人工光合作用相关分子电催化研究
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摘要
解决能源危机与环境污染的出路在于利用和开发可再生能源。人工光合作用是一种重要的可再生能源利用方式,可将太阳能转化为便于储运的化学燃料。在基于水分解制氢的人工光合作用研究中,分子电催化备受关注,其目标是模拟生物体内的酶催化过程,以有机金属配合物为催化剂,通过电化学或光电化学的方式将水分解为H2和02。本论文工作开展与人工光合作用相关的分子电催化研究,目标反应包括水氧化反应(WOR)、氢析出反应(HER)和氧还原反应(ORR)。我们设计并合成了27种有机金属配合物分子催化剂,研究其在有机介质和水溶液中的电催化行为；将优选的分子催化剂与无机氧化物半导体光电极相结合,探索其光电化学应用。取得的主要研究进展如下：
1.半夹心Ru配合物的水氧化电催化
水氧化反应(WOR)动力学缓慢,是制约水分解效率的关键因素。针对目前WOR分子催化剂普遍效率不高且较少应用于光电解水的现状,我们设计并合成5种准四面体构型的五甲基环戊二烯基Ru配合物分子(Rp*-L),通过改变L配体调控配合物的电子构型和中心Ru的电荷密度。此类分子催化剂可在碱性电解液中催化WOR,但对于水溶性Rp*-L分子,其催化活性越高自身越容易发生水解。我们优选出催化活性及稳定性俱佳的Cp*Ru(PPh3)2Cl]C1分子(Rp*-P2),通过吸附的方式将其固定在电极表面进行WOR电催化研究。结合差分电化学质谱(DEMS)研究表明,Rp*-P2/Au表面析出O2仅需350mV极化,是目前WOR分子催化剂中超电势最小的一种。
2.多吡啶Ru配合物的水氧化光电催化
上述Rp*-P2分子催化剂虽然具有较好的WOR催化活性,但与α-Fe2O3光阳极结合后,仍无法实现稳定的WOR光电催化。为解决这一问题,我们合成了具有较高抗氧化性且可以共价成键方式修饰到α-Fe2O3表面的准八面体多吡啶Ru配合物[Ru(tpy)(dcbpy)Cl]Cl (Rt-dcb)和环金属化Ru配合物[Ru(tpy)(pba)Cl](Rt-pba)。此类新型“分子催化剂/半导体”复合光阳极不存在传统“无机催化剂/半导体”光阳极的晶界电阻,且分子催化剂与半导体之间可通过异质结效应促进光生电荷分离,使WOR平台光电流密度显著提高。此外,环金属化配位场使Ruv中间态更易获得,增强了WOR催化活性。与未修饰催化剂的α-Fe2O3光阳极相比,Rt-pba/α-Fe2O3电极在光照下起波电势从0.9V负移至0.7V (vs. RHE),1.23V下光电流增大约140%。
3.多吡啶Ni、Co配合物的水还原电催化
水还原氢析出反应的分子电催化是一个备受关注的课题,目前多数HER分子催化剂只能用于非水体系的有机弱酸还原析氢。我们研究了一类多吡啶Ni、 Co配合物,从11种候选分子中筛选出6种可以在酸性到弱碱性水溶液中稳定催化HER的分子,包括[Ni(tpy)2](BF4)2、[Ni(tpy)(bpy)Cl]CK、[Co(tpy)(bpy)Cl]Cl、[Co(tpy)(dmbpy)Cl]Cl、[Co(tpy)(dcbpy)Cl]Cl和[Co(tpy)(phen)Cl]Cl。在非水体系中,这些分子催化有机弱酸还原析氢的TOF值在110～280s-1之间,优于常见的钴肟催化剂。在水溶液中,Co配合物的催化活性远高于相同结构的Ni配合物,且随配体拉电子能力的增强而进一步提高,HER起波超电势约500mV,与文献中为数不多可直接催化水还原HER的分子催化剂性能相当。
4.多吡啶Co配合物的水还原光电催化
如何将分子催化剂高载量地固定到电极表面一直是分子电催化研究的一个难题,我们发现一种利用邻二氮菲(phen)还原电聚合将[Co(tpy)(phen)Cl]Cl分子高载量固定至电极表面的方法。差分电化学质谱(DEMS)研究表明,这种聚[Co(tpy)(phen)Cl]Cl电极(PCo)在pH=3缓冲溶液中的析氢超电势仅370mV,极化470mV时TOF接近10s-1, TON不低于2.2x106,是目前报道的最好的HER分子催化剂之一。采用XPS等表征发现,PCo电极的活性中心仍然为Co配合物,并非Co金属或氧化物。将[Co(tpy)(phen)Cl]Cl聚合到Cu20光阴极表面,首次实现了分子催化剂与p型半导体相结合的光电化学水还原析氢。此PCo/Cu2O光阴极性质稳定,可在0V (vs. RHE)光照条件下长时间工作,HER光电流比Cu20电极增大50%以上。
5.多吡啶Cu配合物的氧还原电催化
氧还原反应(ORR)的分子电催化研究多基于Fe、Co卟啉和酞菁类化合物,但Cu在很多催化ORR的生物酶中都扮演着重要的角色。我们设计合成了7种Cu配合物分子：[Cu(bpy)2](ClO4)2、[Cu(dcbpy)2](ClO4)2、[Cu(bpy)3](ClO4)2、[Cu(tpy)(ClO4)](ClO4)、[Cu(tpy)(bpy)(H2O)](ClO4)2、[Cu(tpy)(dcbpy)(H2O)](ClO4)2和[Cu(tpy)2](ClO4)2。这些分子均能溶解于水溶液中催化ORR,其催化活性主要受生成Cu1中间体的热力学电势的影响,分子结构的影响并不显著。催化剂浓度较低时ORR以2e途径进行,随着催化剂浓度的提高反应电子数增大。从实验现象判断,此类Cu分子在催化ORR过程中可能主要起到氧化还原穿梭电对的作用,内球型的催化作用似乎不显著。
