CN109575086B - 一种钳形膦配体铱类金属催化剂及其制备方法和应用 - Google Patents
一种钳形膦配体铱类金属催化剂及其制备方法和应用 Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
- C07F15/004—Iridium compounds without a metal-carbon linkage
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2495—Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
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Abstract
Description
技术领域
本发明涉及电化学技术领域。更具体地,涉及一种钳形膦配体铱类金属催化剂及其制备方法和应用。
背景技术
化石燃料的大规模应用造成了CO2的过量排放,引发了全球生态环境变化,如温室效应和海洋酸化等,极大地影响了人类的生存与发展。目前解决人类所面临的CO2含量上升问题主要有两种方法:1)捕捉地球上的二氧化碳,使其消失;2)转化二氧化碳,使其成为有用的低的碳材料。
二氧化碳的电化学反应主要有两种:(1)直接电还原二氧化碳合成高附加值有机化学品,例如CH4,C2H4,HCOOH,CH3OH,HCHO等;(2)电化学还原CO2与有机物结合,生成羧基化产物等。分子催化剂作为电催化还原CO2的重要部分,被广泛的研究和应用。在分子催化剂中,铱、钌、钯等贵金属在电催化还原CO2方面具有非常好的效果,活性和选择性都很高,不仅具有环境和经济优势,而且提供了探索新的催化剂的机会。
因此,本发明提供了一种对称四齿膦配体铁类廉价金属催化剂及其制备方法和应用。
发明内容
本发明的第一个目的在于提供一种钳形膦配体铱类金属催化剂,该金属催化剂在电催化还原二氧化碳中对二氧化碳有高度的响应性,能有效地选择性地还原二氧化碳为甲酸,且在所有还原产物中,甲酸所占比例极高。
本发明的第二个目的在于提供一种钳形膦配体铱类金属催化剂的制备方法。
本发明的第三个目的在于提供一种钳形膦配体铱类金属催化剂在电催化还原二氧化碳中的应用。
为达到上述第一个目的,本发明采用下述技术方案:
一种钳形膦配体铱类金属催化剂,其特征在于,所述金属催化剂的结构为六配位的八面体模型结构,其结构式如下式I所示:
其中,R1、R2各自独立地选自氢、烷基、烷氧基、苯基、苄基、胺基、吡啶基或恶唑基;
L1、L2、L3各自独立地选自氢、烷基、三甲基硅基、胺基、亚胺基、烷氧基、苄基、乙腈基、四氢呋喃基或卤素;
Ln为第VIII族的金属元素。
优选地,所述R1、R2各自独立地表示1-6个碳原子的烷基。例如,包括但不限于各自独自地为叔丁基、异丙基等。
优选地,所述Ln选自VIII族的金属元素。
优选地,所述卤素选自F、Cl、Br或I中的一种。
为达到上述第二个目的,本发明采用下述技术方案:
一种钳形膦配体铱类金属催化剂的制备方法,包括如下步骤:
将M的胺溶液加入到2,6-二羟基吡啶盐酸盐的悬浊液中,得混合液;将该混合液在搅拌条件下,于氮气气氛中加热至70℃-90℃进行回流反应,反应完全后冷却至室温,过滤,取液体进行蒸馏,冷冻凝固后得钳形配体;
在搅拌的条件下,将Ln(coe)2Cl]2的悬浊液加入到所述钳形配体的乙腈溶液中,至溶液变为透明的橙黄色溶液;再将该透明的橙黄色溶液在氢气气氛中于2.5MPa-10MPa、90℃-120℃条件下反应完全,再冷却至室温,将得到的混合物过滤、取液体蒸馏、重结晶得到所述钳形膦配体铱类金属催化剂;
其中,所述M选自烷基氯化膦、烷氧基氯化膦、苯基氯化膦、苄基氯化膦、胺基氯化膦、吡啶基氯化膦或恶唑基氯化膦;
所述Ln(coe)2Cl]2中,Ln为第VIII族的金属元素,coe为环辛烯。
优选地,钳形配体的制备方法采用文献(Bernskoetter,W.H.H.,S.K.;Buzak,S.K.;Davis,Z.;White,P.S.;Swartz,R.;Goldberg,K.I.;Brookhart,M.,J.Am.Chem.Soc.2009,131,8603-8613.)中的方法制得。
