Spectroscopically Visualizing the Evolution of Hydrogen-Bonding Interactions

Yi, Xianfeng; Chen, Wei; Xiao, Yao; Liu, Fengqing; Yu, Xin; Zheng, Anmin

doi:10.1021/jacs.3c08723

Cited by 9 publications

(4 citation statements)

References 46 publications

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“…According to the Grotthuss mechanism, the proton transfer in an aqueous solution occurs via a series of proton-involved reactions that accompany the migration of topological defects in the H-bond network. ,− Therefore, by breaking and/or reshaping the original H-bond network, the proton transfer and hydrogen-related reaction kinetics can be regulated. ,, In the field of aqueous zinc batteries, several effective and low-cost additives have been utilized to decrease the side reactions associated with water by regulating the H-bond environment among water molecules. − Among these, sulfonate-based molecules are a common type of H-bond acceptors that can modulate the H-bond environment through H-bond interaction between–SO 3 – (the H-bond acceptor) and water (the H-bond donor). Examples of such molecules include sodium dodecyl sulfate (SDS) and sodium dodecyl benzenesulfonate (SDBS) .…”

Section: Resultsmentioning

confidence: 99%

“…The electrocatalytic reaction occurs in the narrow nanoscale region at the electrode–electrolyte interface. − Modifying the components of electrolytes is a significant strategy to regulate the interfacial hydrogen-bond (H-bond) environment and steer the kinetics of hydrogen-related reactions, e.g., HER and CO 2 RR. − For instance, Li et al discovered that alkali-metal cations can modulate proton transfer kinetics by reducing the connectivity of the H-bond network in the electric double layer (EDL) . Xu and co-workers demonstrated that bulky organic cations, such as tetrapropyl ammonium, can foster the formation and lifetime of H-bonds among interfacial water molecules, thereby enhancing the kinetics of HER and hydrogen oxidation reactions (HOR).…”

Section: Introductionmentioning

confidence: 99%

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Modulating Interfacial Hydrogen-Bond Environment by Electrolyte Engineering Promotes Acidic CO₂ Electrolysis

Ge,

Dong,

Wang

et al. 2024

ACS Catal.

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Acidic CO2 electroreduction offers a promising strategy for achieving a high CO2 utilization efficiency. However, it is highly challenging to inhibit the competing hydrogen evolution reactions (HER) due to the high concentration of protons at the electrode–electrolyte interface. The interfacial hydrogen-bond environment greatly affects proton transfer and the kinetics of hydrogen-related reactions, e.g., HER and CO2 reduction. In this work, we demonstrate that sulfonate-based electrolyte additives, including sodium p-styrenesulfonate (SPS), sodium p-toluene sulfonate (STS), and sodium benzenesulfonate (SBS), enable reconstruction of the interfacial hydrogen-bond environment and enhance the CO2 electrolysis performance. Mechanistic studies uncover that the strong hydrogen-bond interactions of these sulfonate-based additives with H2O achieve the construction of a low proton-flux interface. This leads to the suppression of proton concentration-dependent HER. The SPS-assisted acidic CO2 electrolysis yields CO with a high selectivity of 97.8% and a high single-pass carbon efficiency of 66.3% at 250 mA cm–2 on commercial Ag catalysts in acid. This work provides a facile strategy to promote acidic CO2 electrolysis by modulating the interfacial hydrogen-bond environment through electrolyte design.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Modulating Interfacial Hydrogen-Bond Environment by Electrolyte Engineering Promotes Acidic CO₂ Electrolysis

Ge,

Dong,

Wang

et al. 2024

ACS Catal.

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“…[22] As shown in Figure 3d, the addition of 1 μL of H 2 O or D 2 O results in a significant decrease in HMF conversion, with D 2 O showing a reduction of HMF conversion by 2.7 times, indicating that the presence of water can substantially disturb the oxidation of HMF. With the addition of 10 and 100 μL of H 2 O or D 2 O, the conversion of HMF was completely impeded, probably due to water being more competitive as hydrogen bonding donors than À OH and À CHO groups in HMF, [23] as urea linkages in TBUPPÀ Cu serve as hydrogen bonding acceptors. Completely replacing MeCN with water leads to ~75 % HMF conversion with < 1 % selectivity of furan compounds, most of which are over-oxidised by * OH produced from the direct combination of O 2 with protons provided by water (O 2 !*OOH!…”

Section: Methodsmentioning

confidence: 99%

Hydrogen‐Bond‐Enhanced Photoreforming of Biomass Furans over a Urea‐Incorporated Cu(II) Porphyrin Framework