Exploiting sustainable energy is a key to rescuing the approaching crisis of energy and environment. As an important technology of sustainable energy, artificial photosynthesis aims at converting the solar energy into chemical energies, which are storable and transportable. In the study of artificial photosynthesis based on water splitting, tremendous research efforts have been devoted to the molecular electrocatalysis, in which organometallic complexes are employed as the catalyst to mimic the biocatalytic process of enzyme, and the water molecules are split electrochemically or photoelectrochemically into H2and O2. The theme of the present work is molecular electrocatalysis for reactions relevant to artificial photosynthesis, including the water oxidation reaction (WOR), the hydrogen evolution reaction (HER), and the oxygen reduction reaction (ORR). In this work, about27organometallic complexes were synthesized and studied; according to their electrochemical and catalytic behaviors in organic and aqueous media, high-performance molecules were screened and integrated with metal-oxide photoelectrodes for photoelectrochemical study. Major achievements of this research are summarized as follows:
1. Half-sandwich Ru complexes for electrocatalysis of WOR
At present, most molecular catalysts for the WOR are still inefficient and have rarely been applied in photoelectrochemical water splitting. We synthesized5types of pseudo-tetrahedral Ru complexes ([Cp*RuL2X]n+, abbreviated as Rp*-L) with different electronic configuration in ligand and different charge density at the Ru site. All the molecules are catalytic toward the WOR in basic media, but for those soluble in aqueous solutions, the more active in catalysis the less resistant to the hydrolysis. The [Cp*Ru(PPh3)2Cl]Cl molecule (Rp*-P2), which is relatively active and stable, was fixed onto the electrode surface for heterogeneous catalysis of WOR. Only with350mV in potential polarization, O2can be detected on the Rp*-P2/Au electrode surface by using differential electrochemical mass spectrometry (DEMS). This is among the best molecular catalysts for WOR reported thus far.
