共查询到20条相似文献,搜索用时 31 毫秒
1.
A Noble‐Metal‐Free Nickel(II) Polypyridyl Catalyst for Visible‐Light‐Driven Hydrogen Production from Water 下载免费PDF全文
Dr. Yong‐Jun Yuan Dr. Hong‐Wei Lu Ji‐Ren Tu Dr. Yong Fang Dr. Zhen‐Tao Yu Dr. Xiao‐Xing Fan Prof. Zhi‐Gang Zou 《Chemphyschem》2015,16(14):2925-2930
The complex [Ni(bpy)3]2+ (bpy=2,2′‐bipyridine) is an active catalyst for visible‐light‐driven H2 production from water when employed with [Ir(dfppy)2(Hdcbpy)] [dfppy=2‐(3,4‐difluorophenyl)pyridine, Hdcbpy=4‐carboxy‐2,2′‐bipyridine‐4′‐carboxylate] as the photosensitizer and triethanolamine as the sacrificial electron donor. The highest turnover number of 520 with respect to the nickel(II) catalyst is obtained in a 8:2 acetonitrile/water solution at pH 9. The H2‐evolution system is more stable after the addition of an extra free bpy ligand, owing to faster catalyst regeneration. The photocatalytic results demonstrate that the nickel(II) polypyridyl catalyst can act as a more effective catalyst than the commonly utilized [Co(bpy)3]2+. This study may offer a new paradigm for constructing simple and noble‐metal‐free catalysts for photocatalytic hydrogen production. 相似文献
2.
Three platinum(II) terpyridylacetylide charge-transfer complexes possessing a lone ancillary ligand systematically varied in phenylacetylide π-conjugation length, [Pt((t)Bu(3)tpy)([C≡CC(6)H(4)](n)H)]ClO(4) (n = 1-3), are evaluated as photosensitizers (PSs) for visible-light-driven (λ > 420 nm) hydrogen production in the presence of a cobaloxime catalyst and the sacrificial electron donor triethanolamine (TEOA). Excited-state reductive quenching of the PS by TEOA produces PS(-) (k(q) scales with the driving force as 1 > 2 > 3), enabling thermal electron transfer to the cobalt catalyst. The initial H(2) evolution is directly proportional to the incident photon flux and visible-light harvesting capacity of the sensitizer, 3 > 2 > 1. The combined data suggest that PSs exhibiting attenuated bimolecular reductive quenching constants with respect to the diffusion limit can overcome this deficiency through improved light absorption in homogeneous H(2)-evolving compositions. 相似文献
3.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(12):3377-3381
A ruthenium complex, porphyrin sensitizer, fullerene acceptor molecular pentad has been synthesized and a long‐lived hole–electron pair was achieved in aqueous solution by photoinduced multistep electron transfer: Upon irradiation by visible light, the excited‐state of a zinc porphyrin (1ZnP*) was quenched by fullerene (C60) to afford a radical ion pair, 1,3(ZnP.+‐C60.−). This was followed by the subsequent electron transfer from a water oxidation catalyst unit (RuII) to ZnP.+ to give the long‐lived charge‐separated state, RuIII‐ZnP‐C60.−, with a lifetime of 14 μs. The ZnP worked as a visible‐light‐harvesting antenna, while the C60 acted as an excellent electron acceptor. As a consequence, visible‐light‐driven water oxidation by this integrated photosynthetic model compound was achieved in the presence of sacrificial oxidant and redox mediator. 相似文献
4.
A Poly(cobaloxime)/Carbon Nanotube Electrode: Freestanding Buckypaper with Polymer‐Enhanced H2‐Evolution Performance 下载免费PDF全文
Dr. Bertrand Reuillard Dr. Julien Warnan Jane J. Leung David W. Wakerley Dr. Erwin Reisner 《Angewandte Chemie (International ed. in English)》2016,55(12):3952-3957
A freestanding H2‐evolution electrode consisting of a copolymer‐embedded cobaloxime integrated into a multiwall carbon nanotube matrix by π–π interactions is reported. This electrode is straightforward to assemble and displays high activity towards hydrogen evolution in near‐neutral pH solution under inert and aerobic conditions, with a cobalt‐based turnover number (TONCo) of up to 420. An analogous electrode with a monomeric cobaloxime showed less activity with a TONCo of only 80. These results suggest that, in addition to the high surface area of the porous network of the buckypaper, the polymeric scaffold provides a stabilizing environment to the catalyst, leading to further enhancement in catalytic performance. We have therefore established that the use of a multifunctional copolymeric architecture is a viable strategy to enhance the performance of molecular electrocatalysts. 相似文献
5.
