Tuning the local chemical environment of ZnSe quantum dots with dithiols towards photocatalytic CO<sub>2</sub> reduction

Sahm, Constantin D.; Ciotti, Anna; Mates‐Torres, Eric; Badiani, Vivek M.; Sokołowski, Kamil; Neri, Gaia; Cowan, Alexander J.; García‐Melchor, Max; Reisner, Erwin

doi:10.1039/d2sc00890d

Cited by 20 publications

(17 citation statements)

References 42 publications

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“…Natural bond orbital (NBO) analysis on selected donor–acceptor interactions was performed using the software NBO 6.0 . The analysis of the noncovalent interactions (NCIs) between the ligands and the oxo and hydroxo groups, defining each ligand arm and the Fe–O(H) moiety as a separate fragment, was assessed by means of the Critic2 software, as reported elsewhere. − The wave function used in the NCI analysis was inherited from the geometry optimizations performed in vacuum with Gaussian09.…”

Section: Methodsmentioning

confidence: 99%

Secondary Coordination Sphere Influences the Formation of Fe(III)-O or Fe(III)-OH in Nitrite Reduction: A Synthetic and Computational Study

et al. 2022

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The reduction of nitrite (NO2 –) to generate nitric oxide (NO) is a significant area of research due to their roles in the global nitrogen cycle. Here, we describe various modifications of the tris(5-cyclohexyliminopyrrol-2-ylmethyl)amine H3[N(piR)3] ligand where the steric bulk and acidity of the secondary coordination sphere were explored in the non-heme iron system for nitrite reduction. The cyclohexyl and 2,4,6-trimethylphenyl variants of the ligand were used to probe the mechanism of nitrite reduction. While previously stoichiometric addition of nitrite to the iron(II)-species generated an iron(III)-oxo complex, changing the secondary coordination sphere to mesityl resulted in an iron(III)-hydroxo complex. Subsequent addition of an electron and two protons led to the release of water and regeneration of the starting iron(II) catalyst. This sequence mirrored the proposed mechanism of nitrite reduction in biological systems, where the distal histidine residue shuttles protons to the active site. Computational studies aimed at interrogating the dissimilar behavior of the cyclohexyl and mesityl ligand systems resulting in Fe(III)-oxo and Fe(III)-hydroxo complexes, respectively, shed light on the key role of H-bonds involving the secondary coordination sphere in the relative stability of these species.

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Section: Methodsmentioning

confidence: 99%

Secondary Coordination Sphere Influences the Formation of Fe(III)-O or Fe(III)-OH in Nitrite Reduction: A Synthetic and Computational Study

et al. 2022

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“…In a similar study, the same group has achieved CO product selectivity by inhibiting the H 2 evolution using dithiolated ligands having long chain lengths. 110 These preliminary studies indicate that the surface ligands have the power to control the adsorption−desorption kinetics of reactants, intermediates, and products. For this, one has to regulate the interaction between these species and the catalyst by varying the ligandbinding site (change in the electronic structure of the catalyst) or by changing the ligand terminal group (change in favorable/ unfavorable interactions), so as to have a balance between the efficiency, selectivity, and recyclability of the catalyst.…”

Section: Surface Ligand-directed Catalysis and Photocatalysis: Channe...mentioning

confidence: 98%

“…Apart from improving the catalytic activity, surface ligands can play a crucial role in accomplishing other desirable functions in catalysis as well, such as product selectivity, switchability, and recyclability (Scheme ). − In a study by Grzybowski and co-workers, a mixture of charged and bipy-Cu(I) ligands was used to create active sites on the AuNP catalyst that led to a preorganized channeling of the reactants in a particular orientation (Figure a) . Specifically, the longer [+] charged thiolated ligands acted as “gatekeepers” in controlling the approach and the orientation of incoming alkyne reactants.…”

Section: Surface Ligand-directed Catalysis and Photocatalysis: Channe...mentioning

confidence: 99%

When Design Meets Function: The Prodigious Role of Surface Ligands in Regulating Nanoparticle Chemistry

Jain

Roy

et al. 2022

Chem. Mater.

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The underlying power of "interplay of forces" in controlling the properties and functions at the nanoscale is highlighted in this perspective. This interplay is achieved by installing attractive and repulsive forces, via proper ligand chemistry, which will guide the nanomaterials to interact with their surroundings as per the need. Along with improving the existing properties, the balancing of attractive and repulsive forces holds the prospects of imparting newer functions as well. The concept of "ligand-directed interplay of forces" is extensively practiced by our group and others for addressing many challenges in the areas of self-assembly, catalysis, light harvesting, and nanomedicine. The journey has been rewarding so far in terms of achieving many important feats in nanoscience, such as selfassembly under equilibrium and nonequilibrium regimes, outplaying ligand poisoning in nanocatalysis, channelizing the flow of energy and electron in donor−acceptor systems, multicolor photopatterning using a single nanohybrid system, biospecific targeting and therapy, and so on. As evident from this perspective, the diversity of the areas benefited showcases the breadth and depth of the impact that surface ligands and interplay of forces can have in material science. Furthermore, the implementation of the "ligand of choice" approach is one way to realize distinct and specific functions from a limited set of nanomaterials. All the examples of "liganddirected studies" mentioned in this perspective are based on the regulation of, primarily, electrostatic forces emanating from the charged surface ligands. Thus, it will be logical to try various combinations of ligands and forces, which means that the area of "ligand-directed nanochemistry" will keep on advancing beyond our predictions. Looking forward, there is plenty of room at the NP surface.