2. Polypyridyl cyclometalated Ru complexes for photoelectrocatalysis of WOR
To enhance the stability of molecular catalyst for photoelectrolysis, we synthesized pseudo-octahedral Ru complexes [Ru(tpy)(dcbpy)Cl]Cl (Rt-dcb) and [Ru(tpy)(pba)Cl](Rt-pba) which are oxidation tolerant and can be bound onto the surface of a-Fe2O3. Unlike the traditional "inorganic catalyst/semiconductor" contact, such a "molecular catalyst/semiconductor" interface is free from any grain boundary, and an electronic heterojunction can also be formed in between. These features have benefited the separation of the light-induced charges and thus increased the plateau photocurrent density. Due to the employment of electron-donating C-∧N ligand in Rt-pba, the active Ruv intermediate is more accessible, resulting in an enhanced catalytic activity toward the WOR. Specifically, upon bonding Rt-pba onto the a-Fe2O3surface, the onset potential of photoelectrolysis has shifted from0.9V to0.7V (vs. RHE) and the photocurrent at1.23V increased by ca.140%.
3. Polypyridyl Ni and Co complexes for electrocatalysis of HER
The molecular electrocatalysis for HER is a very active field in recent years, however, most molecular catalysts can only be used in organic media for the electroreduction of organic acid. We investigated a series of polypyridyl Ni and Co complexes, and6molecules, including [Ni(tpy)2](BF4)2,[Ni(tpy)(bpy)Cl]Cl,[Co(tpy)(bpy)Cl]Cl,[Co(tpy)(dmbpy)Cl]Cl,[Co(tpy)(dcbpy)Cl]Cl, and [Co(tpy)(phen)Cl]Cl, were found to be able to catalyze the HER in aqueous solutions, ranging from acid to weak base. In organic system, the turnover frequency (TOF) of the HER catalyzed by these molecules is about110～289s-1, greater than that of the traditional cobaloxime catalyst. In aqueous electrolytes, the catalytic activity of polypyridyl Co is much higher than that of the Ni molecules, and can even be increased by using stronger electron-withdrawing ligands. The overpotential of the HER is about500mV, comparable to the best record in the literature.
4. Polypyridyl Co complex for photoelectrocatalysis of HER
Among the challenges in molecular electrocatalysis is how to increase the catalyst loading on electrode surface. We found that, through the electrochemical polymerization of the1,10-phenanthroline (phen) ligand, the [Co(tpy)(phen)Cl]Cl catalyst can be fabricated on the electrode surface with a very high loading. The DEMS measurements showed that, on such a poly-[Co(tpy)(phen)Cl]Cl electrode (PCo), the overpotential of HER is only370mV in a buffer solution of pH=3, with the TOF being10s-1and a TON of ca.2.2×106, which is among the best molecular catalysts thus found for HER. Characterized by XPS, the active site in PCo was found to be still in molecular state, rather than in metallic or oxide states. By polymerizing the [Co(tpy)(phen)Cl]Cl onto a Cu2O photocathode, we have realized, for the first time, a molecular catalyst/p-type semiconductor photocathode for the HER, which can stably work at0V (vs. RHE) under illumination, with a HER photocurrent increased by50%, in comparison to that on a bare CU2O photocathode.
5. Polypyridyl Cu complexes for electrocatalysis of ORR
The ORR catalyzed by Fe and Co porphyrine or phthalocyanine has been intensively studied in comparison to Cu complexes, though the latter is known to play a key role in relevant biocatalytic process. We synthesized7types of polypyridyl Cu complexes, including [Cu(bpy)2](C104)2,[Cu(dcbpy)2](C104)2,[Cu(bpy)3](C104)2,[Cu(tpy)(C104)](ClO4),[Cu(tpy)(bpy)(H20)](ClO4)2,[Cu(tpy)(dcbpy)(H20)](ClO4)2, and [Cu(tpy)2](C104)2, and used them to catalyze the ORR in aqueous solutions. It turned out that the catalytic activity of these molecules toward the ORR was majorly affected by the electrode potential of the CuⅢ/Ⅰ couple, rather than the electronic property of the ligands. The reaction electron number of the ORR was2at low [Cu] and increases with the [Cu], indicating that the studied Cu complexes seemed to act as a redox shuttle for the ORR, rather than a catalyst of inner-sphere reaction.
