Oxidation Temperature-Dependent Electrochemical Doping of WO3 Deposited via Atomic Layer Deposition DOI
Alexandria R. C. Bredar, Hannah R. M. Margavio, Carrie L. Donley

et al.

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 9, 2024

Silicon-based photoelectrochemical devices show promise for the performance of light-driven CO2 reduction but suffer from instability under conditions relevant to reduction. Coating silicon electrodes with thin layers metal oxides has shown passivate unstable surfaces, and many different can be deposited on using various techniques. In this study, we investigate fundamental WO3-coated photoelectrodes, which were generated by oxidation W-metal films via atomic layer deposition both degenerately doped (nSi+) low-doped (pSi) silicon. Two temperatures investigated (400 600 °C), it was found that monoclinic phase WO3 predominates at more grain boundaries are present in °C film. From X-ray photoelectron spectroscopy, stoichiometry 1:3 W:O, low electron energy loss experiments indicate band gaps 3.0 3.1 eV 400 films, respectively. Cyclic voltammetry showed transfer kinetics increased after continued redox cycling, particularly material produced °C. spectra suggest observed increase electrode conductivity is due formation oxygen vacancies Electrochemical impedance spectroscopy indicated charge transport through impacted formed during Photoelectrochemical studies pSi/WO3 highly variable, only producing a photocurrent photovoltage some samples. Our best sample, °C, 180 mV, lower than what previously been reported (500 mV). We hypothesize variability arose roughened WSiOx interface film preparation. shows as oxide coating silicon, our results high-quality between Si vital performance.

Language: Английский

Photoelectrocatalytic reduction of CO2 to formate using immobilized molecular manganese catalysts on oxidized porous silicon DOI
Young Hyun Hong, Xiaofan Jia, Eleanor Stewart-Jones

et al.

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102462 - 102462

Published: March 1, 2025

Language: Английский

Citations

2
Hydrosilylation of porous silicon: Unusual possibilities and potential challenges DOI
Yit Lung Khung

Advances in Colloid and Interface Science, Journal Year: 2025, Volume and Issue: unknown, P. 103416 - 103416

Published: Jan. 1, 2025

Language: Английский

Citations

0
Semiartificial Photoelectrochemistry for CO2-Mediated Enantioselective Organic Synthesis DOI Creative Commons
Tessel Bouwens, Samuel J. Cobb, Celine W. S. Yeung

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 15, 2025

Photoelectrochemical (PEC) cells are under intensive development for the synthesis of solar fuels, but CO2 reduction typically only results in simple building blocks such as HCOO-. Here, we demonstrate that CO2-converting PEC can drive integrated enzymatic domino catalysis to produce chiral organic molecules by using CO2/HCOO- a sustainable redox couple. First, establish semiartificial electrode consisting three enzymes co-immobilized on high surface area based carbon felt covered mesoporous indium tin oxide (ITO) coating. When applying mild cathodic potential (-0.25 V vs reversible hydrogen (RHE)), is reduced HCOO- W-formate dehydrogenase (FDHNvH) from Nitratidesulfovibrio vulgaris Hildenborough, which then enables NAD+ NADH an NAD+-cofactor-dependent formate Candida boidinii (FDHCB). Subsequently, alcohol (ADH) uses generated cycling reduce acetophenone 1-phenylethanol good enantiomeric excess (93%) and conversion yields (38%). Depending specific ADH (ADHS or ADHR), either (S)- (R)-1-phenylethanol be synthesized at pH 6 20 °C. To illustrate energy utilization, integrate nanoconfined with platform semiconductor photocathode allow enantioselective (at +0.8 RHE) fuel device. This proof-of-principle demonstration shows concepts devices artificial photosynthesis readily translated precise biocatalysis, including production light.

Language: Английский

Citations

0
Heterogeneous Electrocatalytic CO2 Reduction by Supported Molecular Catalysts Well Dispersed on Electrode Surface DOI Creative Commons
Ke Ma, Shiyu Zhang, Weixuan Nie

et al.

ChemElectroChem, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

Electrochemical CO 2 reduction (CO R) to value‐added products using renewable electricity offers a promising approach toward achieving carbon neutrality. Among various electrocatalysts, molecular catalysts, particularly transition metal complexes, stand out due the high selectivity for single specific and desirable tunability, enabling rational optimization of catalytic performance. However, their practical application is hindered by low operating current densities challenges in catalyst recycling. To address these limitations, immobilizing catalysts on electrode surfaces has emerged as an effective strategy integrating selective into heterogeneous catalysis. This mini review focuses distinct category heterogenized catalysts—those molecularly dispersed supported substrates or surfaces‐which exhibit remarkable activity at single‐molecule level ability drive deep (beyond two electrons) under certain conditions. Recent progress this field comprehensively discussed, emphasizing critical impacts molecule‐level dispersion catalyst‐support interactions electronic properties, multi‐electron transfer kinetics, overall Moreover, overview potential applications beyond electrochemical R provided end. aims offer valuable insights future design efficient scalable electrocatalysts sustainable conversion.