优选地,因所述反应物2,6-二羟基吡啶盐酸盐具有怕水怕氧的性质,所述反应在手套箱中进行。
优选地,所述2,6-二羟基吡啶盐酸盐的悬浊液中的溶剂、Ln(coe)2Cl]2的悬浊液中的溶剂各自独立的选自乙腈、THF、甲苯。
优选地,所述M的胺溶液和2,6-二羟基吡啶盐酸盐的悬浊液的混合方式为:将前者逐滴加入后者中并不断搅拌;其中,所述滴加时的温度为10-25℃。其中对搅拌速率并无限定,不影响反应即可。
优选地,所述胺溶液中的胺为二乙胺、三乙胺、丙胺或苯胺。
为达到上述第三个目的,本发明提供一种钳形膦配体铱类金属催化剂在电催化还原二氧化碳中的应用。
本发明中所述金属催化剂对CO2有高度的响应性,能有效地选择性地还原二氧化碳为甲酸。当溶液为乙腈溶液时,在所有还原产物中,甲酸所占比例能达到95%。
优选地,该应用包括:将钳形膦配体铱类金属催化剂应用在电催化还原二氧化碳为甲酸。
优选地,所述应用具体包括:将四丁基六氟磷酸铵溶于乙腈得混合液J,将混合液J和对称四齿膦配体铁类金属催化剂混合得混合液K,通Ar扫电化学CV,换通二氧化碳扫电化学CV。
优选地,所述混合液J中四丁基六氟磷酸铵的浓度为100Mm-1M。
优选地,所述混合液K中对称四齿膦配体铁类金属催化剂的浓度为0.5mM-5mM。
优选地,所述通Ar扫电化学循环伏安曲线后,还包括向混合液K中加入水。
优选地,所述水和混合液K的体积比为1%-10%。
优选地,所述通Ar扫电化学CV的条件为:通入Ar的时间为5min-20min,扫速为10mv~100mv,所施加电压为-1.05V~-1.55V(V vs.NHE),通电电解的时间为1h-8h,气相色谱检测气相电解产物;液体旋干,做氢谱核磁,检测液相产物。
优选地,所述通二氧化碳扫电化学CV的条件为:通入CO2的时间为5min-20min,扫速为10mv-100mv,所施加电压为-1.25V~-1.65V(V vs.NHE),通电电解的时间为1h~8h,气相色谱检测气相电解产物;液体旋干,做氢谱核磁,检测液相产物。
另外,如无特殊说明,本发明中所用原料均可通过市售商购获得,本发明所记载的任何范围包括端值以及端值之间的任何数值以及端值或者端值之间的任意数值所构成的任意子范围。
本发明的有益效果如下:
本发明的钳形膦配体铱类金属催化剂能够有效选择性地还原二氧化碳为甲酸,其选择性能达到95%;且该金属催化剂几乎没有催化产氢的活性。
本发明所述的钳形膦配体铱类金属催化剂的制备方法中,支撑配体由一步实验即可制得,节省配体合成时间,操作简单,经济效率高、环保性好。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的说明。
图1示出本发明实施例1中钳形膦配体铱类配合物的合成路线。
图2示出本发明实施例1中钳形膦配体铱类配合物的1H谱示意图。
图3示出本发明实施例1中钳形膦配体铱类配合物的31P谱示意图。
图4示出本发明实施例2中钳形膦配体铱类配合物的晶体结构示意图。
图5示出本发明实施例3中钳形膦配体铱类配合物的电化学循环伏安曲线图。
图6示出本发明实施例4中Ar气氛下加入体积分数为0~10%vol的水时2.5mM钳形膦配体铱类配合物在0.1M四丁基六氟磷酸铵的乙腈中的电化学循环伏安曲线图。
图7示出本发明实施例5中CO2气氛下加入体积分数为0~10%vol的水时2.5mM钳形膦配体铱类配合物在0.1M四丁基六氟磷酸铵的乙腈中的电化学循环伏安曲线图。
图8示出本发明实施例6中CO2气氛下2.5mM钳形膦配体铱类配合物在0.1M四丁基六氟磷酸铵的乙腈中的恒电位电解曲线。
图9示出本发明实施例7中控制催化剂浓度为2.5Mm,不加水,变换不同电位-1.15Vvs.NHE~1.65V vs.NHE的产物分布。
图10示出本发明实施例8中控制电势为-1.35V vs.NHE,加入体积分数为0~10%vol的水时,钳形膦配体铱类配合物在0.1M四丁基六氟磷酸铵的乙腈中的电解产物分布。
图11示出本发明实施例9中控制电势为-1.35V vs.NHE,催化剂的浓度为0.5mmol-5mmol时,钳形膦配体铱类配合物在0.1M四丁基六氟磷酸铵的乙腈中的电解产物分布。
具体实施方式
