CN114367286A - 一种金属单原子催化剂及其制备方法 - Google Patents
一种金属单原子催化剂及其制备方法 Download PDFInfo
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- CN114367286A CN114367286A CN202210074684.4A CN202210074684A CN114367286A CN 114367286 A CN114367286 A CN 114367286A CN 202210074684 A CN202210074684 A CN 202210074684A CN 114367286 A CN114367286 A CN 114367286A
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- metal
- metal oxide
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 230000001678 irradiating effect Effects 0.000 claims description 24
- 229910052724 xenon Inorganic materials 0.000 claims description 21
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 239000001307 helium Substances 0.000 claims description 15
- 229910052734 helium Inorganic materials 0.000 claims description 15
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 15
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 5
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 4
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
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- 239000007789 gas Substances 0.000 description 25
- 238000004140 cleaning Methods 0.000 description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
- 238000005286 illumination Methods 0.000 description 14
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000007540 photo-reduction reaction Methods 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000000151 deposition Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
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- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- UOFRJXGVFHUJER-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;hydrate Chemical compound [OH-].OCC[NH+](CCO)CCO UOFRJXGVFHUJER-UHFFFAOYSA-N 0.000 description 1
- KMQHGFPNBPHBQE-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;methanol Chemical compound OC.OCCN(CCO)CCO KMQHGFPNBPHBQE-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
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- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
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- 238000007210 heterogeneous catalysis Methods 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
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Abstract
一种金属单原子催化剂及制备方法，将半导体金属氧化物与空穴牺牲剂溶液混合，搅拌均匀，并采用惰性气体吹扫，在光源下照射，得到还原性金属氧化物分散液；将单原子源液滴加到上述还原性金属氧化物分散液中，避光搅拌，分离，烘干，得到金属单原子催化剂；其中，单原子源液中单原子的质量比为半导体金属氧化物质量的0.01‑10％。本发明利用半导体金属氧化物内部存储的光生电子，实现金属单原子在氧化物表面的稳定、高通量负载。本发明金属氧化物存储的电子触发单原子负载，电子释放缓慢，在催化剂表面分散均匀，避免了金属单原子长大为纳米颗粒的缺陷。相较于现有的制备方法，本发明操作简单，单原子负载量大，结构稳定，可大量生产。
Description
技术领域
本发明属于复合材料制备领域，具体涉及一种金属单原子催化剂及其制备方法。
背景技术
在过去的几十年里，纳米材料引领了催化技术的进步。纳米材料与块体材料相比，拥有更大比表面积，能够暴露更多催化活性位点。随着纳米材料尺寸减小，原子配位不饱和度提高，从而表现出更高的催化活性。此外，纳米材料尺寸减小能暴露更多活性位点，进一步提高原子利用率。那么，如果催化材料的尺寸被减小到理论极限，将会得到单原子催化剂。
首先，单原子催化剂拥有单一的、配位不饱和的活性位点，具有极高活性和选择性。其次，单原子将所有的活性位点都暴露出来，实现了最大的原子利用率。在环境催化中，常用贵金属作为助催化剂，例如，Pd催化剂在去除饮用水中的一些典型污染物中得到了大量的应用。当Pd以直径为5nm的纳米颗粒形式存在时，78.6％的Pd原子被埋藏在催化剂的内部而无法发挥出其催化活性。而当Pd以单原子的形式存在，得到相同数量的活性位点时可减少220倍Pd的使用量，这无疑存在巨大的经济价值。另外，单原子催化剂活性位点均一，并且具有均相催化和非均相催化的特点，适合用于环境催化过程和机理研究。总之，单原子催化剂能为碳中和、新能源、水资源、医药化工等一系列问题的解决提供新原理和新思路。
然而，随着尺寸的减小，金属粒子的表面能将会急剧增大，从而自发的聚集成较大的金属粒子。因此，单原子催化剂制备的缺乏限制了其进一步的规模化应用。为了实现单原子催化剂的实际应用，亟需开发简单高效的单原子制备方法。
在传统的光沉积方法中，直接将单原子源溶液与半导体氧化物混合，在光照条件下，还原性的光生电子聚集在半导体氧化物的导带周围，接触金属单原子后，会将光生电子转移到金属单原子上，实现单原子的负载。但是，导带附近一旦沉积了金属单原子，光生电子就会转移到金属单原子上，使得溶液中的金属源趋向于负载到金属单原子上，导致最初负载的金属单原子迅速长大为金属团簇或者纳米颗粒，从而失去了金属单原子的优势。
发明内容
为了解决上述问题，本发明的目的是提供了一种金属单原子催化剂及其制备方法，该方法制备的催化剂催化效率高。
为实现上述目的，本发明采用的技术方案如下：
一种金属单原子催化剂的制备方法，包括以下步骤：
将半导体金属氧化物与空穴牺牲剂溶液混合，搅拌均匀，并采用惰性气体吹扫，在光源下照射，得到还原性金属氧化物分散液；
将单原子源液滴加到上述还原性金属氧化物分散液中，避光搅拌，分离，烘干，得到金属单原子催化剂；其中，单原子源液中单原子的质量比为半导体金属氧化物质量的0.01-10％。