Language: Английский

Citations

0
Fundamental Insights into Photoelectrochemical Carbon Dioxide Reduction: Elucidating the Reaction Pathways DOI
Lujie Zuo, Yuchao Deng, Lu Chen

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(22), P. 16795 - 16833

Published: Oct. 31, 2024

The photoelectrochemical (PEC) reduction of carbon dioxide (CO2) to produce solar fuels presents a sustainable strategy mitigate CO2 emissions and alleviate the global energy crisis. While significant research efforts have been dedicated optimizing cell system configurations designing efficient photoelectrocatalysts, there remains lack in-depth understanding pathway. This review provides comprehensive overview fundamental insights PEC with focus on pathways from perspectives final products adsorption modes. First, key challenges are identified analyzed, including initial activation CO2, competitive hydrogen evolution reaction (HER), complex carbon–carbon (C–C) coupling process. then examines aspects process, covering state-of-the-art devices, their operational principles, methodologies for capturing intermediates. through concerted or sequential proton–electron transfer mechanisms is discussed in detail. Furthermore, potential systematically categorized basis distinct modes that drive insertion, carbon-coordinated oxygen-coordinated monodentate adsorption, bidentate oxygen vacancies. Detailed leading formation C1, C2, C3 compounds elucidated, an emphasis strategies enhance selectivity toward C1 C2+ products. In particular, aids catalyst design. For production, design focuses promoting activation, as rate-determining step (RDS) activation. contrast, formation, aim increase intermediate concentration, thereby enhancing lateral interaction intermediates, which crucial C–C coupling. Finally, summarizes future breakthroughs electron, interfacial, ionic pathways, offering into ongoing technologies.

Language: Английский

Citations

3
Direct Detection of Key Intermediates during the Product Release in Rhenium Bipyridine-Catalyzed CO2 Reduction Reaction DOI Creative Commons
Samir Chattopadhyay, Mun Hon Cheah, Reiner Lomoth

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(21), P. 16324 - 16334

Published: Oct. 22, 2024

Rhenium bipyridine tricarbonyl complexes, fac-[Re(bpy)(CO)3X]n+, are highly effective in selectively converting CO2 to CO under electrochemical and photochemical conditions. Despite numerous mechanistic studies aimed at understanding its reduction reaction (CO2RR) pathway, the intermediates further into catalytic cycle have escaped detection, steps leading product release remained elusive. In this study, employing stopped-flow mixing coupled with time-resolved infrared spectroscopy, we observed, for first time, reduced Re-tetracarbonyl species, [Re(bpy)(CO)4]0, a half-life of approximately 55 ms acetonitrile solvent. This intermediate is proposed be common both CO2RR. Furthermore, directly observed (CO) from intermediate. Additionally, detected accumulation [Re(bpy)(CO)3(CH3CN)]+ as byproduct following release, significant side conditions limited supply reducing equivalents mirroring The process could unambiguously attributed an electron transfer-catalyzed ligand substitution involving [Re(bpy)(CO)4]0 by simultaneous real-time detection all involved species. We believe that significantly impacts CO2RR efficiency class catalysts or during electrocatalysis mild overpotentials.

Language: Английский

Citations

2
Porous Carbon Nanorods Encapsulating Bismuth Nanoparticles Promote p-Si Nanowire Array for Photoelectrocatalytic CO2 Reduction to Formate DOI
Yuanyuan Chen,

Jihu Kang,

Mingyue Zou

et al.

Industrial & Engineering Chemistry Research, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 9, 2024

Photoelectrocatalytic reduction of carbon dioxide to high value-added chemicals is one the effective means reduce greenhouse gas emissions and alleviate energy crisis. In this study, porous nanorods encapsulating bismuth (Bi) nanoparticles were synthesized using a metal–organic framework (MOF)-assisted spatial confinement high-temperature carbonization strategy then modified on silicon nanowires construct Si–Bi@Cx composite photocathode. The presence plasmonic metal Bi enhances light absorption improves selectivity products as reactive substances. At −0.9 V vs RHE, Si–Bi@C800 photocathode achieves faradaic efficiency for formic acid (FEHCOOH) up 91.23%, with production rate 88.5 μmol·h–1·cm–2. Further experimental analysis in situ infrared spectroscopy results showed that strong hydrophobicity not only contact between electrode water inhibit occurrence hydrogen evolution reaction but also accelerate mass transfer CO2 molecules increase local concentration. Simultaneously, promote formation *OCHO intermediate realize efficient conversion acid. This study lays foundation constructing active sites silicon-based semiconductors.

Language: Английский

Citations

1
Interfacial Channel Design on the Charge Migration for PEC Applications DOI

Shengdong Sun,

Cheng Wang, Shikuo Li

et al.

Chinese Journal of Structural Chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 100398 - 100398

Published: July 1, 2024

Language: Английский

Citations

0
Oxidation Temperature-Dependent Electrochemical Doping of WO3 Deposited via Atomic Layer Deposition DOI
Alexandria R. C. Bredar, Hannah R. M. Margavio, Carrie L. Donley

et al.

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 9, 2024

Silicon-based photoelectrochemical devices show promise for the performance of light-driven CO2 reduction but suffer from instability under conditions relevant to reduction. Coating silicon electrodes with thin layers metal oxides has shown passivate unstable surfaces, and many different can be deposited on using various techniques. In this study, we investigate fundamental WO3-coated photoelectrodes, which were generated by oxidation W-metal films via atomic layer deposition both degenerately doped (nSi+) low-doped (pSi) silicon. Two temperatures investigated (400 600 °C), it was found that monoclinic phase WO3 predominates at more grain boundaries are present in °C film. From X-ray photoelectron spectroscopy, stoichiometry 1:3 W:O, low electron energy loss experiments indicate band gaps 3.0 3.1 eV 400 films, respectively. Cyclic voltammetry showed transfer kinetics increased after continued redox cycling, particularly material produced °C. spectra suggest observed increase electrode conductivity is due formation oxygen vacancies Electrochemical impedance spectroscopy indicated charge transport through impacted formed during Photoelectrochemical studies pSi/WO3 highly variable, only producing a photocurrent photovoltage some samples. Our best sample, °C, 180 mV, lower than what previously been reported (500 mV). We hypothesize variability arose roughened WSiOx interface film preparation. shows as oxide coating silicon, our results high-quality between Si vital performance.

Language: Английский

Citations

0