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Journal ArticleDOI: 10.1021/JACS.0C11450

Enhanced Cuprophilic Interactions in Crystalline Catalysts Facilitate the Highly Selective Electroreduction of CO2 to CH4.

02 Mar 2021-Journal of the American Chemical Society (American Chemical Society (ACS))-Vol. 143, Iss: 10, pp 3808-3816
Abstract: Cu(I)-based catalysts have proven to play an important role in the formation of specific hydrocarbon products from electrochemical carbon dioxide reduction reaction (CO2RR). However, it is difficult to understand the effect of intrinsic cuprophilic interactions inside the Cu(I) catalysts on the electrocatalytic mechanism and performance. Herein, two stable copper(I)-based coordination polymer (NNU-32 and NNU-33(S)) catalysts are synthesized and integrated into a CO2 flow cell electrolyzer, which exhibited very high selectivity for electrocatalytic CO2-to-CH4 conversion due to clearly inherent intramolecular cuprophilic interactions. Substitution of hydroxyl radicals for sulfate radicals during the electrocatalytic process results in an in situ dynamic crystal structure transition from NNU-33(S) to NNU-33(H), which further strengthens the cuprophilic interactions inside the catalyst structure. Consequently, NNU-33(H) with enhanced cuprophilic interactions shows an outstanding product (CH4) selectivity of 82% at -0.9 V (vs reversible hydrogen electrode, j = 391 mA cm-2), which represents the best crystalline catalyst for electrocatalytic CO2-to-CH4 conversion to date. Moreover, the detailed DFT calculations also prove that the cuprophilic interactions can effectively facilitate the electroreduction of CO2 to CH4 by decreasing the Gibbs free energy change of potential determining step (*H2COOH → *OCH2). Significantly, this work first explored the effect of intrinsic cuprophilic interactions of Cu(I)-based catalysts on the electrocatalytic performance of CO2RR and provides an important case study for designing more stable and efficient crystalline catalysts to reduce CO2 to high-value carbon products.

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23 results found

Journal ArticleDOI: 10.1016/J.IJHYDENE.2021.03.206
Dandan Wei1, Wujian Tang1, Yinling Wang1Institutions (1)
Abstract: The urea solution electrolysis has become more attractive than water splitting, because it not only produces clean H2 via the cathodic hydrogen evolution reaction (HER) with lower cell voltage, but also treats sewage containing urea through anodic urea oxidation reaction (UOR). However, lack of efficient electrocatalysts for HER and UOR has limited its development. Herein, hairy sphere -like Ni9S8/CuS/Cu2O composites were synthesized on nickel foam (NF) in situ by a two-step hydrothermal method. The Ni9S8/CuS/Cu2O/NF exhibited good electrocatalytic activity for both HER (−0.146 V vs. RHE to achieve 10 mA cm−2) and UOR (1.357 V vs. RHE to achieve 10 mA cm−2). Based on the bifunctional properties of Ni9S8/CuS/Cu2O/NF, a dual-electrode urea solution electrolytic cell was constructed, which only needed a low voltage of 1.47 V to reach a current density of 10 mA cm−2, and displayed a good stability during a 20-h test. In addition, the reason for the good catalytic activity of Ni9S8/CuS/Cu2O/NF was analyzed and the UOR mechanism was discussed in detail. Our research shows that Ni9S8/CuS/Cu2O/NF is a very promising low-cost dual-function electrocatalyst, which can be used for high-efficiency electrolysis of urea solution to produce hydrogen and treat wastewater.

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Topics: Electrocatalyst (53%), Water splitting (52%), Electrolysis (50%)

4 Citations

Journal ArticleDOI: 10.1002/ANIE.202111136
Dong-Li Meng1, Dong-Li Meng2, Meng-Di Zhang1, Duan-Hui Si1  +5 moreInstitutions (3)
22 Nov 2021-Angewandte Chemie
Abstract: Herein, an effective tandem catalysis strategy is developed to improve the selectivity of the CO2 RR towards C2 H4 by multiple distinct catalytic sites in local vicinity. An earth-abundant elements-based tandem electrocatalyst PTF(Ni)/Cu is constructed by uniformly dispersing Cu nanoparticles (NPs) on the porphyrinic triazine framework anchored with atomically isolated nickel-nitrogen sites (PTF(Ni)) for the enhanced CO2 RR to produce C2 H4 . The Faradaic efficiency of C2 H4 reaches 57.3 % at -1.1 V versus the reversible hydrogen electrode (RHE), which is about 6 times higher than the non-tandem catalyst PTF/Cu, which produces CH4 as the major carbon product. The operando infrared spectroscopy and theoretic density functional theory (DFT) calculations reveal that the local high concentration of CO generated by PTF(Ni) sites can facilitate the C-C coupling to form C2 H4 on the nearby Cu NP sites. The work offers an effective avenue to design electrocatalysts for the highly selective CO2 RR to produce multicarbon products via a tandem route.