为了更清楚地说明本发明,下面结合优选实施例和附图对本发明做进一步的说明。附图中相似的部件以相同的附图标记进行表示。本领域技术人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本发明的保护范围。
本发明中,制备方法如无特殊说明则均为常规方法,所述百分比如无特殊说明均为质量百分比,所述单位M如无特殊说明均为mol/L,所述反应条件如无特殊说明均为常温常压条件,所使用药品及溶剂均来自于市售,催化剂合成在手套箱中进行,THF,乙腈由溶剂纯化系统得到,去离子水由超纯水机Master-S15UV Water Purification system得到。其他情况未经说明则无需处理直接使用。
本发明中的电化学实验均用CHI 601E电化学工作站(CH Instruments,Inc.,TX)。三电极体系包括玻碳工作电极、铂丝对电极和银/硝酸银参比电极(BASi,10mM硝酸银,0.1M四丁基六氟磷酸铵的乙腈溶液,0.55V vs NHE),气体填充在两个分开的池子。在每次测试前,玻碳电极(BASi,7.1mm2)都用0.05μm铝浆打磨得到一镜像表面,之后用超纯水和丙酮超声。对于循环伏安实验,工作电极和对电极一侧,参比电极另一侧。对于电解实验,参比电极和对电极一侧,工作电极另一侧。加入二茂铁作为标定物质,通过加上0.55V转化成标准氢电势NHE。气相产物通过Varian 8610C-GC检测,其配备分子筛和PDHID检测器。电化学测试均是在温和的条件下进行,如无特殊声明,不会出现温度剧烈升高等意外情况。
实施例1
钳形膦配体铱类金属催化剂的制备,其合成路线如图1所示,具体包括如下步骤:
(1)制备钳形配体
在手套箱中,将反应物2,6-二羟基吡啶盐酸盐(1513.2mg,10mmol)倒入100mlSchlenk瓶中,加入50ml THF得到悬浊a,二叔丁基氯化膦(3440μL,18.12mmol)和三乙胺(7.68mL,55.12mmol)分别滴入到混合物a中,得到混合物b;将Schlenk瓶拿出手套箱,放入油浴锅中,回流,在搅拌状态下,将所述的装有混合物b的反应器在氮气氛围下加热至70℃,反应7天后将茄瓶取出,冷却至25℃,得到混合物c。将Schlenk瓶抽入手套箱中,过滤,取液体进行真空蒸馏得到油状固体,冷冻凝固后得到钳形配体,为白色固体,产率为71%。纯度由GC-MS检出为99.8%。
核磁归属如下:
1H NMR(d8-THF,400MHz,253K):δ7.50(t,J=7.2Hz,Ar-H,1H),6.75(d,J=7.6Hz,Ar-H,2H),1.15(d,J=11.2Hz,-C(CH3)3,36H).31P NMR(d8-THF,400MHz,253K):δ156.51(s).
(2)钳形膦配体铱类配合物的合成方法如下:
在手套箱中称取步骤(1)制备得到的配体(480mg,1.2mmol)于25ml单口瓶中,加入10ml乙腈成溶液A,[Ir(coe)2Cl]2(1.2mmol)加入5ml THF形成悬浊液B,将悬浊液B缓缓滴入到溶液A中,整个过程不断搅拌。在滴加的过程发现悬浊液不断溶解,最终变为透明的橙黄色溶液C,将所述的装有橙黄色溶液C的反应器在氢气氛围下加压到2.5MPa,加热至90℃继续搅拌12h至反应完全,冷却至25℃,得到混合物D。将装有D的反应瓶抽入手套箱中,过滤,取液体进行真空蒸馏得到淡黄色固体。固体粉末用乙腈跟乙醚做重结晶,析出浅黄色晶体,固液分离,将固体抽干即得到E,产率为90%。将E(314mg,500μmol)溶解在THF中,加入NaH(845mg,35mmol),不断搅拌20h至反应完全,过滤,取液体进行真空蒸馏得到黄色固体F,即为产物钳形膦配体铱类金属催化剂,产率为85%,所述钳形膦配体铱类金属催化剂的结构式如下所示:
核磁谱图如图2,图3所示。核磁归属如下:
1H NMR(THF-d8,400MHz):1H NMR(d8-THF,400MHz,253K):δ7.58(t,J=8Hz,Ar-H,1H),6.68(d,J=8Hz,Ar-H,2H),1.55(t,J=7.2Hz,-C(CH3)3,36H),-10.57(td=17.6Hz,4.8Hz,Ir-H,2H),-16.72(m,Ir-H,1H);31P NMR(d8-THF,400MHz,253K):δ204.87.