Activation of CH Bonds through Oxidant‐Free Photoredox Catalysis: Cross‐Coupling Hydrogen‐Evolution Transformation of Isochromans and β‐Keto Esters 下载免费PDF全文
Ming Xiang Dr. Qing‐Yuan Meng Jia‐Xin Li Yi‐Wen Zheng Chen Ye Dr. Zhi‐Jun Li Dr. Bin Chen Prof. Dr. Chen‐Ho Tung Prof. Dr. Li‐Zhu Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(50):18080-18084
The direct and controlled activation of a C(sp3)?H bond adjacent to an O atom is of particular synthetic value for the conventional derivatization of ethers or alcohols. In general, stoichiometric amounts of an oxidant are required to remove an electron and a hydrogen atom of the ether for subsequent transformations. Herein, we demonstrate that the activation of a C?H bond next to an O atom could be achieved under oxidant‐free conditions through photoredox‐neutral catalysis. By using a commercial dyad photosensitizer (Acr+‐Mes ClO4?, 9‐mesityl‐10‐methylacridinium perchlorate) and an easily available cobaloxime complex (Co(dmgBF2)2?2 MeCN, dmg=dimethylglyoxime), the nucleophilic addition of β‐keto esters to oxonium species, which is rarely observed in photocatalysis, leads to the corresponding coupling products and H2 in moderate to good yields under visible‐light irradiation. Mechanistic studies suggest that both isochroman and the cobaloxime complex quench the electron‐transfer state of this dyad photosensitizer and that benzylic C?H bond cleavage is probably the rate‐determining step of this cross‐coupling hydrogen‐evolution transformation. 相似文献
6.
Oxygen‐Dependent Photocatalytic Water Reduction with a Ruthenium(imidazolium) Chromophore and a Cobaloxime Catalyst 下载免费PDF全文
Maxim Pfeifer Christian Reichardt Dieter Sorsche Dr. Maria Wächtler Prof. Dr. Jürgen Popp Prof. Dr. Benjamin Dietzek Prof. Dr. Sven Rau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(24):8240-8253
Detailed investigations of a photocatalytic system capable of producing hydrogen under pre‐catalytic aerobic conditions are reported. This system consists of the NHC precursor chromophore [Ru(tbbpy)2(RR′ip)][PF6]3 (abbreviated as Ru(RR′ip)[PF6]3; tbbpy=4,4′‐di‐tert‐butyl‐2,2′‐bipyridine, RR′ip=1,3‐disubstituted‐1H‐imidazo[4,5‐f][1,10]phenanthrolinium), the reduction catalyst Co(dmgH)2 (dmgH=dimethylglyoximato), and the electron donor ascorbic acid (AA). Screening studies with respect to solvent, cobaloxime catalyst, electron donor, pH, and concentrations of the individual components yielded optimized photocatalytic conditions. The system shows high activity based on Ru, with turnover numbers up to 2000 under oxygen‐free and pre‐catalytic aerobic conditions. The turnover frequency in the latter case was even higher than that for the oxygen‐free catalyst system. The Ru complexes show high photostability and their first excited state is primarily located on the RR′ip ligand. X‐ray crystallographic analysis of the rigid cyclophane‐type ligand dd(ip)2(Br)2 (dd(ip)2=1,1′,3,3′‐bis(2,3,5,6‐tetramethyl‐1,4‐phenylene)bis(methylene)bis(1H‐imidazo[4,5‐f][1,10]phenanthrolinium)) and the catalytic activity of its Ru complex [{(tbbpy)2Ru}2(μ‐dd(ip)2)][PF6]6 (abbreviated as Ru2(dd(ip)2)[PF6]6) suggest an intermolecular catalytic cycle. 相似文献
7.
