In Situ Electrochemical Cells to Study the Oxygen Evolution Reaction by Near Ambient Pressure X-ray Photoelectron Spectroscopy

Abstract Metal-organic frameworks (MOFs) with carboxylate ligands as co-catalysts are very efficient for oxygen evolution reaction (OER). However, the role of local adsorbed carboxylate ligands around the in situ transformed metal (oxy)hydroxides during OER is often overlooked. Here we reveal the extraordinary role and mechanism of surface adsorbed carboxylate ligands on bi/trimetallic layered double hydroxides (LDHs)/MOFs for OER catalytic activity enhancement. The results of X-ray photoelectron spectroscopy (XPS), synchrotron X-ray absorption spectroscopy and theoretical calculations show that the carboxylic groups around metal (oxy)hydroxides can efficiently induce the interfacial electron redistribution, facilitate abundant high-valence state of nickel species with partial distorted octahedral structure, and optimize the d-band center together with the beneficial Gibbs free energy of intermediate. Furthermore, the results of in-situ Raman and FI-IR spectra firstly reveal that the surface adsorbed carboxylate ligands as Lewis base can promote the sluggish OER kinetics by accelerating proton transfer and facilitating adsorption/ activation/dissociation of hydroxyl ions (OH−). Our findings will offer unique insights into the reason for disclosing the origin of excellent electrocatalytic activity for MOF/NiFe-LDHs catalysts.

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In Situ probing of solid/liquid interfaces of potassium–oxygen batteries via ambient pressure X-ray photoelectron spectroscopy: New reaction pathways and root cause of battery degradation

Energy Storage Materials ◽

10.1016/j.ensm.2021.01.010 ◽

2021 ◽

Vol 36 ◽

pp. 341-346 ◽

Cited By ~ 1

Author(s):

Wanwan Wang ◽

Yu Wang ◽

Chia-Hsin Wang ◽

Yaw-Wen Yang ◽

Yi-Chun Lu

Keyword(s):

Photoelectron Spectroscopy ◽

Ambient Pressure ◽

Reaction Pathways ◽

Liquid Interfaces ◽

X Ray ◽

Root Cause ◽

Battery Degradation ◽

Solid Liquid

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Electrochemical reduction of CO2 in ionic liquid: Mechanistic study of Li–CO2 batteries via in situ ambient pressure X-ray photoelectron spectroscopy

Nano Energy ◽

10.1016/j.nanoen.2021.105830 ◽

2021 ◽

Vol 83 ◽

pp. 105830

Author(s):

Yu Wang ◽

Wanwan Wang ◽

Jing Xie ◽

Chia-Hsin Wang ◽

Yaw-Wen Yang ◽

...

Keyword(s):

Ionic Liquid ◽

Electrochemical Reduction ◽

Photoelectron Spectroscopy ◽

Ambient Pressure ◽

Mechanistic Study ◽

X Ray ◽

Reduction Of Co2

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In situ monitoring of the influence of water on DNA radiation damage by near-ambient pressure X-ray photoelectron spectroscopy

Communications Chemistry ◽

10.1038/s42004-021-00487-1 ◽

2021 ◽

Vol 4 (1) ◽

Author(s):

Marc Benjamin Hahn ◽

Paul M. Dietrich ◽

Jörg Radnik

Keyword(s):

Dna Damage ◽

Radiation Damage ◽

Photoelectron Spectroscopy ◽

Ambient Pressure ◽

In Situ Monitoring ◽

Strong Increase ◽

Oh Radicals ◽

Strand Breaks ◽

X Ray

AbstractIonizing radiation damage to DNA plays a fundamental role in cancer therapy. X-ray photoelectron-spectroscopy (XPS) allows simultaneous irradiation and damage monitoring. Although water radiolysis is essential for radiation damage, all previous XPS studies were performed in vacuum. Here we present near-ambient-pressure XPS experiments to directly measure DNA damage under water atmosphere. They permit in-situ monitoring of the effects of radicals on fully hydrated double-stranded DNA. The results allow us to distinguish direct damage, by photons and secondary low-energy electrons (LEE), from damage by hydroxyl radicals or hydration induced modifications of damage pathways. The exposure of dry DNA to x-rays leads to strand-breaks at the sugar-phosphate backbone, while deoxyribose and nucleobases are less affected. In contrast, a strong increase of DNA damage is observed in water, where OH-radicals are produced. In consequence, base damage and base release become predominant, even though the number of strand-breaks increases further.

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Revealing the structural transformation of rutile RuO2via in situ X-ray absorption spectroscopy during the oxygen evolution reaction

Dalton Transactions ◽

10.1039/c9dt00138g ◽

2019 ◽

Vol 48 (21) ◽

pp. 7122-7129 ◽

Cited By ~ 9

Author(s):

Chia-Jui Chang ◽

You-Chiuan Chu ◽

Hao-Yu Yan ◽

Yen-Fa Liao ◽

Hao Ming Chen

Keyword(s):

Oxygen Evolution ◽

Structural Transformation ◽

Absorption Spectroscopy ◽

Oxygen Evolution Reaction ◽

The State ◽

X Ray ◽

Alkaline Conditions ◽

X Ray Absorption ◽

State Of Art

The state-of-art RuO2 catalyst for the oxygen evolution reaction (OER) is measured by using in situ X-ray absorption spectroscopy (XAS) to elucidate the structural transformation during catalyzing the reaction in acidic and alkaline conditions.