实施例2
实施例3
对实施例1制得的钳形膦配体铱类配合物进行电化学性能表征:
在2.5mL的0.1M四丁基六氟磷酸铵的乙腈中,加入实施例1制得的钳形膦配体铱类配合物,得混合液,其中混合液的浓度为2.5mM(即每L四丁基六氟磷酸铵的乙腈中含有2.5mmol的钳形膦配体铱类配合物),通10min Ar后,于100mV/s的扫速下扫电化学CV;之后,换通10min的二氧化碳后,于100mV/s的扫速下扫电化学CV。
表征结果如图5所示,化合物的循环伏安曲线(CV)在乙腈溶液中Ar或CO2下得到。在CO2下,体系的电流密度明显比Ar下增大,说明钳形膦配体铱类配合物能有效电催化还原CO2。
实施例4
检验Ar气氛下,加入不同体积分数的水对实施例1制得的钳形膦配体铱类配合物的电化学性能的影响,步骤如下:
在2.5mL 0.1M四丁基六氟磷酸铵的乙腈中,加入实施例1制得的钳形膦配体铱类配合物,得混合液,其中混合液的浓度为2.5mM(即每L四丁基六氟磷酸铵的乙腈中含有2.5mmol的钳形膦配体铱类配合物),通10min Ar后,于100mV/s的扫速下扫电化学CV。之后向混合液中加入不同体积分数的水,其中水分别占混合液体积的0%vol、1%vol、3%vol、5%vol、7%vol、10%vol,于100mV/s的扫速下扫电化学CV。
图6显示Ar下2.5mM 1-H3在0-10%水的乙腈中的CV。与干燥情况下相比,体系的峰高几乎没有变化,说明钳形膦配体铱类配合物不是产氢催化剂。
实施例5
检验CO2气氛下,加入不同体积分数的水对实施例1制得的钳形膦配体铱类配合物的电化学性能的影响,步骤如下:
向2.5mL 0.1M四丁基六氟磷酸铵的乙腈中,加入2.5mM的实施例1制得的钳形膦配体铱类配合物,然后分别加入0%vol、1%vol、3%vol、5%vol、7%vol、10%vol的水,通5min的二氧化碳后,于100mV/s的扫速下扫电化学CV。
结果如图7所示:
在CO2情况下,当水分数从0增加到10%时,体系的电流密度显著增大,说明水的加入能增大体系对CO2的电还原效果。
实施例6
控制电势电解实验:
在2.5mL 0.1M四丁基六氟磷酸铵的乙腈中,加入实施例1制得的钳形膦配体铱类配合物,得混合液,其中混合液的浓度为2.5mM(即每L四丁基六氟磷酸铵的乙腈中含有2.5mmol的钳形膦配体铱类配合物),通15min的二氧化碳后,封闭电解池,进行电解,当电解电量到1.0-2.0C时,停止电解,用进样针抽取2mL气相气体,打入气相色谱中,检测气相电解产物;之后取1mL液相液体,旋干,加入10微升的100mM的N,N-二甲基甲酰胺的乙腈溶液标样,做氢谱核磁,检测液相产物。
控制电势电催化(CPE)实验在-1.35V vs NHE下进行,在8h的电解过程中,其显示出相当稳定的电流密度。
如图8,在整个电解过程中,催化电流平均密度维持在平均4.5mA/cm2。这就显示出,在整个催化过程中,化合物钳形膦配体铱类配合物是稳定的。
实施例7
检验不同电位的影响,即方法步骤同实施例6,不同之处仅在于:控制电势分别为:-1.15V vs.NHE、-1.25V vs.NHE、-1.35V vs.NHE、-1.45V vs.NHE、-1.55V vs.NHE、-1.65V vs.NHE。电化学电解池中的产生的气体用气相色谱来分析,液相溶液用核磁NMR来进行表征。结果如图9所示,在-1.15V vs.NHE进行电解2h,产生甲酸的选择性最高到达95%。
实施例8
检验加入不同体积分数的水对电解产物的影响,即方法步骤同实施例6,不同之处仅在于:向混合液中分别加入体积分别为0%vol、1%vol、3%vol、5%vol、10%vol的水,然后再通二氧化碳进行电解。
控制电势电催化(CPE)实验在-1.35V vs NHE下进行,结果如图10所示,随着加水量逐渐增加,甲酸的法拉第效率降低,H2的法拉第效率逐渐升高,但甲酸仍然是绝对主产物。
实施例9
检验催化剂浓度对电解产物的影响,即方法步骤同实施例6,不同之处仅在于:控制混合液中催化剂浓度分别为0mM、0.5mM、1mM、2.5mM、5mM,然后再通二氧化碳进行电解。