1.半夹心Ru配合物的水氧化电催化
水氧化反应(WOR)动力学缓慢,是制约水分解效率的关键因素。针对目前WOR分子催化剂普遍效率不高且较少应用于光电解水的现状,我们设计并合成5种准四面体构型的五甲基环戊二烯基Ru配合物分子(Rp*-L),通过改变L配体调控配合物的电子构型和中心Ru的电荷密度。此类分子催化剂可在碱性电解液中催化WOR,但对于水溶性Rp*-L分子,其催化活性越高自身越容易发生水解。我们优选出催化活性及稳定性俱佳的Cp*Ru(PPh3)2Cl]C1分子(Rp*-P2),通过吸附的方式将其固定在电极表面进行WOR电催化研究。结合差分电化学质谱(DEMS)研究表明,Rp*-P2/Au表面析出O2仅需350mV极化,是目前WOR分子催化剂中超电势最小的一种。
2.多吡啶Ru配合物的水氧化光电催化
上述Rp*-P2分子催化剂虽然具有较好的WOR催化活性,但与α-Fe2O3光阳极结合后,仍无法实现稳定的WOR光电催化。为解决这一问题,我们合成了具有较高抗氧化性且可以共价成键方式修饰到α-Fe2O3表面的准八面体多吡啶Ru配合物[Ru(tpy)(dcbpy)Cl]Cl (Rt-dcb)和环金属化Ru配合物[Ru(tpy)(pba)Cl](Rt-pba)。此类新型“分子催化剂/半导体”复合光阳极不存在传统“无机催化剂/半导体”光阳极的晶界电阻,且分子催化剂与半导体之间可通过异质结效应促进光生电荷分离,使WOR平台光电流密度显著提高。此外,环金属化配位场使Ruv中间态更易获得,增强了WOR催化活性。与未修饰催化剂的α-Fe2O3光阳极相比,Rt-pba/α-Fe2O3电极在光照下起波电势从0.9V负移至0.7V (vs. RHE),1.23V下光电流增大约140%。
3.多吡啶Ni、Co配合物的水还原电催化
水还原氢析出反应的分子电催化是一个备受关注的课题,目前多数HER分子催化剂只能用于非水体系的有机弱酸还原析氢。我们研究了一类多吡啶Ni、 Co配合物,从11种候选分子中筛选出6种可以在酸性到弱碱性水溶液中稳定催化HER的分子,包括[Ni(tpy)2](BF4)2、[Ni(tpy)(bpy)Cl]CK、[Co(tpy)(bpy)Cl]Cl、[Co(tpy)(dmbpy)Cl]Cl、[Co(tpy)(dcbpy)Cl]Cl和[Co(tpy)(phen)Cl]Cl。在非水体系中,这些分子催化有机弱酸还原析氢的TOF值在110～280s-1之间,优于常见的钴肟催化剂。在水溶液中,Co配合物的催化活性远高于相同结构的Ni配合物,且随配体拉电子能力的增强而进一步提高,HER起波超电势约500mV,与文献中为数不多可直接催化水还原HER的分子催化剂性能相当。
4.多吡啶Co配合物的水还原光电催化
如何将分子催化剂高载量地固定到电极表面一直是分子电催化研究的一个难题,我们发现一种利用邻二氮菲(phen)还原电聚合将[Co(tpy)(phen)Cl]Cl分子高载量固定至电极表面的方法。差分电化学质谱(DEMS)研究表明,这种聚[Co(tpy)(phen)Cl]Cl电极(PCo)在pH=3缓冲溶液中的析氢超电势仅370mV,极化470mV时TOF接近10s-1, TON不低于2.2x106,是目前报道的最好的HER分子催化剂之一。采用XPS等表征发现,PCo电极的活性中心仍然为Co配合物,并非Co金属或氧化物。将[Co(tpy)(phen)Cl]Cl聚合到Cu20光阴极表面,首次实现了分子催化剂与p型半导体相结合的光电化学水还原析氢。此PCo/Cu2O光阴极性质稳定,可在0V (vs. RHE)光照条件下长时间工作,HER光电流比Cu20电极增大50%以上。
5.多吡啶Cu配合物的氧还原电催化
氧还原反应(ORR)的分子电催化研究多基于Fe、Co卟啉和酞菁类化合物,但Cu在很多催化ORR的生物酶中都扮演着重要的角色。我们设计合成了7种Cu配合物分子：[Cu(bpy)2](ClO4)2、[Cu(dcbpy)2](ClO4)2、[Cu(bpy)3](ClO4)2、[Cu(tpy)(ClO4)](ClO4)、[Cu(tpy)(bpy)(H2O)](ClO4)2、[Cu(tpy)(dcbpy)(H2O)](ClO4)2和[Cu(tpy)2](ClO4)2。这些分子均能溶解于水溶液中催化ORR,其催化活性主要受生成Cu1中间体的热力学电势的影响,分子结构的影响并不显著。催化剂浓度较低时ORR以2e途径进行,随着催化剂浓度的提高反应电子数增大。从实验现象判断,此类Cu分子在催化ORR过程中可能主要起到氧化还原穿梭电对的作用,内球型的催化作用似乎不显著。
