Zhi-Jun Li

Enhancement of the Efficiency of Photocatalytic Reduction of Protons to Hydrogen via Molecular Assembly

Conspectus One of the best solutions for meeting future energy demands is the conversion of water into hydrogen fuel using solar energy. The splitting of water into molecular hydrogen (H2) and oxygen (O2) using light involves two half-reactions: the oxidation of water to O2 and the reduction of protons to H2. To take advantage of the full range of the solar spectrum, researchers have extensively investigated artificial photosynthesis systems consisting of two photosensitizers and two catalysts with a Z-configuration: one photosensitizer-catalyst pair for H2 evolution and the other for O2 evolution. This type of complete artificial photosynthesis system is difficult to build and optimize; therefore, researchers typically study the reductive half-reaction and the oxidative half-reaction separately. To study the two half-reactions, researchers use a sacrificial electron donor to provide electrons for the reductive half-reaction, and a sacrificial electron acceptor to capture electrons for the oxidative half-reaction. After optimization, they can eliminate the added donors and acceptors as the two half reactions are coupled to a complete photocatalytic water spitting system. Most photocatalytic systems for the H2 evolution half-reaction consist of a photosensitizer, a catalyst, and a sacrificial electron donor. To promote photoinduced electron transfer and photocatalytic H2 production, these three components should be assembled together in a controlled manner. Researchers have struggled to design a photocatalytic system for H2 evolution that uses earth-abundant materials and is both efficient and durable. This Account reviews advances our laboratory has made in the development of new systems for photocatalytic H evolution that uses earth-abundant materials and is both efficient and durable. We used organometallic complexes and quantum-confined semiconductor nanocrystals (QDs) as photosensitizers, and [FeFe]-H2ase mimics and inorganic transition metal salts as catalysts to construct photocatalytic systems with sacrificial electron donors. Covalently linked Re(I) complex-[FeFe]-H2ase mimic dyads and ferrocene-Re(I) complex-[FeFe]-H2ase mimic triads could photocatalyze H2 production in organic solutions, but these photocatalytic systems tended to decompose. We also constructed several assemblies of CdTe and CdSe QDs as photosensitizers with [FeFe]-H2ase mimics as catalysts. These assemblies produced H2 in aqueous solutions photocatalytically and efficiently, with turnover numbers (TONs) up to tens of thousands. Assemblies of 3-mercaptopropionic acid (MPA)-capped CdTe QDs with Co(2+) ions formed Coh-CdTe hollow nanospheres, and MPA capped-CdSe QDs with Ni(+) ions produced Nih-CdSe/CdS core/shell hybrids in situ in aqueous solutions upon irradiation. The resulting photocatalytic systems proved robust for H2 evolution. These systems showed excellent activity and impressive durability in the photocatalytic reaction, suggesting that they can serve as a valuable part of an overall water splitting system.

A Cascade Cross-Coupling Hydrogen Evolution Reaction by Visible Light Catalysis

Cross-dehydrogenative-coupling reaction has long been recognized as a powerful tool to form a C-C bond directly from two different C-H bonds. Most current processes are performed by making use of stoichiometric amounts of oxidizing agents. We describe here a new type of reaction, namely cross-coupling hydrogen evolution (CCHE), with no use of any sacrificial oxidants, and only hydrogen (H2) is generated as a side product. By combining eosin Y and a graphene-supported RuO2 nanocomposite (G-RuO2) as a photosensitizer and a catalyst, the desired cross-coupling products and H2 are achieved in quantitative yields under visible light irradiation at room temperature.

Mechanistic Insights into the Interface‐Directed Transformation of Thiols into Disulfides and Molecular Hydrogen by Visible‐Light Irradiation of Quantum Dots

Quantum dots (QDs) offer new and versatile ways to harvest light energy. However, there are few examples involving the utilization of QDs in organic synthesis. Visible-light irradiation of CdSe QDs was found to result in virtually quantitative coupling of a variety of thiols to give disulfides and H2 without the need for sacrificial reagents or external oxidants. The addition of small amounts of nickel(II) salts dramatically improved the efficiency and conversion through facilitating the formation of hydrogen atoms, thereby leading to faster regeneration of the ground-state QDs. Mechanistic studies reveal that the coupling reaction occurs on the QD surfaces rather than in solution and offer a blueprint for how these QDs may be used in other photocatalytic applications. Because no sacrificial agent or oxidant is necessary and the catalyst is reusable, this method may be useful for the formation of disulfide bonds in proteins as well as in other systems sensitive to the presence of oxidants.