控制电势电催化(CPE)实验在-1.35V vs NHE下进行,结果如图11所示,随着催化剂浓度逐渐增加,甲酸和H2的法拉第效率几乎都没有变化,催化剂浓度对产物分布影响不大。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定,对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,这里无法对所有的实施方式予以穷举,凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (5)
2.如权利要求1所述的钳形膦配体铱类金属催化剂的制备方法,其特征在于,包括如下步骤:
将M的胺溶液加入到2,6-二羟基吡啶盐酸盐的悬浊液中,得混合液;将该混合液在搅拌条件下,于氮气气氛中加热至70℃-90℃进行回流反应,反应完全后冷却至室温,过滤,取液体进行蒸馏,冷冻凝固后得钳形配体;
在搅拌的条件下,将[Ln(coe)2]Cl2的悬浊液加入到所述钳形配体的乙腈溶液中,至溶液变为透明的橙黄色溶液;再将该透明的橙黄色溶液在氢气气氛中于2.5MPa-10MPa、90℃-120℃条件下反应完全,再冷却至室温,将得到的混合物过滤、取液体蒸馏、重结晶得到所述钳形膦配体铱类金属催化剂;
其中,所述M选自1-6个碳原子的烷基氯化膦;
所述[Ln(coe)2]Cl2中,Ln为铱,coe为环辛烯。
3.根据权利要求2所述的制备方法,其特征在于,所述2,6-二羟基吡啶盐酸盐的悬浊液中的溶剂、[Ln(coe)2]Cl2的悬浊液中的溶剂各自独立的选自乙腈、THF、甲苯。
4.根据权利要求2所述的制备方法,其特征在于,所述胺溶液中的胺为二乙胺、三乙胺、丙胺或苯胺。
5.如权利要求1所述的钳形膦配体铱类金属催化剂在电催化还原二氧化碳中的应用。
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CN102558108A (zh) * | 2011-12-22 | 2012-07-11 | 南开大学 | 用铱-钳形配体络合物催化剂制备γ-戊内酯的方法 |
CN108276453A (zh) * | 2018-01-23 | 2018-07-13 | 中国科学院理化技术研究所 | 一种对称四齿膦配体铁类金属催化剂及其制备方法和应用 |
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CN102558108A (zh) * | 2011-12-22 | 2012-07-11 | 南开大学 | 用铱-钳形配体络合物催化剂制备γ-戊内酯的方法 |
CN108276453A (zh) * | 2018-01-23 | 2018-07-13 | 中国科学院理化技术研究所 | 一种对称四齿膦配体铁类金属催化剂及其制备方法和应用 |
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Title |
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Investigations of Iridium-Mediated Reversible C-H Bond Cleavage: Characterization of a 16-Electron Iridium(III) Methyl Hydride Complex;Wesley H. Bernskoetter等,;《J. AM. CHEM. SOC.》;20090602;第8603–8613页,尤其是第8607页右栏、第8612页右栏最后一段 * |
Mechanism of Hydrogenolysis of an Iridium−Methyl Bond: Evidence for a Methane Complex Intermediate;Jesús Campos等,;《J. Am. Chem. Soc.》;20130111;第135卷;第1217-1220页,尤其是第1219页图4 * |
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