进一步的，半导体金属氧化物为MnO2、MoO3、V2O5、Fe2O3、WO3、VO2、Co3O4、SnO2、TiO2、ZnO、Nb2O5、CeO2与Cu2O中的一种。
进一步的，空穴牺牲剂为水、甲醇、乙醇、三乙醇胺与亚硫酸钠溶液中的一种或多种混合。
进一步的，半导体金属氧化物与空穴牺牲剂溶液的用量比为0.001-10g：10-1000mL。
进一步的，惰性气体为氦气、氮气、氩气中的一种或多种任意比混合气体，吹扫时间为0.5-24h。
进一步的，光源为自然太阳光与氙灯光源中的一种，照射时间为0.5-24h。
进一步的，单原子源液为含Pt、Pd、Au、Fe、Ni、Cu或Ag单原子金属源溶液中的一种；单原子源液的浓度为0.1-0.5mol/L。
进一步的，含Pt单原子金属源为H2PtCl6与Pt(NH3)4Cl2中的一种；
含Pd单原子金属源为PdCl4与Na2PdCl4中的一种；
含Au单原子金属源为HAuCl4；
含Ag单原子金属源为AgNO3；
含Fe单原子金属源为FeCl3与FeCl2中的一种；
含Ni单原子金属源为NiCl2；
含Cu单原子金属源为CuCl2与Cu(NO3)2中的一种。
进一步的，避光搅拌的转速为100-1000转/分钟，搅拌时间为0.5-24h；烘干温度为40-90℃，时间为6-24h。
一种根据如上所述的方法制得的金属单原子催化剂。
与现有技术相比，本发明具有如下有益效果：
本发明提供的金属单原子制备方法，以半导体金属氧化物和单原子源液为原料，利用半导体金属氧化物内部存储的光生电子，实现金属单原子在氧化物表面的稳定、高通量负载(单原子负载量可高达1wt％)。本发明利用了金属氧化物存储的电子触发单原子负载，电子释放缓慢，在催化剂表面分散均匀，避免了金属单原子长大为纳米颗粒的缺陷。相较于现有的制备方法，本发明操作简单，单原子负载量大，结构稳定，可大量生产。本发明的制备过程中避免了高温煅烧或者氢气还原等步骤，反应条件温和。由于单原子沉积过程中是避光的，避免了单原子团聚成团簇或者纳米颗粒。并且该方法制备的单原子催化剂有着优异的光催化还原二氧化碳性能，有着很好的应用前景。
本发明制备的金属单原子催化剂具有高效光催化二氧化碳还原，由于单原子和载体的相互作用，可改变氧化物半导体的能带结构，增强对可见光的吸收，实现了全光谱的光吸收。由于金属单原子活性位点的存在，能够实现高效的光催化二氧化碳还原产甲烷。并且由于活性位点单一，产物的选择性更高，产物对甲烷选择性可接近100％。
附图说明
为了进一步理解本发明，对本发明进行附图描述。
图1是实施例1制备的Pt单原子沉积MoO3的球差校正扫描透射电子显微镜(AC-STEM)图。
图2是实施例1制备的Pt单原子沉积MoO3的XPS对比图。
图3是实施例1制备的单原子Pt负载MoO3光催化还原CO2性能的对比图。
图4是实施例1制备的单原子Pt负载MoO3光催化还原CO2的循环稳定图。
具体实施方式
下面结合具体的实施案例，对发明的技术方案、目的和优点进一步详细说明。
本发明的一种金属单原子的制备方法，包括以下步骤：将0.001-10g半导体金属氧化物与10-1000mL空穴牺牲剂混合搅拌，并使用10-200mL/min的惰性气体彻底吹扫溶液0.5-24h。随后，在光源下照射0.5-24h，得到还原性金属氧化物分散液。最后，将一定量的单原子源液滴加到上述还原性金属氧化物分散液中，避光搅拌一段时间，2000-12000转/分钟离心分离出沉淀，清洗烘干，得到金属单原子催化剂。
其中，半导体金属氧化物为MnO2、MoO3、V2O5、Fe2O3、WO3、VO2、Co3O4、SnO2、TiO2、ZnO、Nb2O5、CeO2与Cu2O中的一种。
空穴牺牲剂为纯水、甲醇、乙醇、三乙醇胺与1mol/L的亚硫酸钠溶液中的一种或多种混合。
惰性气体为氦气、氮气与氩气中的一种或多种任意比混合，吹扫时间为0.5-24h。
光照的光源可以为自然太阳光与氙灯光源中的一种，照射时间为0.5-24h。
单原子源液为含Pt、Pd、Au、Fe、Ni、Cu或Ag单原子金属源溶液中的一种。
单原子源液中单原子的质量为半导体金属氧化物质量的0.01-10％。
单原子源液的浓度为0.1-0.5mol/L。
优选的，含Pt单原子金属源为H2PtCl6与Pt(NH3)4Cl2中的一种；