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3 Citations

Journal ArticleDOI: 10.1039/D1CC03799D
Qiu-Qin Huang1, Mei-Yue Hu1, Yan-Li Li1, Nan-Nan Chen1  +4 moreInstitutions (2)
Abstract: Two newly synthesized ultra-small copper nanoclusters, [Cu3(μ3-H)(μ2-dppy)4](ClO4)2 (1) and [Cu4(μ4-H)(μ2-dppy)4(μ2-Cl)2](ClO4) (2) (dppy = diphenyl-2-pyridylphosphine), have been shown to exhibit ultrabright yellow and yellow-green room-temperature phosphorescence (RTP) emission, with high quantum yields of 71.8% and 63.5%, respectively. Therefore, nanocluster 1 has been applied for the first time as a single component phosphor for yellow and white light-emitting diodes (LEDs) with favourable characteristics.

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Topics: Phosphor (54%), Phosphorescence (53%)

2 Citations

Open accessJournal ArticleDOI: 10.3390/CRYST11060574
01 May 2021-
Abstract: Two Co(II)-based metal–organic frameworks (MOFs) with open channels, [(CH3)2NH2]2[Co5L(H2O)8]·4H2O (1) and [Co6L(DMF)2(H2O)8]·2H2O (2), were synthesized using resorcin[4]arene ligand (H12L). Compounds 1 and 2 exhibit different 3D microporous framework structures: 1 possesses two kinds of open channels parallel to the a-axis (ca. 5.0 × 5.0 A) and the b-axis (ca. 4.0 × 6.0 A), and 2 is an open framework with a window size of 5.6 × 5.6 A. The activated crystal 1 involves many Lewis acid sites; thus, 1 shows prominent activity and recyclability for the reaction of carbon dioxide coupled with epoxides. Most strikingly, catalyst 1 can be reused for five successive cycles and provides outstanding catalytic activity.

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Topics: Lewis acids and bases (54%), Catalysis (53%), Ligand (52%) ... show more

1 Citations

Journal ArticleDOI: 10.1002/SMLL.202102629
Juan Du1, Yu Xin1, Minghua Dong1, Junjuan Yang1  +3 moreInstitutions (1)
12 Sep 2021-Small
Abstract: Electrochemical reduction of CO2 (CO2 RR) to formate is a promising route to prepare value-added chemical. Developing low-cost and efficient electrocatalysts with high product selectivity is still a grand challenge. Herein, a novel Cu anchored on hollow carbon spheres catalysts (HCS/Cu-x, x represents the mass of CuCl2 added in the system) is designed with controllable copper/carbon heterogenous interfaces. Rich copper/carbon heterogenous interfaces and hollow structure of optimized HCS/Cu-0.12 catalyst are beneficial to charge transmission. Compared with the CO2 RR occurred in aqueous electrolyte over Cu-based catalyst that has been reported to date, it exhibits highest formate Faradaic efficiency (FE) of 82.4% with a current density of 26 mA cm-2 and remarkable stability in a H-cell.

