CN108772067B - 常温降解VOCs的负载双过渡金属单原子的ACF催化剂的制备方法 - Google Patents
常温降解VOCs的负载双过渡金属单原子的ACF催化剂的制备方法 Download PDFInfo
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- 229910017813 Cu—Cr Inorganic materials 0.000 claims abstract description 10
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- 229910018669 Mn—Co Inorganic materials 0.000 claims abstract description 10
- 229910017709 Ni Co Inorganic materials 0.000 claims abstract description 10
- 229910003267 Ni-Co Inorganic materials 0.000 claims abstract description 10
- 229910003262 Ni‐Co Inorganic materials 0.000 claims abstract description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 7
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 2
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- 238000007254 oxidation reaction Methods 0.000 description 7
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
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- 239000007789 gas Substances 0.000 description 3
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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- 229910052707 ruthenium Inorganic materials 0.000 description 1
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
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- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本发明公开了常温降解VOCs的负载双过渡金属单原子的ACF催化剂的制备方法,包括ACF在体积浓度为3‑30%的HCl溶液中进行预处理,预处理后浸渍负载双过渡金属元素Cu‑Cr、Mn‑Fe、Fe‑Cu、Ni‑Co、Fe‑Zn和Mn‑Co,再经超声分散0.5‑4h使其分散均匀,烘干后置于100‑600℃的马弗炉中煅烧2‑10h,制得负载双过渡金属氧化物的ACF催化剂,再经H2还原得到双过渡金属单原子ACF催化剂。本发明制备的双过渡金属单原子ACF催化剂能实现常温空气氛围下对VOCs的高效降解,催化剂活性高、成本低,极具应用前景。
Description
技术领域
本发明涉及环境治理领域,特别涉及常温降解VOCs的负载双过渡金属单原子的ACF催化剂的制备方法。
背景介绍
挥发性有机物(Volatile Organic Compounds,简称VOCs)产生于化工生产的各个领域,如石油炼制、印刷、涂料、制药、皮革等。大量排放的有机废气不但污染环境,还严重危害了人们的健康。随着人们生活水平的提高,公众对生活环境的要求也越来越高,VOCs的治理越来越成为研究的热点。