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In situ investigation of degradation at organometal halide perovskite surfaces by X-ray photoelectron spectroscopy at realistic water vapour pressure

Chemical Communications ◽

10.1039/c7cc01538k ◽

2017 ◽

Vol 53 (37) ◽

pp. 5231-5234 ◽

Cited By ~ 37

Author(s):

Jack Chun-Ren Ke ◽

Alex S. Walton ◽

David J. Lewis ◽

Aleksander Tedstone ◽

Paul O'Brien ◽

...

Keyword(s):

Water Vapour ◽

Photoelectron Spectroscopy ◽

Ambient Pressure ◽

Water Vapour Pressure ◽

Lead Iodide ◽

X Ray ◽

In Situ Investigation ◽

Organometal Halide Perovskite ◽

Methylammonium Lead Iodide

Near-ambient-pressure X-ray photoelectron spectroscopy enables the study of the reaction of in situ-prepared methylammonium lead iodide (MAPI) perovskite at realistic water vapour pressures for the first time.

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An in situ near-ambient pressure X-ray Photoelectron Spectroscopy study of Mn polarised anodically in a cell with solid oxide electrolyte

Electrochimica Acta ◽

10.1016/j.electacta.2015.05.173 ◽

2015 ◽

Vol 174 ◽

pp. 532-541 ◽

Cited By ~ 11

Author(s):

Benedetto Bozzini ◽

Matteo Amati ◽

Patrizia Bocchetta ◽

Simone Dal Zilio ◽

Axel Knop-Gericke ◽

...

Keyword(s):

Photoelectron Spectroscopy ◽

Ambient Pressure ◽

Solid Oxide ◽

Spectroscopy Study ◽

Solid Oxide Electrolyte ◽

X Ray ◽

A Cell ◽

Oxide Electrolyte

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Nitrogen-Doped Sponge Ni Fibers as Highly Efficient Electrocatalysts for Oxygen Evolution Reaction

Nano-Micro Letters ◽

10.1007/s40820-019-0253-5 ◽

2019 ◽

Vol 11 (1) ◽

Cited By ~ 19

Author(s):

Kaili Zhang ◽

Xinhui Xia ◽

Shengjue Deng ◽

Yu Zhong ◽

Dong Xie ◽

...

Keyword(s):

Oxygen Evolution ◽

Photoelectron Spectroscopy ◽

Oxygen Evolution Reaction ◽

Active Sites ◽

High Performance ◽

Active Phase ◽

X Ray ◽

Highly Active ◽

N Doping ◽

Energy Conversion Devices

Abstract Controllable synthesis of highly active micro/nanostructured metal electrocatalysts for oxygen evolution reaction (OER) is a particularly significant and challenging target. Herein, we report a 3D porous sponge-like Ni material, prepared by a facile hydrothermal method and consisting of cross-linked micro/nanofibers, as an integrated binder-free OER electrocatalyst. To further enhance the electrocatalytic performance, an N-doping strategy is applied to obtain N-doped sponge Ni (N-SN) for the first time, via NH3 annealing. Due to the combination of the unique conductive sponge structure and N doping, the as-obtained N-SN material shows improved conductivity and a higher number of active sites, resulting in enhanced OER performance and excellent stability. Remarkably, N-SN exhibits a low overpotential of 365 mV at 100 mA cm−2 and an extremely small Tafel slope of 33 mV dec−1, as well as superior long-term stability, outperforming unmodified sponge Ni. Importantly, the combination of X-ray photoelectron spectroscopy and near-edge X-ray adsorption fine structure analyses shows that γ-NiOOH is the surface-active phase for OER. Therefore, the combination of conductive sponge structure and N-doping modification opens a new avenue for fabricating new types of high-performance electrodes with application in electrochemical energy conversion devices.

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Carbide-Modified Pd on ZrO2 as Active Phase for CO2-Reforming of Methane—A Model Phase Boundary Approach

Catalysts ◽

10.3390/catal10091000 ◽

2020 ◽

Vol 10 (9) ◽

pp. 1000

Author(s):

Norbert Köpfle ◽

Kevin Ploner ◽

Peter Lackner ◽

Thomas Götsch ◽

Christoph Thurner ◽

...

Keyword(s):

Phase Boundary ◽

Photoelectron Spectroscopy ◽

Batch Reactor ◽

Ambient Pressure ◽

Composite Layer ◽

Reaction Rates ◽

Near Surface ◽

X Ray ◽

Zro2 Phase

Starting from subsurface Zr0-doped “inverse” Pd and bulk-intermetallic Pd0Zr0 model catalyst precursors, we investigated the dry reforming reaction of methane (DRM) using synchrotron-based near ambient pressure in-situ X-ray photoelectron spectroscopy (NAP-XPS), in-situ X-ray diffraction and catalytic testing in an ultrahigh-vacuum-compatible recirculating batch reactor cell. Both intermetallic precursors develop a Pd0–ZrO2 phase boundary under realistic DRM conditions, whereby the oxidative segregation of ZrO2 from bulk intermetallic PdxZry leads to a highly active composite layer of carbide-modified Pd0 metal nanoparticles in contact with tetragonal ZrO2. This active state exhibits reaction rates exceeding those of a conventional supported Pd–ZrO2 reference catalyst and its high activity is unambiguously linked to the fast conversion of the highly reactive carbidic/dissolved C-species inside Pd0 toward CO at the Pd/ZrO2 phase boundary, which serves the role of providing efficient CO2 activation sites. In contrast, the near-surface intermetallic precursor decomposes toward ZrO2 islands at the surface of a quasi-infinite Pd0 metal bulk. Strongly delayed Pd carbide accumulation and thus carbon resegregation under reaction conditions leads to a much less active interfacial ZrO2–Pd0 state.

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