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“…Moreover, the charge separation lifetime of ZnSe QDs is generally longer than that of cadmium‐based counterparts, [5] providing higher probability of photogenerated electrons and holes participating in corresponding redox reactions. The pioneer work using ZnSe QDs for photocatalytic CO 2 reduction in water indicates that the ratio of CO to H 2 is about 1 : 2 with the help of an external co‐catalyst, [6] and more than 20 % selectivity for CO 2 photoreduction over H 2 evolution can be realized by modifying ZnSe QDs with imidazolium ligands, [7] or tailoring the local chemical environment of ZnSe QDs with dithiols [8] . From the kinetics and thermodynamics, H 2 evolution is more favorable than CO 2 reduction in water.…”

Section: Figurementioning

confidence: 99%

“…The pioneer work using ZnSe QDs for photocatalytic CO 2 reduction in water indicates that the ratio of CO to H 2 is about 1 : 2 with the help of an external co-catalyst, [6] and more than 20 % selectivity for CO 2 photoreduction over H 2 evolution can be realized by modifying ZnSe QDs with imidazolium ligands, [7] or tailoring the local chemical environment of ZnSe QDs with dithiols. [8] From the kinetics and thermodynamics, H 2 evolution is more favorable than CO 2 reduction in water. The inhibition of H 2 evolution of CO 2 photoreduction in aqueous solution is still a huge challenge.…”

mentioning

confidence: 99%

Reductive Carbon–Carbon Coupling on Metal Sites Regulates Photocatalytic CO₂ Reduction in Water Using ZnSe Quantum Dots

et al. 2022

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Colloidal quantum dots (QDs) consisting of precious-metal-free elements show attractive potentials towards solar-driven CO 2 reduction. However, the inhibition of hydrogen (H 2 ) production in aqueous solution remains a challenge. Here, we describe the first example of a carbon-carbon (CÀ C) coupling reaction to block the competing H 2 evolution in photocatalytic CO 2 reduction in water. In a specific system taking ZnSe QDs as photocatalysts, the introduction of furfural can significantly suppress H 2 evolution leading to CO evolution with a rate of � 5.3 mmol g À 1 h À 1 and a turnover number (TON) of > 7500 under 24 h visible light. Meanwhile, furfural is upgraded to the selfcoupling product with a yield of 99.8 % based on the consumption of furfural. Mechanistic insights show that the reductive furfural coupling reaction occurs on surface Zn-sites to consume electrons and protons originally used for H 2 production, while the CO formation pathway at surface anion vacancies from CO 2 remains.

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Tuning the local chemical environment of ZnSe quantum dots with dithiols towards photocatalytic CO₂ reduction

Abstract: Sunlight-driven CO2 reduction to renewable fuels is a promising strategy towards a closed carbon cycle in a circular economy. Colloidal quantum dots (QDs) have emerged as a versatile light absorber...

Cited by 20 publications

References 42 publications

Secondary Coordination Sphere Influences the Formation of Fe(III)-O or Fe(III)-OH in Nitrite Reduction: A Synthetic and Computational Study

Secondary Coordination Sphere Influences the Formation of Fe(III)-O or Fe(III)-OH in Nitrite Reduction: A Synthetic and Computational Study

When Design Meets Function: The Prodigious Role of Surface Ligands in Regulating Nanoparticle Chemistry

Reductive Carbon–Carbon Coupling on Metal Sites Regulates Photocatalytic CO₂ Reduction in Water Using ZnSe Quantum Dots

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Tuning the local chemical environment of ZnSe quantum dots with dithiols towards photocatalytic CO2 reduction

Abstract: Sunlight-driven CO2 reduction to renewable fuels is a promising strategy towards a closed carbon cycle in a circular economy. Colloidal quantum dots (QDs) have emerged as a versatile light absorber...

Cited by 20 publications

References 42 publications

Secondary Coordination Sphere Influences the Formation of Fe(III)-O or Fe(III)-OH in Nitrite Reduction: A Synthetic and Computational Study

Secondary Coordination Sphere Influences the Formation of Fe(III)-O or Fe(III)-OH in Nitrite Reduction: A Synthetic and Computational Study

When Design Meets Function: The Prodigious Role of Surface Ligands in Regulating Nanoparticle Chemistry

Reductive Carbon–Carbon Coupling on Metal Sites Regulates Photocatalytic CO2 Reduction in Water Using ZnSe Quantum Dots

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Resources

About

Tuning the local chemical environment of ZnSe quantum dots with dithiols towards photocatalytic CO₂ reduction

Reductive Carbon–Carbon Coupling on Metal Sites Regulates Photocatalytic CO₂ Reduction in Water Using ZnSe Quantum Dots