目前国内外在VOCs处理方面用到的技术有许多,如吸附法、吸收法、冷凝法、燃烧法(包括直接焚烧法和催化燃烧法)、等离子体法、生物降解法和光催化降解法和常温催化氧化法等。在以上各种处理方法中,常温催化氧化法最具有前景,它能实现常温高效降解VOCs,从而省去了大量的运行成本,节约了能源。常温催化氧化技术的核心在于催化剂的制备,在高效催化剂作用下实现常温催化氧化VOCs,从而使其彻底分解为CO2、H2O和部分无机盐。
专利号CN103372430A公开了一种负载贵金属催化剂的制备方法。首先将金属氧化物前驱体制成水相,然后将贵金属前驱体溶于油制成油相,将水相与油相按一定比例与表面活性剂混合,经雾化、点火、燃烧、冷却、团聚制得负载贵金属的粉体,可用于常温VOCs的消解,但制备方法过于复杂。专利号CN105013477A公开了一种用于催化氧化VOCs的催化剂,该催化剂使用锐钛矿相二氧化钛修饰的金红石相二氧化钛作为载体,活性组分为钌或钌的氧化物,混相二氧化钛与活性组分之间存在协同作用,进而提高了催化剂对VOCs的催化氧化性能。以上两种催化剂制备过程均使用到了贵金属,造成催化剂成本过高,此外,贵金属在使用过程中易中毒失活,不利于工业上长期应用。
单原子是一类新型的催化剂,它以单个原子位点为反应活性位,实现了极低负载量与高效催化活性的完美统一。我国大连物化所的张涛教授通过浸渍法实现了Pt催化剂的单原子分布,并且发现该单原子催化剂具有较高的催化活性。目前,对于双非贵金属单原子催化剂的制备尚未见报道。
发明内容
本发明的目的在于克服已有技术的缺点,提供一种实现了在空气气氛中常温高效降解VOCs的负载双过渡金属单原子的ACF催化剂的制备方法。
为达到上述目的,本发明采用的技术方案是:
本发明涉及的一种常温降解VOCs的负载双过渡金属单原子的ACF催化剂的制备方法,包括以下步骤:
步骤一、ACF的预处理:
将ACF浸没在体积浓度为3-30%的HCl溶液中,并将溶液置于40-100℃水浴锅中反应2-10h,然后取出ACF,并用蒸馏水洗涤至中性,自然晾干,所述ACF的比表面积为800-3000m2/g,外表面积为0.2-2.0m2/g;
步骤二、浸渍负载双过渡金属:
取双过渡金属可溶性盐,加蒸馏水溶解,待完全溶解后加入预处理后的ACF,超声分散0.5-4h,超声结束后静置2-30h,然后取出,在50-120℃烘箱中烘干,两种过渡金属元素摩尔比为(0.1-10):1,双过渡金属元素总质量与ACF质量比为0.1-5%;
步骤三、程序升温煅烧:
将烘干后的负载双过渡金属元素的ACF放入程序升温马弗炉中,以1-15℃/min升到100-600℃,然后恒温2-10h,制得负载双过渡金属氧化物的ACF催化剂;
步骤四、H2还原:
将制备的负载双过渡金属氧化物的ACF催化剂置于管式炉中,在H2体积百分比为1-40%的H2和He组成的氛围中还原,还原温度为100-700℃,还原时间为0.1-10h,得到还原的双过渡金属单原子ACF催化剂。
与现有技术相比,本发明具有以下有益效果:
1.首次制备出双过渡金属单原子催化剂,能实现常温空气氛围中对VOCs高效催化氧化降解,去除效率高、稳定性强。
2.采用活性碳纤维(ACF)做催化剂载体,催化剂比表面积非常高,孔道丰富,便于废气穿透,不会造成管路堵塞,便于工业化应用。
3.催化剂完全采用过渡金属,成本低廉,制备方法简单。
具体实施方式
本发明常温降解VOCs的双过渡金属单原子ACF催化剂的制备方法,包括以下步骤:
步骤一、ACF的预处理:
将ACF浸没在体积浓度为3-30%的HCl溶液中,并将溶液置于40-100℃水浴锅中反应2-10h。然后取出ACF,并用蒸馏水洗涤至中性,自然晾干,所述ACF的比表面积为800-3000m2/g,外表面积为0.2-2.0m2/g。
优选的,HCl体积浓度为8-15%,HCl浓度适中,既能溶解掉大多数可溶性杂质,同时又避免了浓度过高对碳纤维结构的破坏。
优选的,水浴锅的温度范围为60-80℃,反应时间为3-6h,加快反应速率,同时避免高温造成HCl挥发过快。