含Pd单原子金属源为PdCl4与Na2PdCl4中的一种；
含Au单原子金属源为HAuCl4；
含Ag单原子金属源为AgNO3；
含Fe单原子金属源为FeCl3与FeCl2中的一种；
含Ni单原子金属源为NiCl2；
含Cu单原子金属源为CuCl2与Cu(NO3)2中的一种。
避光搅拌的条件为100-1000转/分钟，搅拌时间为0.5-24h。
烘干温度为40-90℃，时间为6-24h。
一种根据上述的方法制得的金属单原子负载碳氮聚合物催化剂，主要成分为金属单原子位点和金属氧化物载体材料。
下面为具体实施例。
实施例1
(1)取1g MoO3加入到100mL的甲醇水体积比为1：10的甲醇溶液中。
(2)使用100mL/min的氦气吹扫步骤(1)得到的溶液0.5h。
(3)使用氙灯照射步骤(2)吹扫后的溶液1h，得到还原性的金属氧化物分散液。
(4)取1mL的0.1mol/L的H2PtCl6溶液滴加步骤(3)得到的还原性金属氧化物分散液中，以400转/分钟速度避光搅拌24h。
(5)以10000转/分钟离心分离出搅拌后的金属氧化物，清洗后在70℃下烘24h，得到金属单原子催化剂，记作Pt/MoO3-LD。
通过电感耦合等离子体质谱(ICP-MS)对Pt单原子含量测试，发现Pt单原子的负载量(质量比)高达1％，可见本方法可实现单原子的高通量负载。
取0.1g Pt/MoO3-LD均匀分散在200mL圆柱形反应器底部，反应器四周和底部有不锈钢组成，顶端是石英窗口，并预留了加入和抽取气体的端口。向反应器中注入1MPa的CO2气体，将300W氙灯提供的光源垂直照射到催化剂表面上，光照1h后检测气体中CO和CH4的浓度，计算得到Pt/MoO3-LD光还原CO2产生CO和CH4的效率分别为0.1和9.8μmol g-1h-1。
从图1可见，Pt以单原子的形式负载到了MoO3表面上，并且没有团簇和纳米颗粒的出现。
从图2可见，Pt成功的负载到了MoO3的表面上。
从图3可见，Pt负载后MoO3的催化性能得到了提升，并有助于生成多电子产物CH4。
从图4可见，经过3次循环测试，催化剂的催化性能并没有明显的下降，说明所制备的Pt/MoO3-LD催化剂有较好的稳定性。
实施例2
(1)取1g MoO3加入到100mL的甲醇水体积比为1：10的甲醇溶液中。
(2)使用100mL/min的氦气吹扫步骤(1)得到的溶液0.5h。
(3)使用氙灯照射步骤(2)吹扫后的溶液1h，得到还原性的金属氧化物分散液。
(4)取1mL的0.1mol/L的AgNO3溶液滴加步骤(3)得到的还原性金属氧化物分散液中，以400转/分钟速度避光搅拌24h。
(5)以10000转/分钟离心分离出搅拌后的金属氧化物，清洗后在70℃下烘24h，得到金属单原子催化剂，记作Ag/MoO3-LD。
取0.1g Ag/MoO3-LD均匀分散在200mL圆柱形反应器底部，反应器四周和底部有不锈钢组成，顶端是石英窗口，并预留了加入和抽取气体的端口。向反应器中注入1MPa的CO2气体，将300W氙灯提供的光源垂直照射到催化剂表面上，光照1h后检测气体中CO和CH4的浓度，计算得到Ag/MoO3-LD光还原CO2产生CO和CH4的效率分别为0.5和3μmol g-1h-1。
实施例3
(1)取1g MoO3加入到100mL的甲醇水体积比为1：10的甲醇溶液中。
(2)使用100mL/min的氦气吹扫步骤(1)得到的溶液0.5h。
(3)使用氙灯照射步骤(2)吹扫后的溶液1h，得到还原性的金属氧化物分散液。
(4)取1mL的0.1mol/L的HAuCl4溶液滴加步骤(3)得到的还原性金属氧化物分散液中，以400转/分钟速度避光搅拌24h。
(5)以10000转/分钟离心分离出搅拌后的金属氧化物，清洗后在70℃下烘24h，得到金属单原子催化剂，记作Au/MoO3-LD。
取0.1g Au/MoO3-LD均匀分散在200mL圆柱形反应器底部，反应器四周和底部有不锈钢组成，顶端是石英窗口，并预留了加入和抽取气体的端口。向反应器中注入1MPa的CO2气体，将300W氙灯提供的光源垂直照射到催化剂表面上，光照1h后检测气体中CO和CH4的浓度，计算得到Au/MoO3-LD光还原CO2产生CO和CH4的效率分别为1.1和3.1μmol g-1h-1。
实施例4
(1)取1g TiO2加入到100mL的甲醇水体积比为1：10的甲醇溶液中。
