A thin‐film, two‐layer organic photovoltaiccell has been fabricated from copper phthalocyanine and a perylene tetracarboxylic derivative. A power conversion efficiency of about 1% has been achieved under simulated AM2 illumination. A novel feature of the device is that the charge‐generation efficiency is relatively independent of the bias voltage, resulting in cells with fill factor values as high as 0.65. The interface between the two organic materials, rather than the electrode/organic contacts, is crucial in determining the photovoltaicproperties of the cell.

Two‐layer organic photovoltaic cell

4.3. Reaction Mechanism 2373 4.4. Asymmetric Synthesis 2374 4.5. Outlook 2374 5. Alternating Polymerization of Oxiranes and CO2 2374 5.1. Reaction Outlines 2374 5.2. Catalyst 2376 5.3. Asymmetric Polymerization 2377 5.4. Immobilized Catalysts 2377 6. Synthesis of Urea and Urethane Derivatives 2378 7. Synthesis of Carboxylic Acid 2379 8. Synthesis of Esters and Lactones 2380 9. Synthesis of Isocyanates 2382 10. Hydrogenation and Hydroformylation, and Alcohol Homologation 2382

Transformation of carbon dioxide.

Owing to the increasing emissions of carbon dioxide (CO2), human life and the ecological environment have been affected by global warming and climate changes. To mitigate the concentration of CO2 in the atmosphere various strategies have been implemented such as separation, storage, and utilization of CO2. Although it has been explored for many years, hydrogenation reaction, an important representative among chemical conversions of CO2, offers challenging opportunities for sustainable development in energy and the environment. Indeed, the hydrogenation of CO2 not only reduces the increasing CO2 buildup but also produces fuels and chemicals. In this critical review we discuss recent developments in this area, with emphases on catalytic reactivity, reactor innovation, and reaction mechanism. We also provide an overview regarding the challenges and opportunities for future research in the field (319 references).

Recent advances in catalytic hydrogenation of carbon dioxide

Catalysis for the valorization of exhaust carbon: from CO2 to chemicals, materials, and fuels. technological use of CO2.

The increase in atmospheric carbon dioxide is linked to climate changes; hence there is an urgent need to reduce the accumulation of CO2 in the atmosphere. The utilization of CO2 as a raw material in the synthesis of chemicals and liquid energy carriers offers a way to mitigate the increasing CO2 buildup. This review covers six important CO2 transformations namely: chemical transformations, photochemical reductions, chemical and electrochemical reductions, biological conversions, reforming and inorganic transformations. Furthermore, the vast research area of carbon capture and storage is reviewed briefly. This review is intended as an introduction to CO2, its synthetic reactions and their possible role in future CO2 mitigation schemes that has to match the scale of man-made CO2 in the atmosphere, which rapidly approaches 1 teraton.

The teraton challenge. A review of fixation and transformation of carbon dioxide

Formic acid was catalytically synthesized from carbon dioxide and hydrogen by a combination of group VIII transition-metal complexes and bases in the presence of water far less than the equivalent amount of the catalyst.

Catalytic fixation of carbon dioxide to formic acid by transition-metal complexes under mild conditions

The catalytic addition of CO2 to butadiene by Pd-phosphine complexes to yield 2-ethylidenehept-5-en-4-olide was achieved in a polar, aprotic solvent such as dimethylformamide (DMF).

Reaction of carbon dioxide with butadiene catalysed by palladium complexes. Synthesis of 2-ethylidenehept-5-en-4-olide

Ni(cod)2–Ph2P(CH2)4PPh2 system (cod=1,5-cyclooctadiene) catalyzed the reaction of 3-hexyne, for example, with CO2 to give a CO2 incorporated product, i.e., tetraethyl-2-pyrone, in a fairly good yield together with novel two cyclotrimers of the alkyne having cyclopentadiene structures, i.e., pentaethyl-5-(1-propenyl)-1,3-cyclopentadiene and pentaethyl-5-allyl-1,3-cyclopentadiene. The novel two cyclotrimers were formed selectively on Ni(cod)2–PPh3 system under CO2, whereas under N2 the main trimer was hexaethylbenzene. A nickelacyclopentadiene intermediate has been proposed for the pyrone formation. The novel two cyclotrimers were also formed on the oligomerization catalyzed by a cationic nickel hydride complex, [HNi(Ph2PCH2CH2PPh2)2]OCOCF3, together with a novel dimer having a methylenecyclobutene structure, i.e., 1,2,4-triethyl-3-ethylidenecyclobutene. The effect of phosphine added and that of active-hydrogen compounds on the novel oligomerization are mentioned.

Reaction of dialkyl-substituted alkynes with carbon dioxide catalyzed by nickel(0) complexes. Incorporation of carbon dioxide in alkyne dimers and novel cyclotrimerization of the alkynes.

Axially dissymmetric bisphosphine ligands, (R)- and (S)-2,2′-bis(diphenylphosphinoamino)-1,1′-binaphthyl (BDPAB) and (R)-2,2′-bis[N-(diphenylphosphino)methylamino]-1,1′-binaphthyl (Me-BDPAB) were conveniently prepared from 2,2′-diamino-1,1′-binaphthyl The rhodium(I)-catalyzed asymmetric hydrogenation of α-acylamidoacrylic acids and esters gave the corresponding amino acids of up to 95% optical purity The sign of the centro-chirality of the product amino acids was always the same to that of the axial chirality of the ligand in both cases of BDPAB and Me-BDPAB

Axially dissymmetric bis(aminophosphine)s derived from 2,2'-diamino-1,1'-binaphthyl. Synthesis and application to rhodium(I)-catalyzed asymmetric hydrogenations.

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Harukichi Hashimoto

Papers

Catalytic fixation of carbon dioxide to formic acid by transition-metal complexes under mild conditions

Reaction of carbon dioxide with butadiene catalysed by palladium complexes. Synthesis of 2-ethylidenehept-5-en-4-olide

Reaction of dialkyl-substituted alkynes with carbon dioxide catalyzed by nickel(0) complexes. Incorporation of carbon dioxide in alkyne dimers and novel cyclotrimerization of the alkynes.

Axially dissymmetric bis(aminophosphine)s derived from 2,2'-diamino-1,1'-binaphthyl. Synthesis and application to rhodium(I)-catalyzed asymmetric hydrogenations.

Vat Dyes of Acenaphthene Series. IV. Condensation of Perylenetetracarboxylic Acid Anhydride with o-Phenylenediamine