Exploiting sustainable energy is a key to rescuing the approaching crisis of energy and environment. As an important technology of sustainable energy, artificial photosynthesis aims at converting the solar energy into chemical energies, which are storable and transportable. In the study of artificial photosynthesis based on water splitting, tremendous research efforts have been devoted to the molecular electrocatalysis, in which organometallic complexes are employed as the catalyst to mimic the biocatalytic process of enzyme, and the water molecules are split electrochemically or photoelectrochemically into H2and O2. The theme of the present work is molecular electrocatalysis for reactions relevant to artificial photosynthesis, including the water oxidation reaction (WOR), the hydrogen evolution reaction (HER), and the oxygen reduction reaction (ORR). In this work, about27organometallic complexes were synthesized and studied; according to their electrochemical and catalytic behaviors in organic and aqueous media, high-performance molecules were screened and integrated with metal-oxide photoelectrodes for photoelectrochemical study. Major achievements of this research are summarized as follows:
1. Half-sandwich Ru complexes for electrocatalysis of WOR
At present, most molecular catalysts for the WOR are still inefficient and have rarely been applied in photoelectrochemical water splitting. We synthesized5types of pseudo-tetrahedral Ru complexes ([Cp*RuL2X]n+, abbreviated as Rp*-L) with different electronic configuration in ligand and different charge density at the Ru site. All the molecules are catalytic toward the WOR in basic media, but for those soluble in aqueous solutions, the more active in catalysis the less resistant to the hydrolysis. The [Cp*Ru(PPh3)2Cl]Cl molecule (Rp*-P2), which is relatively active and stable, was fixed onto the electrode surface for heterogeneous catalysis of WOR. Only with350mV in potential polarization, O2can be detected on the Rp*-P2/Au electrode surface by using differential electrochemical mass spectrometry (DEMS). This is among the best molecular catalysts for WOR reported thus far.