(2)使用100mL/min的氦气吹扫步骤(1)得到的溶液0.5h。
(3)使用氙灯照射步骤(2)吹扫后的溶液1h，得到还原性的金属氧化物分散液。
(4)取1mL的0.1mol/L的H2PtCl6溶液滴加步骤(3)得到的还原性金属氧化物分散液中，以400转/分钟速度避光搅拌24h。
(5)以10000转/分钟离心分离出搅拌后的金属氧化物，清洗后在70℃下烘24h，得到金属单原子催化剂，记作Pt/TiO2-LD。
取0.1g Pt/TiO2-LD均匀分散在200mL圆柱形反应器底部，反应器四周和底部有不锈钢组成，顶端是石英窗口，并预留了加入和抽取气体的端口。向反应器中注入1MPa的CO2气体，将300W氙灯提供的光源垂直照射到催化剂表面上，光照1h后检测气体中CO和CH4的浓度，计算得到Pt/TiO2-LD光还原CO2产生CO和CH4的效率分别为10.2和1.5μmol g-1h-1。
实施例5
(1)取1g Cu2O加入到100mL的甲醇水体积比为1：10的甲醇溶液中。
(2)使用100mL/min的氦气吹扫步骤(1)得到的溶液0.5h。
(3)使用氙灯照射步骤(2)吹扫后的溶液1h，得到还原性的金属氧化物分散液。
(4)取1mL的0.1mol/L的H2PtCl6溶液滴加步骤(3)得到的还原性金属氧化物分散液中，以400转/分钟速度避光搅拌24h。
(5)以10000转/分钟离心分离出搅拌后的金属氧化物，清洗后在70℃下烘24h，得到金属单原子催化剂，记作Pt/Cu2O-LD。
取0.1g Pt/Cu2O-LD均匀分散在200mL圆柱形反应器底部，反应器四周和底部有不锈钢组成，顶端是石英窗口，并预留了加入和抽取气体的端口。向反应器中注入1MPa的CO2气体，将300W氙灯提供的光源垂直照射到催化剂表面上，光照1h后检测气体中CO和CH4的浓度，计算得到Pt/Cu2O-LD光还原CO2产生CO和CH4的效率分别为6.6和1.3μmol g-1h-1。
实施例6
(1)取1g WO3加入到100mL的甲醇水体积比为1：10的甲醇溶液中。
(2)使用100mL/min的氦气吹扫步骤(1)得到的溶液0.5h。
(3)使用氙灯照射步骤(2)吹扫后的溶液1h，得到还原性的金属氧化物分散液。
(4)取1mL的0.1mol/L的H2PtCl6溶液滴加步骤(3)得到的还原性金属氧化物分散液中，以400转/分钟速度避光搅拌24h。
(5)以10000转/分钟离心分离出搅拌后的金属氧化物，清洗后在70℃下烘24h，得到金属单原子催化剂，记作Pt/WO3-LD。
取0.1g Pt/WO3-LD均匀分散在200mL圆柱形反应器底部，反应器四周和底部有不锈钢组成，顶端是石英窗口，并预留了加入和抽取气体的端口。向反应器中注入1MPa的CO2气体，将300W氙灯提供的光源垂直照射到催化剂表面上，光照1h后检测气体中CO和CH4的浓度，计算得到Pt/WO3-LD光还原CO2产生CO和CH4的效率分别为12.1和1.2μmol g-1h-1。
实施例7
(1)取0.001g MnO2加入到10mL的乙醇中。
(2)使用100mL/min的氮气吹扫步骤(1)得到的溶液24h。
(3)使用自然太阳光照射步骤(2)吹扫后的溶液1h，得到还原性的金属氧化物分散液。
(4)取0.5mol/L的Pt(NH3)4Cl2溶液滴加步骤(3)得到的还原性金属氧化物分散液中，以800转/分钟速度避光搅拌5h。其中，Pt的质量为MnO2质量的8％。
(5)以10000转/分钟离心分离出搅拌后的金属氧化物，清洗后在40℃下烘24h，得到金属单原子催化剂。
实施例8
(1)取0.01g V2O5加入到10mL的质量比为5％的三乙醇胺水中。
(2)使用100mL/min的氦气吹扫步骤(1)得到的溶液0.5h。
(3)使用自然太阳光照射步骤(2)吹扫后的溶液0.5h，得到还原性的金属氧化物分散液。
(4)取0.4mol/L的PdCl4溶液滴加步骤(3)得到的还原性金属氧化物分散液中，以700转/分钟速度避光搅拌10h。其中，Pd的质量为V2O5质量的5％。
(5)以10000转/分钟离心分离出搅拌后的金属氧化物，清洗后在90℃下烘6h，得到金属单原子催化剂。
实施例9
(1)取0.1g Fe2O3加入到50mL的1mol/L的亚硫酸钠溶液。
