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121.
The electrochemical carbon dioxide reduction reaction (CO2RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels. Single atom catalysts (SACs) are encouraging to catalyze the electrochemical CO2RR due to the tunable electronic structure of the central metal atoms, which can regulate the adsorption energy of reactants and reaction intermediates. Moreover, SACs form a bridge between homogeneous and heterogeneous catalysts, providing an ideal platform to explore the reaction mechanism of electrochemical reactions. In this review, we first discuss the strategies for promoting the CO2RR performance, including suppression of the hydrogen evolution reaction (HER), generation of C1 products and formation of C2+ products. Then, we summarize the recent developments in regulating the structure of SACs toward the CO2RR based on the above aspects. Finally, several issues regarding the development of SACs for the CO2RR are raised and possible solutions are provided.The electrochemical carbon dioxide reduction reaction (CO2RR) offers a promising solution to mitigate carbon emission and at the same time generate valuable carbonaceous chemicals/fuels. 相似文献
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Yongjin Xu Beisheng Kang Xuetai Chen Yuanba Cai Yonghan Hu Jiaxi Lu 《Journal of Cluster Science》1992,3(2):167-177
Complex Co4mp4(Hmp)(PBu
3
n
)3 (1) (H2mp=o-Mercaptophenol) was obtained from the reaction of CoCl2 and H2mp in the presence of PBu
n
3 and NaOMe with restricted oxidation. X-ray crystallographic data: triclinic, space group
,a=15.657(5) Å,b=20.469(8) Å,c=12.383(3) Å,=93.59(3)°, =112.45(2)°, =93.65(3)°,V=3648.7 Å3,Z=2,D
c
=1.33 g/cm3;R=0.065. The molecule consists of four cobalt atoms unsymmetrically bridged by S or S and O atoms from four of the five mp ligands. The fifth mp is terminally chelated to Co(4) which is in a distorted trigonal bipyramidal geometry, while Co(1)-Co(3) are square pyramidal. Atom Co(2) is bonded to Co(1) and Co(3) (average distance 2.632 Å) with strong interactions while Co(4) is only loosely connected to Co(1) (3.402 Å) and Co(3) (2.956 Å) through oxygen bridges and a hydrogen bond. The different coordination environments O2S2P, S4P, and O4S of the cobalt atoms make the molecule highly asymmetrical. XPS fitting data confirm the difference of the Co atoms. FABMS data indicate the possible fragmentation routes. The complex is paramagnetic with eff=5.2 B. 相似文献
125.
Summary We provide a convergence rate analysis for a variant of the domain decomposition method introduced by Gropp and Keyes for solving the algebraic equations that arise from finite element discretization of nonsymmetric and indefinite elliptic problems with Dirichlet boundary conditions in 2. We show that the convergence rate of the preconditioned GMRES method is nearly optimal in the sense that the rate of convergence depends only logarithmically on the mesh size and the number of substructures, if the global coarse mesh is fine enough.This author was supported by the National Science Foundation under contract numbers DCR-8521451 and ECS-8957475, by the IBM Corporation, and by the 3M Company, while in residence at Yale UniversityThis author was supported by the Applied Mathematical Sciences subprogram of the Office of Energy Research, U.S. Department of Energy under Contract W-31-109-Eng-38This author was supported by the National Science Foundation under contract number ECS-8957475, by the IBM Corporation, and by the 3M Company 相似文献
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127.
Wu G Cai ZW Bednarz MS Kocy OR Gavai AV Godfrey JD Washburn WN Poss MA Sher PM 《Journal of combinatorial chemistry》2005,7(1):99-108
Benzylic and allylic organozinc and Grignard reagents have been added to resin-bound imines to provide alpha-branched secondary amines. Many functional groups, including electrophilic groups, were compatible with this methodology. Three modules--a resin-bound primary amine, an aromatic aldehyde, and the organometallic--were independently varied to produce a combinatorial library of alpha-branched secondary amines designed as beta-3 adrenergic receptor agonists. 相似文献
128.