步骤二、浸渍负载双过渡金属:
取双过渡金属可溶性盐,如硝酸盐、硫酸盐、醋酸盐等,加蒸馏水溶解,待完全溶解后加入预处理后的ACF,超声分散0.5-4h。超声结束后静置2-30h。然后取出,在50-120℃烘箱中烘干。两种过渡金属元素的摩尔比为(0.1-10):1,双过渡金属元素总质量与ACF质量比为0.1-5%。
所述的过渡金属元素包括Mn、Fe、Cu、Ni、Co、Zn、Cr等中的任意两种。优选的,双过渡金属元素为Cu-Cr,Mn-Fe,Fe-Cu,Ni-Co,Fe-Zn或者Mn-Co,它们具有较好的催化降解VOCs能力。
优选的,双过渡金属元素摩尔比为(0.5-3):1,在该比例下双过渡金属单原子能发挥最好的协同作用。
优选的,过渡金属可溶性盐为过渡金属的硝酸盐,硝酸根加热即分解,形成的杂质少。优选的,双过渡金属元素总质量与ACF质量比为0.5-1%,这样形成单原子比例最多,催化降解性能最好。
优选的,超声分散时间为1-3h,可以使过渡金属元素均匀地负载在ACF上,时间过低则负载不均匀,过高则耗时长。
步骤三、程序升温煅烧:
将烘干后的负载双过渡金属元素的ACF放入程序升温马弗炉中,以1-15℃/min升到100-600℃,然后恒温2-10h,制得负载双过渡金属氧化物的ACF催化剂。
优选的,程序升温幅度为3-6℃/min,可以使样品中的硝酸根充分脱除。优选的,温度范围为200-400℃,可以形成稳定的金属氧化物同时又避免了温度过高对ACF材料的破坏。优选的,恒温时间为4-8h,形成的金属氧化物晶型较好。
步骤四、H2还原:
将制备的负载双过渡金属氧化物的ACF催化剂置于管式炉中,在H2的体积百分比为1-40%的H2和He组成的氛围中还原,还原温度为100-700℃,还原时间为0.1-10h,得到还原的双过渡金属单原子ACF催化剂。优选的,H2在H2和He组成的氛围中的体积百分比为5-20%,还原时间为0.5-4h,保证了充分还原,同时节省了氢气用量和时间。优选的,还原温度为200-400℃,在该温度下能得到较好的还原效果且不损坏ACF。
实施例1
(1)ACF的预处理。将ACF浸没在浓度为3%的HCl溶液中,并将溶液置于40℃水浴锅中反应10h。然后取出ACF,并用蒸馏水洗涤至中性,自然晾干。所述ACF的比表面积为800m2/g,外表面积为0.2m2/g。
(2)浸渍负载Cu-Cr双过渡金属。按Cu-Cr摩尔比为0.1:1分别称取硝酸铜和硝酸铬,加蒸馏水溶解。待完全溶解后加入预处理后的ACF,使得Cu-Cr双过渡金属元素总质量与ACF质量比为0.1%。超声分散0.5h。超声结束后静置30h。静置后取出,在50℃烘箱中烘干。
(3)程序升温煅烧。将烘干后的负载Cu-Cr元素的ACF放入程序升温马弗炉中,以1℃/min升到100℃,然后恒温10h,制得负载Cu-Cr双过渡金属氧化物的ACF催化剂。
(4)H2还原。将上步制备的负载Cu-Cr双过渡金属氧化物的ACF催化剂置于管式炉中,在H2组成为1%的H2和He组成的氛围中还原,还原温度为100℃,还原时间为0.1h,得到还原的负载Cu-Cr双过渡金属单原子的ACF催化剂。
催化剂性能评价。废气中苯的浓度为400mg/m3,空气占比60%,空速为3000h-1。苯的去除效率达到80%以上,稳定时间超过80h。
实施例2
(1)ACF的预处理。将ACF浸没在浓度为8%的HCl溶液中,并将溶液置于60℃水浴锅中反应6h。然后取出ACF,并用蒸馏水洗涤至中性,自然晾干。所述ACF的比表面积为1200m2/g,外表面积为0.6m2/g。
(2)浸渍负载Mn-Fe双过渡金属。按Mn-Fe摩尔比为0.5:1分别称取硝酸锰和硝酸铁,加蒸馏水溶解。待完全溶解后加入预处理后的ACF,使得Mn-Fe双过渡金属元素总质量与ACF质量比为0.5%。超声分散1h。超声结束后静置15h。静置后取出,在70℃烘箱中烘干。
(3)程序升温煅烧。将烘干后的负载Mn-Fe元素的ACF放入程序升温马弗炉中,以3℃/min升到200℃,然后恒温8h,制得负载Mn-Fe双过渡金属氧化物的ACF催化剂。