2. Polypyridyl cyclometalated Ru complexes for photoelectrocatalysis of WOR
To enhance the stability of molecular catalyst for photoelectrolysis, we synthesized pseudo-octahedral Ru complexes [Ru(tpy)(dcbpy)Cl]Cl (Rt-dcb) and [Ru(tpy)(pba)Cl](Rt-pba) which are oxidation tolerant and can be bound onto the surface of a-Fe2O3. Unlike the traditional "inorganic catalyst/semiconductor" contact, such a "molecular catalyst/semiconductor" interface is free from any grain boundary, and an electronic heterojunction can also be formed in between. These features have benefited the separation of the light-induced charges and thus increased the plateau photocurrent density. Due to the employment of electron-donating C-∧N ligand in Rt-pba, the active Ruv intermediate is more accessible, resulting in an enhanced catalytic activity toward the WOR. Specifically, upon bonding Rt-pba onto the a-Fe2O3surface, the onset potential of photoelectrolysis has shifted from0.9V to0.7V (vs. RHE) and the photocurrent at1.23V increased by ca.140%.
3. Polypyridyl Ni and Co complexes for electrocatalysis of HER
The molecular electrocatalysis for HER is a very active field in recent years, however, most molecular catalysts can only be used in organic media for the electroreduction of organic acid. We investigated a series of polypyridyl Ni and Co complexes, and6molecules, including [Ni(tpy)2](BF4)2,[Ni(tpy)(bpy)Cl]Cl,[Co(tpy)(bpy)Cl]Cl,[Co(tpy)(dmbpy)Cl]Cl,[Co(tpy)(dcbpy)Cl]Cl, and [Co(tpy)(phen)Cl]Cl, were found to be able to catalyze the HER in aqueous solutions, ranging from acid to weak base. In organic system, the turnover frequency (TOF) of the HER catalyzed by these molecules is about110～289s-1, greater than that of the traditional cobaloxime catalyst. In aqueous electrolytes, the catalytic activity of polypyridyl Co is much higher than that of the Ni molecules, and can even be increased by using stronger electron-withdrawing ligands. The overpotential of the HER is about500mV, comparable to the best record in the literature.
4. Polypyridyl Co complex for photoelectrocatalysis of HER
Among the challenges in molecular electrocatalysis is how to increase the catalyst loading on electrode surface. We found that, through the electrochemical polymerization of the1,10-phenanthroline (phen) ligand, the [Co(tpy)(phen)Cl]Cl catalyst can be fabricated on the electrode surface with a very high loading. The DEMS measurements showed that, on such a poly-[Co(tpy)(phen)Cl]Cl electrode (PCo), the overpotential of HER is only370mV in a buffer solution of pH=3, with the TOF being10s-1and a TON of ca.2.2×106, which is among the best molecular catalysts thus found for HER. Characterized by XPS, the active site in PCo was found to be still in molecular state, rather than in metallic or oxide states. By polymerizing the [Co(tpy)(phen)Cl]Cl onto a Cu2O photocathode, we have realized, for the first time, a molecular catalyst/p-type semiconductor photocathode for the HER, which can stably work at0V (vs. RHE) under illumination, with a HER photocurrent increased by50%, in comparison to that on a bare CU2O photocathode.
5. Polypyridyl Cu complexes for electrocatalysis of ORR
The ORR catalyzed by Fe and Co porphyrine or phthalocyanine has been intensively studied in comparison to Cu complexes, though the latter is known to play a key role in relevant biocatalytic process. We synthesized7types of polypyridyl Cu complexes, including [Cu(bpy)2](C104)2,[Cu(dcbpy)2](C104)2,[Cu(bpy)3](C104)2,[Cu(tpy)(C104)](ClO4),[Cu(tpy)(bpy)(H20)](ClO4)2,[Cu(tpy)(dcbpy)(H20)](ClO4)2, and [Cu(tpy)2](C104)2, and used them to catalyze the ORR in aqueous solutions. It turned out that the catalytic activity of these molecules toward the ORR was majorly affected by the electrode potential of the CuⅢ/Ⅰ couple, rather than the electronic property of the ligands. The reaction electron number of the ORR was2at low [Cu] and increases with the [Cu], indicating that the studied Cu complexes seemed to act as a redox shuttle for the ORR, rather than a catalyst of inner-sphere reaction.
引文
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