Synthesis and Characterization of Donor–π‐Acceptor‐Based Porphyrin Sensitizers: Potential Application of Dye‐Sensitized Solar Cells 下载免费PDF全文
Mareedu Sreenivasu Akira Suzuki Dr. Mitsuhiro Adachi Challuri Vijay Kumar Dr. Bingi Srikanth S. Rajendar Dasa Rambabu Dr. Rangaraju Satish Kumar P. Mallesham Dr. N. Vijaya Bhaskar Rao Dr. M. Suresh Kumar Dr. P. Y. Reddy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(43):14074-14083
New porphyrin sensitizers based on donor–π‐acceptor (D‐π‐A) approach have been designed, synthesized, characterized by various spectroscopic techniques and their photovoltaic properties explored. N,N′‐Diphenylamine acts as donor, the porphyrin is the π‐spacer, and either carboxylic acid or cyanoacryclic acid acts as acceptor. All compounds were characterized by using 1H NMR spectroscopy, ESI‐MS, UV–visible emission spectroscopies as well as electrochemical methods. The presence of aromatic groups between porphyrin π‐plane and acceptor group push the absorption of both Soret and Q‐bands of porphyrin towards the red region. The electrochemical properties suggests that LUMO of these sensitizers above the TiO2 conduction band. Finally, the device was fabricated using liquid redox electrolyte (I?/I3?) and its efficiency was compared with that of a leading sensitizer. 相似文献
8.
A Periodic Mesoporous Organosilica‐Based Donor–Acceptor System for Photocatalytic Hydrogen Evolution
Masataka Ohashi Dr. Masao Aoki Dr. Ken‐ichi Yamanaka Kiyotaka Nakajima Dr. Tetsu Ohsuna Dr. Takao Tani Dr. Shinji Inagaki Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(47):13041-13046
A new solid‐sate donor–acceptor system based on periodic mesoporous organosilica (PMO) has been constructed. Viologen (Vio) was covalently attached to the framework of a biphenyl (Bp)‐bridged PMO. The diffuse reflectance spectrum showed the formation of charge‐transfer (CT) complexes of Bp in the framework with Vio in the mesochannels. The transient absorption spectra upon excitation of the CT complexes displayed two absorption bands due to radical cations of Bp and Vio species, which indicated electron transfer from Bp to Vio. The absorption bands slowly decayed with a half‐decay period of approximately 10 μs but maintained the spectral shape, thereby suggesting persistent charge separation followed by recombination. To utilize the charge separation for photocatalysis, Vio–Bp–PMO was loaded with platinum and its photocatalytic performance was tested. The catalyst successfully evolved hydrogen with excitation of the CT complexes in the presence of a sacrificial agent. In contrast, reference catalysts without either Bp–PMO or Vio gave no or little hydrogen generation, respectively. In addition, a homogeneous solution system of Bp molecules, methylviologen, and colloidal platinum also evolved no hydrogen, possibly due to a weaker electron‐donating feature of molecular Bp than that of densely packed Bp in Bp–PMO. These results indicated that densely packed Bp and Vio are essential for hydrogen evolution in this system and demonstrated the potential of PMO as the basis for donor–acceptor systems suitable for photocatalysis. 相似文献
9.
《Helvetica chimica acta》2018,101(4)
Photocatalytic hydrogen evolution by an artificial hydrogenase based on the biotin‐streptavidin technology is reported. A biotinylated cobalt pentapyridyl‐based hydrogen evolution catalyst (HEC) was incorporated into different mutants of streptavidin. Catalysis with [Ru(bpy)3]Cl2 as a photosensitizer (PS) and ascorbate as sacrificial electron donor (SED) at different pH values highlighted the impact of close lying amino acids that may act as a proton relay under the reaction conditions (Asp, Arg, Lys). In the presence of a close‐lying lysine residue, both, the rates were improved, and the reaction was initiated much faster. The X‐ray crystal structure of the artificial hydrogenase reveals a distance of 8.8 Å between the closest lying Co‐moieties. We thus suggest that the hydrogen evolution mechanism proceeds via a single Co centre. Our findings highlight that streptavidin is a versatile host protein for the assembly of artificial hydrogenases and their activity can be fine‐tuned via mutagenesis. 相似文献
10.