(4)H2还原。将上步制备的负载Mn-Fe双过渡金属氧化物的ACF催化剂置于管式炉中,在H2组成为5%的H2和He组成的氛围中还原,还原温度为200℃,还原时间为0.5h,得到还原的负载Mn-Fe双过渡金属单原子的ACF催化剂。
催化剂性能评价。废气中二氯乙烷浓度为600mg/m3,空气占比40%,空速为20000h-1。二氯乙烷去除效率达到95%以上,稳定时间超过80h。
实施例3
(1)ACF的预处理。将ACF浸没在浓度为10%的HCl溶液中,并将溶液置于70℃水浴锅中反应5h。然后取出ACF,并用蒸馏水洗涤至中性,自然晾干。所述ACF的比表面积为1500m2/g,外表面积为0.8m2/g。
(2)浸渍负载Fe-Cu双过渡金属。按Fe-Cu摩尔比为1:1称取硝酸铁和硝酸铜,加蒸馏水溶解,待完全溶解后加入预处理后的ACF,使得Fe-Cu双过渡金属元素总质量与ACF质量比为0.6%。超声分散1.5h。超声结束后静置13h。静置结束后取出,在80℃烘箱中烘干。
(3)程序升温煅烧。将烘干后的负载Fe-Cu元素的ACF放入程序升温马弗炉中,以4℃/min升到300℃,然后恒温7h,制得负载Fe-Cu双过渡金属氧化物的ACF催化剂。
(4)H2还原。将上步制备的负载Fe-Cu双过渡金属氧化物的ACF催化剂置于管式炉中,在H2组成在10%的H2和He组成的氛围中还原,还原温度为300℃,还原时间为1h,得到还原的负载Fe-Cu双过渡金属单原子的ACF催化剂。
催化剂性能评价。废气中甲苯浓度为700mg/m3,空气占比50%,空速为40000h-1。甲苯去除效率达到96%以上,稳定时间超过80h。。
实施例4
(1)ACF的预处理。将ACF浸没在浓度为15%的HCl溶液中,并将溶液置于80℃水浴锅中反应3h。然后取出ACF,并用蒸馏水洗涤至中性,自然晾干。所述ACF的比表面积为2000m2/g,外表面积为1.3m2/g。
(2)浸渍负载Ni-Co双过渡金属。按Ni-Co摩尔比为3:1称取硝酸镍和硝酸钴,加蒸馏水溶解,待完全溶解后加入预处理后的ACF,使得Ni-Co双过渡金属元素总质量与ACF质量比为1%。超声分散3h。超声结束后静置10h。静置结束后取出,在90℃的烘箱中烘干。
(3)程序升温煅烧。将烘干后的负载Ni-Co元素的ACF放入程序升温马弗炉中,以6℃/min升到400℃,然后恒温4h,制得负载Ni-Co双过渡金属氧化物的ACF催化剂。
(4)H2还原。将上步制备的负载Ni-Co双过渡金属氧化物的ACF催化剂置于管式炉中,在H2组成在20%的H2和He组成的氛围中还原,还原温度为400℃,还原时间为4h,得到还原的负载Ni-Co双过渡金属单原子的ACF催化剂。
催化剂性能评价。废气中乙酸甲酯浓度为300mg/m3,空气占比40%,空速为5000h-1。乙酸甲酯去除效率达到100%,稳定时间超过80h。
实施例5
(1)ACF的预处理。将ACF浸没在浓度为30%的HCl溶液中,并将溶液置于100℃水浴锅中反应2h。然后取出ACF,并用蒸馏水洗涤至中性,自然晾干。所述ACF的比表面积为3000m2/g,外表面积为2.0m2/g。
(2)浸渍负载Fe-Zn双过渡金属。按Fe-Zn摩尔比为10:1称取硝酸铁和硫酸锌,加蒸馏水溶解,待完全溶解后加入预处理后的ACF,使得Fe-Zn双过渡金属元素总质量与ACF质量比为5%。超声分散4h。超声结束后静置2h。静置结束后取出,在120℃烘箱中烘干。
(3)程序升温煅烧。将烘干后的负载Fe-Zn元素的ACF放入程序升温马弗炉中,以15℃/min升到600℃,然后恒温2h,制得负载Fe-Zn双过渡金属氧化物的ACF催化剂。
(4)H2还原。将上步制备的负载Fe-Zn双过渡金属氧化物的ACF催化剂置于管式炉中,在H2组成在40%的H2和He组成的氛围中还原,还原温度为700℃,还原时间为10h。得到还原的负载Fe-Zn双过渡金属单原子的ACF催化剂。
催化剂性能评价。废气中甲醇浓度为800mg/m3,空气占比30%,空速为60000h-1。甲醇去除效率达到85%以上,稳定时间超过80h。
实施例6
