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High-performance light-driven heterogeneous CO2 catalysis with near-unity selectivity on metal phosphides.

ABSTRACT: Akin to single-site homogeneous catalysis, a long sought-after goal is to achieve reaction site precision in heterogeneous catalysis for chemical control over patterns of activity, selectivity and stability. Herein, we report on metal phosphides as a class of material capable of realizing these attributes and unlock their potential in solar-driven CO2 hydrogenation. Selected as an archetype, Ni12P5 affords a structure based upon highly dispersed nickel nanoclusters integrated into a phosphorus lattice that harvest light intensely across the entire solar spectral range. Motivated by its panchromatic absorption and unique linearly bonded nickel-carbonyl-dominated reaction route, Ni12P5 is found to be a photothermal catalyst for the reverse water gas shift reaction, offering a CO production rate of 960?±?12?mmol?gcat-1?h-1, near 100% selectivity and long-term stability. Successful extension of this idea to Co2P analogs implies that metal phosphide materials are poised as a universal platform for high-rate and highly selective photothermal CO2 catalysis.

SUBMITTER: Xu YF

PROVIDER: S-EPMC7555895 | biostudies-literature | 2020 Oct

REPOSITORIES: biostudies-literature

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High-performance light-driven heterogeneous CO2 catalysis with near-unity selectivity on metal phosphides.

Xu Yang-Fan YF Duchesne Paul N PN Wang Lu L Tavasoli Alexandra A Ali Feysal M FM Xia Meikun M Liao Jin-Feng JF Kuang Dai-Bin DB Ozin Geoffrey A GA

Nature communications 20201013 1

Akin to single-site homogeneous catalysis, a long sought-after goal is to achieve reaction site precision in heterogeneous catalysis for chemical control over patterns of activity, selectivity and stability. Herein, we report on metal phosphides as a class of material capable of realizing these attributes and unlock their potential in solar-driven CO2 hydrogenation. Selected as an archetype, Ni12P5 affords a structure based upon highly dispersed nickel nanocluste ...[more]

PMID: 33051460

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Project description:Outer-shell s0/p0 orbital mixing with d10 orbitals and symmetry reduction upon cupriphication of cyclic trinuclear trigonal-planar gold(I) complexes are found to sensitize ground-state Cu(I)-Au(I) covalent bonds and near-unity phosphorescence quantum yields. Heterobimetallic Au4Cu2 {[Au4(?-C2,N3-EtIm)4Cu2(µ-3,5-(CF3)2Pz)2], (4a)}, Au2Cu {[Au2(?-C2,N3-BzIm)2Cu(µ-3,5-(CF3)2Pz)], (1) and [Au2(?-C2,N3-MeIm)2Cu(µ-3,5-(CF3)2Pz)], (3a)}, AuCu2 {[Au(?-C2,N3-MeIm)Cu2(µ-3,5-(CF3)2Pz)2], (3b) and [Au(?-C2,N3-EtIm)Cu2(µ-3,5-(CF3)2Pz)2], (4b)} and stacked Au3/Cu3 {[Au(?-C2,N3-BzIm)]3[Cu(µ-3,5-(CF3)2Pz)]3, (2)} form upon reacting Au3 {[Au(?-C2,N3-(N-R)Im)]3 ((N-R)Im = imidazolate; R = benzyl/methyl/ethyl = BzIm/MeIm/EtIm)} with Cu3 {[Cu(?-3,5-(CF3)2Pz)]3 (3,5-(CF3)2Pz = 3,5-bis(trifluoromethyl)pyrazolate)}. The crystal structures of 1 and 3a reveal stair-step infinite chains whereby adjacent dimer-of-trimer units are noncovalently packed via two Au(I)?Cu(I) metallophilic interactions, whereas 4a exhibits a hexanuclear cluster structure wherein two monomer-of-trimer units are linked by a genuine d10-d10 polar-covalent bond with ligand-unassisted Cu(I)-Au(I) distances of 2.8750(8) Å each-the shortest such an intermolecular distance ever reported between any two d10 centers so as to deem it a "metal-metal bond" vis-à-vis "metallophilic interaction." Density-functional calculations estimate 35-43 kcal/mol binding energy, akin to typical M-M single-bond energies. Congruently, FTIR spectra of 4a show multiple far-IR bands within 65-200 cm-1, assignable to vCu-Au as validated by both the Harvey-Gray method of crystallographic-distance-to-force-constant correlation and dispersive density functional theory computations. Notably, the heterobimetallic complexes herein exhibit photophysical properties that are favorable to those for their homometallic congeners, due to threefold-to-twofold symmetry reduction, resulting in cuprophilic sensitization in extinction coefficient and solid-state photoluminescence quantum yields approaching unity (?PL = 0.90-0.97 vs. 0-0.83 for Au3 and Cu3 precursors), which bodes well for potential future utilization in inorganic and/or organic LED applications.

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High-performance light-driven heterogeneous CO2 catalysis with near-unity selectivity on metal phosphides.

Publications

High-performance light-driven heterogeneous CO<sub>2</sub> catalysis with near-unity selectivity on metal phosphides.

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