Zhang,

Zhang

et al. 2024

Angew Chem Int Ed

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Solar‐driven upgrading of biomass‐derived 5‐hydroxylmethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA) holds great promise for sustainable production of bio‐plastics and resins. However, the process is limited by poor selectivity and sluggish kinetics due to the vertical coordination of HMF at relatively strong metal sites. Here, we purposely developed a Cu(II) porphyrin framework featuring side‐chain incorporated urea linkages, denoted as TBUPP‐Cu MOF, to render HMF a weak hydrogen bond at the urea site and flat adsorption via π–π stacking with the benzyl moiety. The unique configuration promotes the approaching of –CHO of HMF to the photoexcited porphyrin ring towards kinetically and thermodynamically favourable intermediate formation and subsequent desorption. The charge localization and orbital energy alignment enable the selective activation of O2 over the porphyrin to generate ·O2− and 1O2 instead of highly oxidative H2O2 and ·OH via spin‐flip electron transfer, which drive the ambient oxidation of proximal –CHO. The effective utilisation of redox species and circumvented over‐oxidation facilitate a FDCA selectivity of >90% with a high turnover number of 193 molHMF molCu−1. The facile purification of high‐purity FDCA and zero‐waste recycling of intermediates and durable catalyst feature TBUPP‐Cu MOF a promising photo‐oxidation platform towards net‐zero biorefining and organic transformations.

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“…Another interesting approach proposed bond order calculations as an electronic descriptor for acid strength, including the local interaction between a probe molecule and the proton . The proton donating ability of solid acids, including zeolites or tungstophosphoric acid, was investigated with various weak proton acceptors via 1 H– 13 C heteronuclear dipolar interactions . By this means, a complex dependence of 1 H NMR chemical shifts of the solid acids and 13 C chemical shifts of the molecular probes was observed, thus tracking the potential energy surface of proton transfer.…”

Section: Introductionmentioning

confidence: 99%

Response of Hydrogen-Bonded Brønsted Acid Sites in ZSM-5 to Adsorption and H/D Exchange of Hydrocarbons

Koller,

Hunger

2024

J. Phys. Chem. C

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The interaction and H/D exchange of free and hydrogen-bonded Bro̷ nsted acid sites (BAS) of zeolite ZSM-5 (Si/Al = 14) with n-hexane were investigated by 1 H MAS NMR spectroscopy and DFT cluster model calculations. Three model sites were selected from the greater variety of possible BAS locations for model calculations to represent free BAS (Al12-O26(H)-Si12, site I) and strong (Al2-O7(H)-Si6, site II) or weakly hydrogen-bonded (Al5-O12(H)-Si4, site III) BAS. The molecule interacts with the BAS via van der Waals and Coulomb interactions. Strong hydrogen bonds of site II in 5-rings remain intact after n-hexane adsorption, whereas a rupture of weak hydrogen bonds of site III in 6-rings occurred. H/D exchange of the BAS with n-hexane is found for sites I and II at 423 K, but site III is not reactive at this temperature, indicating that the reactivity does not correlate with hydrogen bond strength. This is, at least to some extent, due to the strong adsorption of n-hexane in the groove of the zigzag channel of ZSM-5 for site III. These results contribute to deeper insights into hydrocarbon reactions with zeolite catalysts.

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Spectroscopically Visualizing the Evolution of Hydrogen-Bonding Interactions

Cited by 9 publications

References 46 publications

Modulating Interfacial Hydrogen-Bond Environment by Electrolyte Engineering Promotes Acidic CO₂ Electrolysis

Modulating Interfacial Hydrogen-Bond Environment by Electrolyte Engineering Promotes Acidic CO₂ Electrolysis

Hydrogen‐Bond‐Enhanced Photoreforming of Biomass Furans over a Urea‐Incorporated Cu(II) Porphyrin Framework

Response of Hydrogen-Bonded Brønsted Acid Sites in ZSM-5 to Adsorption and H/D Exchange of Hydrocarbons

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Spectroscopically Visualizing the Evolution of Hydrogen-Bonding Interactions

Cited by 9 publications

References 46 publications

Modulating Interfacial Hydrogen-Bond Environment by Electrolyte Engineering Promotes Acidic CO2 Electrolysis

Modulating Interfacial Hydrogen-Bond Environment by Electrolyte Engineering Promotes Acidic CO2 Electrolysis

Hydrogen‐Bond‐Enhanced Photoreforming of Biomass Furans over a Urea‐Incorporated Cu(II) Porphyrin Framework

Response of Hydrogen-Bonded Brønsted Acid Sites in ZSM-5 to Adsorption and H/D Exchange of Hydrocarbons

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Modulating Interfacial Hydrogen-Bond Environment by Electrolyte Engineering Promotes Acidic CO₂ Electrolysis

Modulating Interfacial Hydrogen-Bond Environment by Electrolyte Engineering Promotes Acidic CO₂ Electrolysis