(2)使用100mL/min的氩气吹扫步骤(1)得到的溶液4h。
(3)使用自然太阳光照射步骤(2)吹扫后的溶液24h，得到还原性的金属氧化物分散液。
(4)取0.3mol/L的Na2PdCl4溶液滴加步骤(3)得到的还原性金属氧化物分散液中，以600转/分钟速度避光搅拌15h。其中，Pd的质量为Fe2O3质量的3％。
(5)以10000转/分钟离心分离出搅拌后的金属氧化物，清洗后在50℃下烘20h，得到金属单原子催化剂。
实施例10
(1)取1g WO3加入到500mL的甲醇乙醇体积比为1:1的溶液中。
(2)使用100mL/min的氦气吹扫步骤(1)得到的溶液20h。
(3)使用氙灯照射步骤(2)吹扫后的溶液5h，得到还原性的金属氧化物分散液。
(4)取0.3mol/L的FeCl3溶液滴加步骤(3)得到的还原性金属氧化物分散液中，以200转/分钟速度避光搅拌20h。其中，Fe的质量为WO3质量的1％。
(5)以10000转/分钟离心分离出搅拌后的金属氧化物，清洗后在60℃下烘15h，得到金属单原子催化剂。
实施例11
(1)取5g VO2加入到1000mL的甲醇三乙醇胺体积比为1：5的溶液中。
(2)使用100mL/min的氦气吹扫步骤(1)得到的溶液10h。
(3)使用氙灯照射步骤(2)吹扫后的溶液24h，得到还原性的金属氧化物分散液。
(4)取0.1mol/L的FeCl2溶液滴加步骤(3)得到的还原性金属氧化物分散液中，以1000转/分钟速度避光搅拌0.5h。其中，Fe的质量为VO2质量的0.1％。
(5)以10000转/分钟离心分离出搅拌后的金属氧化物，清洗后在70℃下烘12h，得到金属单原子催化剂。
实施例12
(1)取8g Co3O4加入到100mL的甲醇水体积比为1：10的甲醇溶液中。
(2)使用100mL/min的氦气吹扫步骤(1)得到的溶液15h。
(3)使用氙灯照射步骤(2)吹扫后的溶液10h，得到还原性的金属氧化物分散液。
(4)取0.2mol/L的CuCl2溶液滴加步骤(3)得到的还原性金属氧化物分散液中，以100转/分钟速度避光搅拌24h。其中，Cu的质量为Co3O4质量的0.01％。
(5)以10000转/分钟离心分离出搅拌后的金属氧化物，清洗后在80℃下烘10h，得到金属单原子催化剂。
实施例13
与实施例12不同在于，半导体金属氧化物为SnO2。
实施例14
与实施例12不同在于，半导体金属氧化物为TiO2。
实施例15
与实施例12不同在于，半导体金属氧化物为ZnO。
实施例16
与实施例12不同在于，半导体金属氧化物为Nb2O5。
实施例17
与实施例12不同在于，半导体金属氧化物为CeO2。
实施例18
与实施例12不同在于，半导体金属氧化物为Cu2O。
对比例1
(1)取8g MoO3加入到100mL的甲醇水体积比为1：10的甲醇溶液中。
(2)使用100mL/min的氦气吹扫步骤(1)得到的溶液0.5h。
(3)取1mL的0.1mol/L的H2PtCl6溶液滴加步骤(2)得到的金属氧化物分散液中，以400转/分钟速度避光搅拌24h。
(4)以10000转/分钟离心分离出搅拌后的金属氧化物，清洗后在70℃下烘24h，得到金属单原子催化剂，记作Pt/MoO3-D。
取0.1g Pt/MoO3-D均匀分散在200mL圆柱形反应器底部，反应器四周和底部有不锈钢组成，顶端是石英窗口，并预留了加入和抽取气体的端口。向反应器中注入1MPa的CO2气体，将300W氙灯提供的光源垂直照射到催化剂表面上，光照1h后检测气体中CO和CH4的浓度，计算得到Pt/MoO3-D光还原CO2产生CO和CH4的效率分别为0.1和2μmol g-1h-1。
对比例2
(1)取1g MoO3加入到100mL的甲醇水体积比为1：10的甲醇溶液中。
(2)使用100mL/min的氦气吹扫步骤(1)得到的溶液0.5h。
(3)1mL的0.1mol/L的H2PtCl6溶液滴加步骤(2)得到的金属氧化物分散液中，以400转/分钟速度避光搅拌24h。
(4)使用氙灯照射步骤(3)得到的溶液1h。
(5)以10000转/分钟离心分离出光照后的金属氧化物，清洗后在70℃下烘24h，得到金属单原子催化剂，记作Pt/MoO3-L。