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Topics: Formate (56%), Carbon (51%), Copper (51%) ... show more

1 Citations


60 results found

Open accessJournal ArticleDOI: 10.1007/S00214-007-0310-X
Yan Zhao1, Donald G. Truhlar1Institutions (1)
Abstract: We present two new hybrid meta exchange- correlation functionals, called M06 and M06-2X. The M06 functional is parametrized including both transition metals and nonmetals, whereas the M06-2X functional is a high-nonlocality functional with double the amount of nonlocal exchange (2X), and it is parametrized only for nonmetals.The functionals, along with the previously published M06-L local functional and the M06-HF full-Hartree–Fock functionals, constitute the M06 suite of complementary functionals. We assess these four functionals by comparing their performance to that of 12 other functionals and Hartree–Fock theory for 403 energetic data in 29 diverse databases, including ten databases for thermochemistry, four databases for kinetics, eight databases for noncovalent interactions, three databases for transition metal bonding, one database for metal atom excitation energies, and three databases for molecular excitation energies. We also illustrate the performance of these 17 methods for three databases containing 40 bond lengths and for databases containing 38 vibrational frequencies and 15 vibrational zero point energies. We recommend the M06-2X functional for applications involving main-group thermochemistry, kinetics, noncovalent interactions, and electronic excitation energies to valence and Rydberg states. We recommend the M06 functional for application in organometallic and inorganometallic chemistry and for noncovalent interactions.

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18,691 Citations

Journal ArticleDOI: 10.1063/1.448975
Abstract: Ab initio effective core potentials (ECP’s) have been generated to replace the innermost core electron for third‐row (K–Au), fourth‐row (Rb–Ag), and fifth‐row (Cs–Au) atoms The outermost core orbitals—corresponding to the ns2np6 configuration for the three rows here—are not replaced by the ECP but are treated on an equal footing with the nd, (n+1)s and (n+1)p valence orbitals These ECP’s have been derived for use in molecular calculations where these outer core orbitals need to be treated explicitly rather than to be replaced by an ECP The ECP’s for the forth and fifth rows also incorporate the mass–velocity and Darwin relativistic effects into the potentials Analytic fits to the potentials are presented for use in multicenter integral evaluation Gaussian orbital valence basis sets are developed for the (3s, 3p, 3d, 4s, 4p), (4s, 4p, 4d, 5s, 5p), and (5s, 5p, 5d, 6s, 6p) ortibals of the three respective rows

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Topics: Gaussian orbital (56%), Core electron (54%), Ab initio (52%) ... show more

12,824 Citations

Journal ArticleDOI: 10.1021/CR9904009
26 Jul 2005-Chemical Reviews
Abstract: 6.2.2. Definition of Effective Properties 3064 6.3. Response Properties to Magnetic Fields 3066 6.3.1. Nuclear Shielding 3066 6.3.2. Indirect Spin−Spin Coupling 3067 6.3.3. EPR Parameters 3068 6.4. Properties of Chiral Systems 3069 6.4.1. Electronic Circular Dichroism (ECD) 3069 6.4.2. Optical Rotation (OR) 3069 6.4.3. VCD and VROA 3070 7. Continuum and Discrete Models 3071 7.1. Continuum Methods within MD and MC Simulations 3072

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11,599 Citations

Journal ArticleDOI: 10.1063/1.1674902
Abstract: An extended basis set of atomic functions expressed as fixed linear combinations of Gaussian functions is presented for hydrogen and the first‐row atoms carbon to fluorine. In this set, described as 4–31 G, each inner shell is represented by a single basis function taken as a sum of four Gaussians and each valence orbital is split into inner and outer parts described by three and one Gaussian function, respectively. The expansion coefficients and Gaussian exponents are determined by minimizing the total calculated energy of the atomic ground state. This basis set is then used in single‐determinant molecular‐orbital studies of a group of small polyatomic molecules. Optimization of valence‐shell scaling factors shows that considerable rescaling of atomic functions occurs in molecules, the largest effects being observed for hydrogen and carbon. However, the range of optimum scale factors for each atom is small enough to allow the selection of a standard molecular set. The use of this standard basis gives theoretical equilibrium geometries in reasonable agreement with experiment.

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Topics: STO-nG basis sets (64%), Basis set (59%), Molecular orbital (57%) ... show more

7,677 Citations

Open accessJournal ArticleDOI: 10.1073/PNAS.0602439103
Kyo Sung Park1, Zheng Ni1, Adrien P. Côté1, Jae Yong Choi2  +5 moreInstitutions (4)
Abstract: Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) have been synthesized as crystals by copolymerization of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, respectively. In addition, one example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m 2 /g), high thermal stability (up to 550°C), and remarkable chemical resistance to boiling alkaline water and organic solvents.

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Topics: Zeolitic imidazolate framework (80%), Imidazolate (70%), Chemical stability (53%) ... show more

4,525 Citations

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