Gyanaranjan Prusty Amit K. Guria Indranil Mondal Anirban Dutta Dr. Ujjwal Pal Dr. Narayan Pradhan 《Angewandte Chemie (International ed. in English)》2016,55(8):2705-2708
A generic modular synthetic strategy for the fabrication of a series of binary‐ternary group II‐VI and group I‐III‐VI coupled semiconductor nano‐heterostructures is reported. Using Ag2Se nanocrystals first as a catalyst and then as sacrificial seeds, four dual semiconductor heterostructures were designed with similar shapes: CdSe‐AgInSe2, CdSe‐AgGaSe2, ZnSe‐AgInSe2, and ZnSe‐AgGaSe2. Among these, dispersive type‐II heterostructures are further explored for photocatalytic hydrogen evolution from water and these are observed to be superior catalysts than the binary or ternary semi‐conductors. Details of the chemistry of this modular synthesis have been studied and the photophysical processes involved in catalysis are investigated. 相似文献
11.
Clean Donor Oxidation Enhances the H2 Evolution Activity of a Carbon Quantum Dot–Molecular Catalyst Photosystem 下载免费PDF全文
Benjamin C. M. Martindale Evelyne Joliat Dr. Cyril Bachmann Prof. Dr. Roger Alberto Dr. Erwin Reisner 《Angewandte Chemie (International ed. in English)》2016,55(32):9402-9406
Carbon quantum dots (CQDs) are new‐generation light absorbers for photocatalytic H2 evolution in aqueous solution, but the performance of CQD‐molecular catalyst systems is currently limited by the decomposition of the molecular component. Clean oxidation of the electron donor by donor recycling prevents the formation of destructive radical species and non‐innocent oxidation products. This approach allowed a CQD‐molecular nickel bis(diphosphine) photocatalyst system to reach a benchmark lifetime of more than 5 days and a record turnover number of 1094±61 molH2 (molNi)?1 for a defined synthetic molecular nickel catalyst in purely aqueous solution under AM1.5G solar irradiation. 相似文献
12.
McCormick TM Calitree BD Orchard A Kraut ND Bright FV Detty MR Eisenberg R 《Journal of the American Chemical Society》2010,132(44):15480-15483
Rhodamine photosensitizers (PSs) substituting S or Se for O in the xanthene ring give turnover numbers (TONs) as high as 9000 for the generation of hydrogen via the reduction of water using [Co(III)(dmgH)(2)(py)Cl] (where dmgH = dimethylglyoximate and py = pyridine) as the catalyst and triethanolamine as the sacrificial electron donor. The turnover frequencies were 0, 1700, and 5500 mol H(2)/mol PS/h for O, S, and Se derivatives, respectively (Φ(H(2)) = 0%, 12.2%, and 32.8%, respectively), which correlates well with relative triplet yields estimated from quantum yields for singlet oxygen generation. Phosphorescence from the excited PS was quenched by the sacrificial electron donor. Fluorescence lifetimes were similar for the O- and S-containing rhodamines (~2.6 ns) and shorter for the Se analog (~0.1 ns). These data suggest a reaction pathway involving reductive quenching of the triplet excited state of the PS giving the reduced PS(-) that then transfers an electron to the Co catalyst. The longer-lived triplet state is necessary for effective bimolecular electron transfer. While the cobalt/rhodamine/triethanolamine system gives unprecedented yields of hydrogen for the photoreduction of water, mechanistic insights regarding the overall reaction pathway as well as system degradation offer significant guidance to developing even more stable and efficient photocatalytic systems. 相似文献
13.
Hironobu Ozawa Dr. Masayuki Kobayashi Bijitha Balan Dr. Shigeyuki Masaoka Dr. Ken Sakai Prof. Dr. 《化学:亚洲杂志》2010,5(8):1860-1869
The mechanism of photoinduced hydrogen evolution from water driven by the first photo‐hydrogen‐evolving molecular catalyst ( 1 ), given by a coupling of [Ru(bpy)2(5‐amino‐phen)]2+ and [PtCl2(4,4′‐dicarboxy‐bpy)] (bpy=2,2′‐bipyridine, phen=1,10‐phenanthroline), was investigated in detail. The H2 evolution rate was found to obey Michaelis–Menten enzymatic kinetics with regard to the concentration of EDTA (ethylenediamine tetra‐acetic acid disodium salt, sacrificial electron donor), which indicates that an ion‐pair formation between the dicationic 1 and the dianionic form of EDTA (pH 5) is a key step leading to H2 formation. A 2:1 coupling product of 1 and ethylenediamine (i.e., a {RuII2PtII2} complex 2 ) was found to show significantly higher photo‐hydrogen‐evolving (PHE) activity than 1 , which revealed the validity of the bimolecular activation proposed in our previous study. The PHE activity of 2 was also observed to be linear to the concentration of 2 , which indicates that H2 formation through the intermolecular path competes with the intramolecular path. Molecular orbital diagrams, conformational features, and Pt???H(water or acetic acid) hydrogen bonds were characterized by DFT calculations. 相似文献
14.