(1)ACF的预处理。将ACF浸没在浓度为25%的HCl溶液中,并将溶液置于90℃水浴锅中反应4h。然后取出ACF,并用蒸馏水洗涤至中性,自然晾干。所述ACF的比表面积为2400m2/g,外表面积为1.6m2/g。
(2)浸渍负载Mn-Co双过渡金属。按Mn-Co摩尔比为7:1称取硝酸锰和硝酸钴,加蒸馏水溶解,待完全溶解后加入预处理后的ACF,使得Mn-Co双过渡金属元素总质量与ACF质量比为4%。超声分散3h。超声结束后静置8h。静置结束后取出,在100℃烘箱中烘干。
(3)程序升温煅烧。将烘干后的负载Mn-Co元素的ACF放入程序升温马弗炉中,以10℃/min升到500℃,然后恒温3h,制得负载Mn-Co双过渡金属氧化物的ACF催化剂。
(4)H2还原。将上步制备的负载Mn-Co双过渡金属氧化物的ACF催化剂置于管式炉中,在H2组成在30%的H2和He组成的氛围中还原,还原温度为600℃,还原时间为8h。得到还原的负载Mn-Co双过渡金属单原子的ACF催化剂。
催化剂性能评价。废气中二氯甲烷浓度为400mg/m3,空气占比60%,空速为100000h-1。二氯甲烷去除效率达到80%以上,稳定时间超过80h。
Claims (10)
1.一种常温降解VOCs的负载双过渡金属单原子的ACF催化剂的制备方法,其特征在于包括以下步骤:
步骤一、ACF的预处理:
将ACF浸没在体积浓度为3-30%的HCl溶液中,并将溶液置于40-100℃水浴锅中反应2-10h,然后取出ACF,并用蒸馏水洗涤至中性,自然晾干,所述ACF的比表面积为800-3000m2/g,外表面积为0.2-2.0m2/g;
步骤二、浸渍负载双过渡金属:
取双过渡金属可溶性盐,加蒸馏水溶解,待完全溶解后加入预处理后的ACF,超声分散0.5-4h,超声结束后静置2-30h,然后取出,在50-120℃烘箱中烘干,两种过渡金属元素摩尔比为(0.1-10):1,双过渡金属元素总质量与ACF质量比为0.1-5%;
步骤三、程序升温煅烧:
将烘干后的负载双过渡金属元素的ACF放入程序升温马弗炉中,以1-15℃/min升到100-600℃,然后恒温2-10h,制得负载双过渡金属氧化物的ACF催化剂;
步骤四、H2还原:
将制备的负载双过渡金属氧化物的ACF催化剂置于管式炉中,在H2的体积百分比为1-40%的H2和He组成的氛围中还原,还原温度为100-700℃,还原时间为0.1-10h,得到还原的双过渡金属单原子ACF催化剂。
2.根据权利要求1所述的负载双过渡金属单原子的ACF催化剂的制备方法,其特征在于:所述的过渡金属元素包括Mn、Fe、Cu、Ni、Co、Zn、Cr中的任意两种。
3.根据权利要求2所述的负载双过渡金属单原子的ACF催化剂的制备方法,其特征在于:所述的双过渡金属元素为Cu-Cr,Mn-Fe,Fe-Cu,Ni-Co,Fe-Zn或者Mn-Co。
4.根据权利要求1-3之一所述的负载双过渡金属单原子的ACF催化剂的制备方法,其特征在于:所述的过渡金属可溶性盐为过渡金属的硝酸盐。
5.根据权利要求4所述的负载双过渡金属单原子的ACF催化剂的制备方法,其特征在于:所述的双过渡金属元素摩尔比为(0.5-3):1,双过渡金属元素总质量与ACF质量比为0.5-1%。
6.根据权利要求1所述的负载双过渡金属单原子的ACF催化剂的制备方法,其特征在于:HCl体积浓度为8-15%。
7.根据权利要求1所述的负载双过渡金属单原子的ACF催化剂的制备方法,其特征在于:所述的步骤一中溶液置于60-80℃水浴锅中反应3-6h。
8.根据权利要求1所述的负载双过渡金属单原子的ACF催化剂的制备方法,其特征在于:所述的步骤二中超声分散时间为1-3h。
9.根据权利要求1所述的负载双过渡金属单原子的ACF催化剂的制备方法,其特征在于:将负载双过渡金属元素的ACF放入程序升温马弗炉中,以3-6℃/min升到200-400℃,然后恒温4-8h。
10.根据权利要求1所述的负载双过渡金属单原子的ACF催化剂的制备方法,其特征在于:H2在H2和He组成的氛围中的体积百分比为5-20%,还原温度为200-400℃,还原时间为0.5-4h。
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