Predicted Efficient Visible-Light Driven Water Splitting and Carbon

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C: Surfaces, Interfaces, Porous Materials, and Catalysis

Predicted Efficient Visible-Light Driven Water Splitting and Carbon Dioxide Reduction Using Photoredox Active UiO-NDI Metal Organic Framework Saied Md Pratik, and Christopher J. Cramer J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.9b05693 • Publication Date (Web): 23 Jul 2019 Downloaded from pubs.acs.org on July 25, 2019

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The Journal of Physical Chemistry

Predicted Efficient Visible-Light Driven Water Splitting and Carbon Dioxide Reduction Using Photoredox Active UiO-NDI Metal Organic Framework Saied Md Pratik*, Christopher J. Cramer* Department of Chemistry, Minnesota Supercomputing Institute, and Chemical Theory Center, University of Minnesota, Minneapolis, Minnesota 55455, United States Corresponding Authors *E-mail: [email protected] and [email protected].

Abstract: The structural and electronic properties of metal-organic frameworks (MOFs) constructed from stable Zr(IV) oxide-based nodes and naphthalenediimide-based linkers (UiO(Zr)-NDI) can be tuned to make them useful for specific photoredox processes. The NDI linker presents outside, inside, and core positions where functionalization can influence its optical properties, and such substitution in combination with suitable optical band gaps and band edge positions in UiO(Zr)-NDI offers a platform for the design of efficient MOF-based photocatalysts for water splitting and CO2 reduction. The band gaps and edge positions remain similar for UiO nodes when Zr is substituted with Ti, Th, or Ce. However, in contrast to the case for Zr-, Ti-, and Thbased UiO-NDIs, where photoexcitation remains localized on the NDI linkers owing to the very high energies of unoccupied node-based bands, for UiO(Ce)-NDI the availability of low-lying empty f orbitals in the metal node offers the potential for energy transfer and exciton migration, which could further boost photocatalytic performance by extending exciton lifetimes. Introductions: Metal organic frameworks (MOFs) are continuing to evolve as an important class of materials due to their inherent structural diversity and demonstrated applicability to such diverse fields as gas storage and separation, catalysis, chemical sensing, and optical devices.1-12 Of particular interest is the potential to tune MOFs as semiconductors in order to harvest solar photons for optoelectronic applications and photoinduced catalysis.13-15 When combining large surface areas and permanent porosities, MOFs are especially appealing as photocatalysts since they provide sufficient space for protected catalyst-substrate interactions as well as product 1 ACS Paragon Plus Environment

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release.15-18 Importantly, the modular nature of MOFs offers an efficient means to combine diverse linkers and nodes and thus tailor optical properties (as well as possibly efficient electron– hole (e–h) separation) so as to maximize their photocatalytic performance for specific applications, e.g., water splitting, CO2 reduction, organic transformations, and others.15-16,19-21 A number of experimental and theoretical reports addressing MOFs as photocatalysts have appeared, but achieving high efficiency remains a challenge.19,22-26 The investigation of MOFs as photocatalysts has accelerated since Garcia et al. reported that photoexcitation of semiconducting MOF-5 leads to charge-separated states that decay on the microsecond time scale.27 To date, UiO-66(Zr), MIL-125(Ti), and related derivatives have been most extensively studied for the design of MOF-based photocatalysts, in part because they offer excellent thermal and chemical stability.22-23,26,28-30 While certain advantages have been noted above, there are also limitations for MOFs as efficient photocatalysts, including poor light harvesting properties, low charge-separation and energy-transfer efficiencies resulting in short lifetimes of excitons, and possible mismatches between sites of substrate adsorption and electronic excitation.13,15 Several strategies have emerged to address such limitations.31-32 Incorporation of a photoredox-active dye molecule as a linker in the MOF scaffold is a particularly attractive approach.16,33-35 Many dyes having large optical cross sections and long excitonic lifetimes are known and have the potential to be adapted for use as linkers.36-38 Indeed, when installed as linkers in a rigid framework, the formation of H or J aggregates is suppressed, and different MOF topologies can control the distance between dyes, permitting tuning to obtain better performance and space for reactant activation and product release.13,39-40 With higher levels of architectural control, hierarchically arranged light-harvesting chromophores within the framework can open unique pathways for fast exciton migration and improved photocatalytic performance.41 For instance, Hupp and coworkers reported linker-to-linker exciton hopping in porphyrin-based MOFs exhibiting long-distance and directional energy transfer.42 In addition, Zhang et. al., reported for a truxene-derived MOF step-by-step “through space” exciton hopping beyond the nearest neighbor to account for up to 67% of the energy transfer rate.43 Of key importance, obviously, is the selection of the dye. Naphthalene diimides (NDI) are planar, uncharged, aromatic compounds that are simultaneously electron deficient and photoredox active, making them particularly useful in the designing of organic n-type semiconductors.44-47 Core-functionalized NDI derivatives are 2 ACS Paragon Plus Environment