Du P Schneider J Li F Zhao W Patel U Castellano FN Eisenberg R 《Journal of the American Chemical Society》2008,130(15):5056-5058
Platinum(II) bi- and terpyridyl chloro complexes, Pt(dcbpy)Cl2 and [Pt(ttpy)Cl]+, where dcbpy = 4,4'-dicarboxyl-2,2'-bipyridine and ttpy = 4-tolyl-2,2':6',2'-terpyridine, are used to investigate the nature of the active catalyst for the photocatalytic production of hydrogen from water. In a Pt(II) chloro system that contains a sacrificial electron donor, either MeOH or triethanolamine (TEOA), and titanium dioxide (TiO2) as an electron relay, sizable amounts of H2 can be observed upon UV bandgap irradiation. The quantity of H2 can be significantly reduced in the presence of mercury under the same conditions. Using a known sensitizer, [Pt(ttpy)(phenylacetylide)]+ (1), combined with a Pt(II) chloro complex in a similar system, there is a substantial induction period until the evolution of H2, under visible light (lambda > 410 nm) irradiation. It is suggested that the Pt(II) chloro complexes are simply acting as precursors to Pt colloids that function as the H2 generating catalyst 相似文献
15.
[{Ni4(OH)3AsO4}4(B‐α‐PW9O34)4]28−: A New Polyoxometalate Structural Family with Catalytic Hydrogen Evolution Activity 下载免费PDF全文
Hongjin Lv Dr. Yingnan Chi Jan van Leusen Prof. Paul Kögerler Dr. Zheyuan Chen Dr. John Bacsa Dr. Yurii V. Geletii Weiwei Guo Prof. Tianquan Lian Prof. Craig L. Hill 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(48):17363-17370
A new structural polyoxometalate motif, [{Ni4(OH)3AsO4}4(B‐α‐PW9O34)4]28?, which contains the highest nuclearity structurally characterized multi‐nickel‐containing polyanion to date, has been synthesized and characterized by single‐crystal X‐ray diffraction, temperature‐dependent magnetism and several other techniques. The unique central {Ni16(OH)12O4(AsO4)4} core shows dominant ferromagnetic exchange interactions, with maximum χmT of 69.21 cm3 K mol?1 at 3.4 K. Significantly, this structurally unprecedented complex is an efficient, water‐compatible, noble‐metal‐free catalyst for H2 production upon visible light irradiation (photosensitizer=[Ir(ppy)2(dtbbpy)][PF6]; sacrificial electron donor=triethylamine or triethanolamine). The highest turnover number of approximately 580, corresponding to a best quantum yield of approximately 4.07 %, is achieved when using triethylamine as electron donor in the presence of water. The mechanism of this photodriven process has been probed by time‐solved luminescence and by static emission quenching. 相似文献
16.
A Water‐Soluble Copper–Polypyridine Complex as a Homogeneous Catalyst for both Photo‐Induced and Electrocatalytic O2 Evolution 下载免费PDF全文
Rui‐Juan Xiang Prof. Dr. Hong‐Yan Wang Zhi‐Juan Xin Dr. Cheng‐Bo Li Ya‐Xing Lu Dr. Xue‐Wang Gao Dr. Hua‐Ming Sun Prof. Dr. Rui Cao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(5):1602-1607
The water‐soluble polypyridine copper complex [Cu(F3TPA)(ClO4)2] [ 1 ; F3TPA=tris(2‐fluoro‐6‐pyridylmethyl)amine] catalyzes water oxidation in a pH 8.5 borate buffer at a relatively low overpotential of 610 mV. Assisted by photosensitizer and an electron acceptor, 1 also exhibits activity as a homogeneous catalyst for photo‐induced O2 evolution with a maximum turnover frequency (TOF) of (1.58±0.03)×10?1 s?1 and a maximum turnover number (TON) of 11.61±0.23. In comparison, the reference [Cu(TPA)(ClO4)2] [TPA=tris(2‐pyridylmethyl)amine] displayed almost no activity under either set of conditions, implying the crucial role of the ligand in determining the behavior of the catalyst. Experimental evidence indicate the molecular catalytic nature of 1 , leading to a potentially practical strategy to apply the copper complex in a photoelectrochemical device for water oxidation. 相似文献
17.