The title reactions occur stepwise, the first and fastest being MeReO3 + Eu2+ --> Re(VI) + Eu3+ (k298 = 2.7 x 10(4) L mol(-1) s(-1)), followed by rapid reduction of Re(VI) by Eu2+ to MeReO2. The latter species is reduced by a third Eu2+ to Re(IV), a metastable species characterized by an intense charge transfer band, epsilon410 = 910 L mol(-1) cm(-1) at pH 1; the rate constant for its formation is 61.3 L mol(-1) s(-1), independent of [H+]. Yet another reduction step occurs, during which hydrogen is evolved at a rate v = k[Re(IV)][Eu2+][H+](-1), with k = 2.56 s(-1) at mu = 0.33 mol L(-1). The 410 nm Re(IV) species bears no ionic charge on the basis of the kinetic salt effect. We attribute hydrogen evolution to a reaction between H-ReVO and H3O+, where the hydrido complex arises from the unimolecular rearrangement of Re(III)-OH in a reaction that cannot be detected directly. Chromium(II) ions do not evolve H2, despite E(Cr) degrees approximately E(EU) degrees. We attribute this lack of reactivity to the Re(IV) intermediate being captured as [Re(IV)-O-Cr(III)]2+, with both metals having substitutionally inert d3 electronic configurations. Hydrogen evolution occurs in chloride or triflate media; with perchlorate present, MeReO2 reduces perchlorate to chloride, as reported previously [Abu-Omar, M. M.; Espenson, J. H. Inorg. Chem. 1995, 34, 6239-6240]. 相似文献
129.
Stereochemical effects in supramolecular self-assembly at surfaces: 1-D versus 2-D enantiomorphic ordering for PVBA and PEBA on Ag(111) 总被引:2,自引:0,他引:2
Barth JV Weckesser J Trimarchi G Vladimirova M De Vita A Cai C Brune H Günter P Kern K 《Journal of the American Chemical Society》2002,124(27):7991-8000
We present investigations on noncovalent bonding and supramolecular self-assembly of two related molecular building blocks at a noble metal surface: 4-[trans-2-(pyrid-4-yl-vinyl)]benzoic acid (PVBA) and 4-[(pyrid-4-yl-ethynyl)]benzoic acid (PEBA). These rigid, rodlike molecules comprising the same complementary moieties for hydrogen bond formation are comparable in shape and size. For PVBA, the ethenylene moiety accounts for two-dimensional (2-D) chirality upon confinement to a surface; PEBA is linear and thus 2-D achiral. Molecular films were deposited on a Ag(111) surface by organic molecular beam epitaxy and characterized by scanning tunneling microscopy. At low temperatures (around 150 K), both species form irregular networks of flat lying molecules linked via their endgroups in a diffusion-limited aggregation process. In the absence of kinetic limitations (adsorption or annealing at room temperature), hydrogen-bonded supramolecular assemblies form which are markedly different. With PVBA, enantiomorphic twin chains in two mirror-symmetric species running along a high-symmetry direction of the substrate lattice form by diastereoselective self-assembly of one enantiomer. The chirality signature is strictly correlated between neighboring twin chains. Enantiopure one-dimensional (1-D) supramolecular nanogratings with tunable periodicity evolve at intermediate coverages, reflecting chiral resolution in micrometer domains. In contrast, PEBA assembles in 2-D hydrogen-bonded islands, which are enantiomorphic because of the orientation of the supramolecular arrangements along low-symmetry directions of the substrate. Thus, for PVBA, chiral molecules form 1-D enantiomorphic supramolecular structures because of mesoscopic resolution of a 2-D chiral species, whereas with PEBA, the packing of an achiral species causes 2-D enantiomorphic arrangements. Model simulations of supramolecular ordering provide a deeper understanding of the stability of these systems. 相似文献
130.