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capable of harvesting significant regions of the solar spectrum.46-47 In addition, with a low standard reduction potential, the NDI radical anion (NDI•−, ENDI(0)/NDI(1−) ∼ −0.5 V vs saturated calomel electrode (SCE)) can be readily generated through chemical, electrochemical or photoreduction methods, and excited-state *NDI•− has been shown to serve as an efficient electron donor to generate solar fuels from CO2 through a photoinduced electron transfer (PET) mechanism.48,49 Such redox active linkers have been incorporated in MOFs for purposes of sensing, electro-/photochromism, electrocatalysis, and to design conductive MOFs, and recently Wasielewski and co-workers have synthesized a MOF combining the highly stable Zr(IV)-oxidebased node of the UiO series with N,N-bis(2,6-dimethyl-4-benzoic acid)-NDI as the linker (UiO-NDI).48,50-55 They found that the large separation between the NDI linkers in UiO-NDI prevents electronic coupling through space and that the redox inactivity of the Zr6 nodes (or, put differently, the high energy of associated node conduction bands) suppresses deactivation of the excited states through energy transfer. Our goal in this work is to use density functional theory (DFT) to explore the structural and electronic properties of modified UiO-NDI MOFs, and in particular to assess the influence of perturbations introduced by substitution at various positions of the NDI linker as well as substitutions of the metal in the M6O8 core of the UiO framework. We target specifically band gaps appropriate for the photocatalysis of water splitting and CO2 reduction, although fundamental understanding of trends as a function of substitution is already of inherent interest. Computational Details: Periodic density functional calculations were performed using the projector augmented wave (PAW) approach as implemented in the Vienna ab initio simulation package (VASP 5.4.4).56 Electron exchange-correlation was described by the generalized gradient approximation (GGA) using the semi-local PBEsol functional specifically designed for the solid state.57 Ultrasoft pseudopotentials were used for core-electron interactions. During geometry optimizations for all structures other than parent UiO(Zr)-NDI-(CH3)4 (see below), Γ-point sampling of the first Brillouin zone was done with an electronic energy convergence criterion of 10−6 eV and a planewave kinetic energy cut-off of 500 eV. All atomic positions were relaxed to Hellman−Feynman forces 4.0 eV for UiO(Th)-NDI MOF. More significantly still, the low-lying empty 4f orbitals of Ce4+ move UiO(Ce)-NDI MOF’s band edge down to a level only 0.25 eV above the bottom of the LUCO, making this band readily accessible following photoexcitation and bonding well for extending exciton lifetimes in UiO(Ce)-NDI MOFs. For all 4 metals, the vacuum alignments of the UiO-NDI band extrema are found to be suitable for photocatalytic water splitting and CO2 reduction (Figure S8).

Table3. Calculated HOCO-LUCO gaps (Eg) and ligand to metal charge transfer energy (ΔELMCT) for Zr, Ti, Th and Ce based UiO-NDI MOFs. Inorganometallic nodes

Eg, eV

ΔELMCT, eV

Zr

2.75

3.46

Ti

2.73

1.32

Th

2.77

>4.00

Ce

2.76

0.25

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Conclusions Solid-state density functional theory calculations indicate that UiO-type MOFs incorporating naphthalenediimide linkers have potential for use as photocatalysts. Their photophysical properties, including especially their band gaps and vacuum alignment of band levels, can be tailored through suitable substitutions at inside, outside, or core positions of the NDI linker, as well as by choice of metal in the UiO-type node. For Zr-, Ti-, Th-, and Ce-based options, optical band gaps and edge positions are predicted to be appropriate for photoinduced water splitting and CO2 reduction. Excitons are predicted to be effectively molecular in nature, i.e., localized on linkers, and the MOF framework guarantees that individual linkers will be well isolated from one another. Extension of excitonic lifetimes through promotion of hot electrons to node-based orbitals/bands is unlikely for Zr- and Th-based materials, but node doping with Ti, and especially Ce, is predicted to significantly lower the energy of node-based bands, offering the potential for efficient charge-carrier separation. These results should generalize to other MOFs incorporating either NDI chromophores or UiO-type nodes. Supporting Information: Computed lattice parameters, different linker functionalization, electronic structures of various UiO(Zr)-NDI MOFs, and band alignment with respect to vacuum for photocatalysis and other related data. Acknowledgment: This research was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under Award DE-FG0217ER16362. Computer resources were provided by the Minnesota Supercomputing Institute at the University of Minnesota. We are grateful to Professor Chris Hendon for assistance with the band alignment procedure with respect to the vacuum.


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Predicted Efficient Visible-Light Driven Water Splitting and Carbon

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