通过将磷配体与氨基硫脲结合进一步增加螯合配体的配位能力,并引入磺酸根增强其水溶性,合成了一个钴配合物Co-NSP(配体HNSP:4-[2-(2-二苯基膦-苯烯基)-氨基硫脲腙] 苯甲酸),利用其氧化还原特性开展均相体系的光驱动从水中制备氢气的研究.新的NSP三齿配体能够稳定低价的金属中心,有助于提升催化剂的催化性能.利用其与荧光素所构筑的光催化体系,在电子牺牲剂三乙胺存在下显示出良好的性能,光照6 h其TON(turnover number)可达2 000 mol H2每摩尔催化剂.为了研究和比较其性能特点,对这一光催化体系的 荧光滴定和氧化还原性能也进行了较细致的研究. 相似文献
18.
Dr. Shihuai Wang Tai Wu Shuyang Wu Dr. Jingjing Guo Dr. Ting He Dr. Yinglong Wu Dr. Wei Yuan Dr. Zhengyang Zhang Prof. Yong Hua Prof. Yanli Zhao 《Angewandte Chemie (International ed. in English)》2023,62(44):e202311082
We report an azide-functionalized cobaloxime proton-reduction catalyst covalently tethered into the Wurster-type covalent organic frameworks (COFs). The cobaloxime-modified COF photocatalysts exhibit enhanced photocatalytic activity for hydrogen evolution reaction (HER) in alcohol-containing solution with no presence of a typical sacrificial agent. The best performing cobaloxime-modified COF hybrid catalyzes hydrogen production with an average HER rate up to 38 μmol h−1 in ethanol/phosphate buffer solution under 4 h illumination. Ultrafast transient optical spectroscopy characterizations and charge carrier analysis reveal that the alcohol contents functioning as hole scavengers could be oxidized by the photogenerated holes of COFs to form aldehydes and protons. The consumption of the photogenerated holes thus suppresses exciton recombination of COFs and improves the ratio of free electrons that were effectively utilized to drive catalytic reaction for HER. This work demonstrates a great potential of COF-catalyzed HER using alcohol solvents as hole scavengers and provides an example toward realizing the accessibility to the scope of reaction conditions and a greener route for energy conversion. 相似文献
19.
通过将磷配体与氨基硫脲结合进一步增加螯合配体的配位能力,并引入磺酸根增强其水溶性,合成了一个钴配合物Co-NSP(配体HNSP:4-[2-(2-二苯基膦-苯烯基)-氨基硫脲腙]苯甲酸),利用其氧化还原特性开展均相体系的光驱动从水中制备氢气的研究。新的NSP三齿配体能够稳定低价的金属中心,有助于提升催化剂的催化性能。利用其与荧光素所构筑的光催化体系,在电子牺牲剂三乙胺存在下显示出良好的性能,光照6h其TON(turnover number)可达2000molH2每摩尔催化剂。为了研究和比较其性能特点,对这一光催化体系的荧光滴定和氧化还原性能也进行了较细致的研究。 相似文献
20.
Prof. Dr. Martin Goez Christoph Kerzig Robert Naumann 《Angewandte Chemie (International ed. in English)》2014,53(37):9914-9916
Hydrated electrons are highly aggressive species that can force chemical transformations of otherwise unreactive molecules such as the reductive detoxification of halogenated organic compounds. We present the first example of the sustainable production of hydrated electrons through a homogeneous catalytic cycle driven entirely by green light (532 nm, coinciding with the maximum of the terrestrial solar spectrum). The catalyst is a metal complex serving as a “container” for a radical anion. This active center is generated from a ligand through quenching by a sacrificial electron donor, is shielded by the complex such that it stores the energy of the photon for much longer than a free radical anion could, and is finally ionized by another photon to regenerate the ligand and recover the starting complex quantitatively. The sacrificial donor can be a bioavailable reagent such as ascorbic acid. 相似文献