取0.1g Pt/MoO3-L均匀分散在200mL圆柱形反应器底部，反应器四周和底部有不锈钢组成，顶端是石英窗口，并预留了加入和抽取气体的端口。向反应器中注入1MPa的CO2气体，将300W氙灯提供的光源垂直照射到催化剂表面上，光照1h后检测气体中CO和CH4的浓度，计算得到Pt/MoO3-L光还原CO2产生CO和CH4的效率分别为0.9和3μmol g-1h-1。
通过对比例1与实施例1对比，本发明的制备方法得到的单原子催化剂性能优于传统浸渍沉积方法制备的催化剂。
通过对比例2与实施例1对比，本发明的制备方法得到的单原子催化剂优于传统浸渍沉积方法制备的催化剂。
本发明利用半导体金属氧化物在光照过程中存储的电子实现了单原子的温度、高通量负载，具体过程如下(以MoO3为例说明)：
光照+MoO3→电子+空穴(被空穴牺牲剂消耗) 1
电子+Mo+6O3→Mo+5O3(电子被MoO3存储) 2
Mo+5O3+金属阳离子→单原子负载Mo+6O3催化剂 3
基本原理为合适的光照射到金属半导体上，由于光电效应，在半导体内产生光生电子空穴对，空穴会被空穴牺牲剂消耗(式1)。光生电子会被晶格的六价Mo+6原子捕获，原位生成五价Mo+5原子，实现对还原性电子的存储(式2)。在结束光照后，避光条件下加入金属阳离子，Mo+5会将电子释放出来，转移到金属阳离子上，实现单原子的稳定负载(式3)。值得一提的是，在Mo变价的过程中会引入一定量的晶格畸变，因此具有很强的还原性，可实现绝大多数金属阳离子的还原过程，适用性很广。相较于传统的单原子制备方法(Chem.Rev.2019,119,1806-1854)，本发明的制备过程中避免了高温煅烧或者氢气还原等步骤，反应条件温和。由于单原子沉积过程中是避光的，避免了单原子团聚成团簇或者纳米颗粒。并且该方法制备的单原子催化剂有着优异的光催化还原二氧化碳性能，有着很好的应用前景。
Claims (10)
1.一种金属单原子催化剂的制备方法，其特征在于，包括以下步骤：
将半导体金属氧化物与空穴牺牲剂溶液混合，搅拌均匀，并采用惰性气体吹扫，在光源下照射，得到还原性金属氧化物分散液；
将单原子源液滴加到上述还原性金属氧化物分散液中，避光搅拌，分离，烘干，得到金属单原子催化剂；其中，单原子源液中单原子的质量比为半导体金属氧化物质量的0.01-10％。
2.根据权利要求1所述的一种金属单原子催化剂的制备方法，其特征在于，半导体金属氧化物为MnO2、MoO3、V2O5、Fe2O3、WO3、VO2、Co3O4、SnO2、TiO2、ZnO、Nb2O5、CeO2与Cu2O中的一种。
3.根据权利要求1所述的一种金属单原子催化剂的制备方法，其特征在于，空穴牺牲剂为水、甲醇、乙醇、三乙醇胺与亚硫酸钠溶液中的一种或多种混合。
4.根据权利要求1所述的一种金属单原子催化剂的制备方法，其特征在于，半导体金属氧化物与空穴牺牲剂溶液的用量比为0.001-10g：10-1000mL。
5.根据权利要求1所述的一种金属单原子催化剂的制备方法，其特征在于，惰性气体为氦气、氮气、氩气中的一种或多种任意比混合气体，吹扫时间为0.5-24h。
6.根据权利要求1所述的一种金属单原子催化剂的制备方法，其特征在于，光源为自然太阳光与氙灯光源中的一种，照射时间为0.5-24h。
7.根据权利要求1所述的一种金属单原子催化剂的制备方法，其特征在于，单原子源液为含Pt、Pd、Au、Fe、Ni、Cu或Ag单原子金属源溶液中的一种；单原子源液的浓度为0.1-0.5mol/L。
8.根据权利要求1所述的一种金属单原子催化剂的制备方法，其特征在于，含Pt单原子金属源为H2PtCl6与Pt(NH3)4Cl2中的一种；
含Pd单原子金属源为PdCl4与Na2PdCl4中的一种；
含Au单原子金属源为HAuCl4；
含Ag单原子金属源为AgNO3；
含Fe单原子金属源为FeCl3与FeCl2中的一种；
含Ni单原子金属源为NiCl2；
含Cu单原子金属源为CuCl2与Cu(NO3)2中的一种。
9.根据权利要求1所述的一种金属单原子催化剂的制备方法，其特征在于，避光搅拌的转速为100-1000转/分钟，搅拌时间为0.5-24h；烘干温度为40-90℃，时间为6-24h。
10.一种根据权利要求1-9中任意一项所述的方法制得的金属单原子催化剂。
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