Chitosan confinement enhances hydrogen photogeneration from a mimic of the diiron subsite of [FeFe]-hydrogenase

Nature has created [FeFe]-hydrogenase enzyme as a hydrogen-forming catalyst with a high turnover rate. However, it does not meet the demands of economically usable catalytic agents because of its limited stability and the cost of its production and purification. Synthetic chemistry has allowed the preparation of remarkably close mimics of [FeFe]-hydrogenase but so far failed to reproduce its catalytic activity. Most models of the active site represent mimics of the inorganic cofactor only, and the enzyme-like reaction that proceeds within restricted environments is less well understood. Here we report that chitosan, a natural polysaccharide, improves the efficiency and durability of a typical mimic of the diiron subsite of [FeFe]-hydrogenase for photocatalytic hydrogen evolution. The turnover number of the self-assembling system increases ~4,000-fold compared with the same system in the absence of chitosan. Such significant improvements to the activity and stability of artificial [FeFe]-hydrogenase-like systems have, to our knowledge, not been reported to date.

An Exceptional Artificial Photocatalyst, Nih‐CdSe/CdS Core/Shell Hybrid, Made In Situ from CdSe Quantum Dots and Nickel Salts for Efficient Hydrogen Evolution

A novel hybrid Nih -CdSe/CdS core/shell quantum dot is a simple and exceptional artificial photocatalyst for H2 production from 2-propanol aqueous solution. Studies on the nature of the artificial photocatalyst and mechanism for H2 production demonstrate that the synthetic strategy is general and the artificial photocatalyst holds promise for light capture, electron transfer, and catalysis at the surface of the Nih -CdSe/CdS core/shell quantum dots, leading to a self-healing system for H2 evolution in harmony.

Cross-coupling hydrogen evolution reaction in homogeneous solution without noble metals.

A highly efficient noble-metal-free homogeneous system for a cross-coupling hydrogen evolution (CCHE) reaction is developed. With cheap, earth-abundant eosin Y and molecular catalyst Co(dmgH)2Cl2, good to excellent yields for coupling reactions with a variety of isoquinolines and indole substrates and H2 have been achieved without any sacrificial oxidants. Mechanistic insights provide rich information on the effective, clean, and economic CCHE reaction.

Interface-directed assembly of a simple precursor of [FeFe]–H2ase mimics on CdSe QDs for photosynthetic hydrogen evolution in water

To prepare a water-soluble catalyst for photocatalytic hydrogen (H2) evolution, a simple hydrophobic precursor of [FeFe]–H2ase mimics, Fe2S2(CO)6, has been successfully assembled on the surface of CdSe QDs using an interface-directed approach in aqueous/organic solution. The resulting photocatalyst shows the highest efficiency known to date for H2 evolution with a turnover number (TON) of 8781 vs. Fe2S2(CO)6 and an initial turnover frequency (TOF) of 596 h−1 under visible light irradiation in water.

A robust “artificial catalyst” in situ formed from CdTe QDs and inorganic cobalt salts for photocatalytic hydrogen evolution

A simple hollow-structured “artificial catalyst” in situ formed from CdTe QDs and CoCl2·6H2O in aqueous ascorbic acid solution has shown exceptional activity and stability for photocatalytic H2 evolution (25 μmol h−1 mg−1, 219 100 mol H2 per mol QDs or 59 600 mol H2 per mol Co turnovers, respectively) under visible light irradiation for 70 h.

A solution-processed, mercaptoacetic acid-engineered CdSe quantum dot photocathode for efficient hydrogen production under visible light irradiation

We describe here a simple, efficient and stable CdSe QDs/NiO photocathode engineered using a molecular linker, mercaptoacetic acid (MAA), for H2 generation from neutral water. This protocol does not require any sacrificial reagent, external cocatalyst, protecting layer and buffer solution as well. Upon visible-light irradiation, photocurrent as high as −60 μA cm−2 is achieved at a bias of −0.1 V vs. NHE in 0.1 M Na2SO4 (pH 6.8). Simultaneously, the photocathode evolves H2 consistently for 45 h with ∼100% Faradic efficiency, which is unprecedented in the field of sensitized photocathodes for H2 production. A mechanistic study reveals that the exceptional performance is derived from the efficient hole transfer process.

Activation of CH Bonds through Oxidant‐Free Photoredox Catalysis: Cross‐Coupling Hydrogen‐Evolution Transformation of Isochromans and β‐Keto Esters

The direct and controlled activation of a C(sp(3) )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.