 yield and FE are shown in Fig. bd, respectively. At 0 V (vs. RHE) and −0.2 V (vs. RHE), Sb 2 Te 3 /CP had a higher NH 3 yield than Sb/CP, which means that Sb 2 Te 3 can obtain
图22为N2程序升温脱附测量图。由图所知，Sb2Te3具有较强的N2化学吸附，证明碲化物中Te元素可以促进Sb的N2吸附。Fig. 22 is a graph showing N 2 temperature programmed desorption measurement. As can be seen from the figure, Sb 2 Te 3 has strong N 2 chemisorption, which proves that Te element in telluride can promote the N 2 adsorption of Sb.
图23是本发明实施例提供的CoTe2，Bi3Te4，CdTe在0V vs.RHE紫外可见光吸收谱图(a)和CoTe2，Bi3Te4，CdTe在0V vs.RHE的产氨量图(b)。.如图所示，CoTe，Bi3Te4，CdTe2均在0V(相对于RHE)下具有较好的NH3的产率，这表明碲化物在低电压下具有催化N2的发展潜力。Figure 23 is the ultraviolet-visible absorption spectrum (a) of CoTe 2 , Bi 3 Te 4 , CdTe at 0V vs. RHE and the ammonia production of CoTe 2 , Bi 3 Te 4 , CdTe at 0V vs. RHE provided by the examples of the present invention Figure (b). .As shown in the figure, CoTe, Bi 3 Te 4 , and CdTe 2 all have better yields of NH 3 at 0 V (relative to RHE), which indicates that tellurides have the potential to catalyze N 2 at low voltage.
图24是吸附在催化剂上的N2的电荷差图：Sb(a)和Sb2Te3(b)。由图所知，发现吸附在Sb2Te3上的N2的Eads约为-0.032eV，远低于Sb的Eads(-0.0084eV)。这表明在Sb2Te3和N2之间形成了更强的共价相互作用，表明N2在碲化物(Sb2Te3)的表面上比在Sb上更有效地被吸附和活化。这与TPD结果一致。Figure 24 is a charge difference diagram of N2 adsorbed on catalyst: Sb (a) and Sb2Te3 (b). From the figure, it is found that the E ads of N 2 adsorbed on Sb 2 Te 3 is about -0.032eV, which is much lower than that of Sb ( -0.0084eV ). This indicates the formation of stronger covalent interactions between Sb 2 Te 3 and N 2 , suggesting that N 2 is more efficiently adsorbed and activated on the surface of telluride (Sb 2 Te 3 ) than on Sb. This is consistent with the TPD results.
图25是催化剂的DOS图：Sb2Te3总图(a)和Sb2Te3拆分图(b)。由图所示相比于Sb，Sb2Te3的费米能级上的电荷密度更高，有利于N2的还原Figure 25 is the DOS diagram of the catalyst: the general diagram of Sb 2 Te 3 (a) and the split diagram of Sb 2 Te 3 (b). As shown in the figure, compared with Sb, the charge density on the Fermi level of Sb 2 Te 3 is higher, which is beneficial to the reduction of N 2
图26是在表面氢化的Sb2Te3进行的N2吸附(a)和*NNH(b)图。如图所示在Sb2Te3的表面上有两个位点，Sb的位点用于N2的吸附，Te原子的表面加氢以提供*H来还原N2。Figure 26 is a graph of N 2 adsorption (a) and *NNH (b) on surface hydrogenated Sb 2 Te 3 . As shown in the figure, there are two sites on the surface of Sb 2 Te 3 , the site of Sb is used for the adsorption of N 2 , and the surface of Te atom is hydrogenated to provide *H to reduce N 2 .
图27为Sb2Te3吸附氢计算图。由图所知，Sb2Te3-H*上的*H解吸自由能较高，这意味着Sb2Te3-H*上发生HER非常难，可以有效抑制析氢，提高选择性。Fig. 27 is a calculation diagram of hydrogen adsorption by Sb 2 Te 3 . As can be seen from the figure, the free energy of *H desorption on Sb 2 Te 3 -H* is relatively high, which means that it is very difficult for HER to occur on Sb 2 Te 3 -H*, which can effectively suppress hydrogen evolution and improve selectivity.
图28为Sb2Te3-H*和Sb的氮还原加氢自由能计算图。由图所知，Sb2Te3-H上N2的氢化比Sb上的快。比较Sb2Te3上NNH*的生成自由能，Te上的*H可以很容易地转移到N2上，极大地加速了N2在Sb2Te3-H*上的氢化过程，并降低了NRR的启动电势，这解释了NH3产量高，过电位低。Fig. 28 is a calculation diagram of the nitrogen reduction hydrogenation free energy of Sb 2 Te 3 -H* and Sb. From the figure, the hydrogenation of N 2 on Sb 2 Te 3 -H is faster than that on Sb. Comparing the free energy of formation of NNH* on Sb 2 Te 3 , *H on Te can be easily transferred to N 2 , which greatly accelerates the hydrogenation process of N 2 on Sb 2 Te 3 -H* and reduces The onset potential of the NRR, which explains the high NH production and low overpotential.
图29为Sb2Te3双原子位点助力电催化NH3还原的方法的机理示意图。根据图，可以看出：氮气吸附在Sb原子上，H吸附在Te原子上，Te-H上的H原子快速转移到Sb的N2上，加快N2还原形成*NNH，继续加氢至NH3脱附。Figure 29 is a schematic diagram of the mechanism of the Sb 2 Te 3 diatomic site-assisted electrocatalytic reduction of NH 3 . According to the figure, it can be seen that nitrogen is adsorbed on the Sb atom, H is adsorbed on the Te atom, and the H atom on Te-H is quickly transferred to the N2 of Sb, which accelerates the reduction of N2 to form *NNH, and continues to hydrogenate to NH 3 desorption.
表1为现阶段报道低电压下催化剂的催化性能。如表所示，碲化物在低电压下催化氮气还原具有较好的前景。Table 1 is the catalytic performance of the catalysts reported at this stage under low voltage. As shown in the table, tellurides are promising for catalyzing nitrogen reduction at low voltages.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. within range.
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