Modulating multi-hole reaction pathways for photoelectrochemical water oxidation on gold nanocatalysts

Zhang, Yuchao; Guo, Wenxiao; Johnston‐Peck, Aaron C.; Hu, Yue; Song, Xiaoyu; Wei, Wei David

doi:10.1039/c9ee04192c

Cited by 53 publications

(49 citation statements)

References 52 publications

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“…Furthermore, one could suggest that the nanocatalysts with more rough surfaces would have a larger amount of active sites, leading to more efficient catalysts. It is also interesting to note that our ideas on importance of charged holes in catalytic processes are related to recent proposals on the role of charged holes in organic electrosynthesis and photochemical water oxidation ( 33 , 34 ).…”

Section: Discussionmentioning

confidence: 59%

Microscopic mechanisms of cooperative communications within single nanocatalysts

Punia

Chaudhury

Kolomeisky

2022

Proc. Natl. Acad. Sci. U.S.A.

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Catalysis is a method of accelerating chemical reactions that is critically important for fundamental research as well as for industrial applications. It has been recently discovered that catalytic reactions on metal nanoparticles exhibit cooperative effects. The mechanism of these observations, however, remains not well understood. In this work, we present a theoretical investigation on possible microscopic origin of cooperative communications in nanocatalysts. In our approach, the main role is played by positively charged holes on metal surfaces. A corresponding discrete-state stochastic model for the dynamics of holes is developed and explicitly solved. It is shown that the observed spatial correlation lengths are given by the average distances migrated by the holes before they disappear, while the temporal memory is determined by their lifetimes. Our theoretical approach is able to explain the universality of cooperative communications as well as the effect of external electric fields. Theoretical predictions are in agreement with experimental observations. The proposed theoretical framework quantitatively clarifies some important aspects of the microscopic mechanisms of heterogeneous catalysis.

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Section: Discussionmentioning

confidence: 59%

Microscopic mechanisms of cooperative communications within single nanocatalysts

Punia

Chaudhury

Kolomeisky

2022

Proc. Natl. Acad. Sci. U.S.A.

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“…The HT induces a reduced conduction band offset, resulting in a more efficient interfacial charge transfer performance. [ 44 ] Moreover, the derivative of d(OCP)/d(time) versus time curves are shown in Figure S7, Supporting Information. The CZTS/CdS (HA) sample shows the sharpest curves upon switching the light on and off.…”

Section: Resultsmentioning

confidence: 99%

Accelerating Electron‐Transfer and Tuning Product Selectivity Through Surficial Vacancy Engineering on CZTS/CdS for Photoelectrochemical CO₂ Reduction

Zhou

Sun

Huang

et al. 2021

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Copper‐based chalcogenides have been considered as potential photocathode materials for photoelectrochemical (PEC) CO2 reduction due to their excellent photovoltaic performance and favorable conduction band alignment with the CO2 reduction potential. However, they suffer from low PEC efficiency due to the sluggish charge transfer kinetics and poor selectivity, resulting from random CO2 reduction reaction pathways. Herein, a facile heat treatment (HT) of a Cu2ZnSnS4(CZTS)/CdS photocathode is demonstrated to enable significant improvement in the photocurrent density (−0.75 mA cm−2 at −0.6 V vs RHE), tripling that of pristine CZTS, as a result of the enhanced charge transfer and promoted band alignment originating from the elemental inter‐diffusion at the CZTS/CdS interface. In addition, rationally regulated CO2 reduction selectivity toward CO or alcohols can be obtained by tailoring the surficial sulfur vacancies by HT in different atmospheres (air and nitrogen). Sulfur vacancies replenished by O‐doping is shown to favor CO adsorption and the CC coupling pathway, and thereby produce methanol and ethanol, whilst the CdS surface with more S vacancies promotes CO desorption capability with higher selectivity toward CO. The strategy in this work rationalizes the interface charge transfer optimization and surface vacancy engineering simultaneously, providing a new insight into PEC CO2 reduction photocathode design.

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“…In recent years, solar-energy-driven water splitting through photoelectrochemical (PEC) process is considered as a great promising strategy for conversion of solar power to chemical energy. [1][2][3][4][5][6] To utilize solar energy efficiently, semiconductor catalysts are highly desired in photoelectrodes. At present, single-catalyst systems, such as TiO 2 , [7][8][9][10] Fe 2 O 3 , [11][12][13] BiVO 4 , [14][15][16] and metallic sulfides, [17][18][19][20] have been studied widely as photoanodes.…”

Section: Introductionmentioning

confidence: 99%

Conjugated π Electrons of MOFs Drive Charge Separation at Heterostructures Interface for Enhanced Photoelectrochemical Water Oxidation

Wang

Sun

Tian

et al. 2021

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Photoanode material with high efficiency and stability is extensively desirable in photoelectrochemical (PEC) water splitting for green/renewable energy source. Herein, novel heterostructures is constructed via coating rutile TiO2 nanorods with metal organic framework (MOF) materials UiO‐66 or UiO‐67 (UiO‐66@TiO2 and UiO‐67@TiO2), respectively. The π electrons in the MOF linkers could increase the local electronegativity near the heterojunction interface due to the conjugation effect, thereby enhancing the internal electric field (IEF) at the heterojunction interface. The IEF could drive charge transfer following Z‐scheme mechanism in the prepared heterostructures, inducing photogenerated charge separation efficiency increasing as 156% and 253% for the UiO‐66@TiO2 and UiO‐67@TiO2, respectively. Correspondingly, the UiO‐66@TiO2 and UiO‐67@TiO2 enhanced the photocurrent density as approximate two‐ and threefolds compared with that of pristine TiO2 for PEC water oxidation in universal pH electrolytes. This work demonstrates an effective method of regulating the IEF of heterojunction toward further improved charge separation.

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Modulating multi-hole reaction pathways for photoelectrochemical water oxidation on gold nanocatalysts

Abstract: Catechol stabilizes photo-generated holes on metal nanoparticles to create a new multi-hole reaction pathway for oxidizing water under visible light.

Cited by 53 publications

References 52 publications

Microscopic mechanisms of cooperative communications within single nanocatalysts

Microscopic mechanisms of cooperative communications within single nanocatalysts

Accelerating Electron‐Transfer and Tuning Product Selectivity Through Surficial Vacancy Engineering on CZTS/CdS for Photoelectrochemical CO₂ Reduction

Conjugated π Electrons of MOFs Drive Charge Separation at Heterostructures Interface for Enhanced Photoelectrochemical Water Oxidation

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Modulating multi-hole reaction pathways for photoelectrochemical water oxidation on gold nanocatalysts

Abstract: Catechol stabilizes photo-generated holes on metal nanoparticles to create a new multi-hole reaction pathway for oxidizing water under visible light.

Cited by 53 publications

References 52 publications

Microscopic mechanisms of cooperative communications within single nanocatalysts

Microscopic mechanisms of cooperative communications within single nanocatalysts

Accelerating Electron‐Transfer and Tuning Product Selectivity Through Surficial Vacancy Engineering on CZTS/CdS for Photoelectrochemical CO2 Reduction

Conjugated π Electrons of MOFs Drive Charge Separation at Heterostructures Interface for Enhanced Photoelectrochemical Water Oxidation

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Accelerating Electron‐Transfer and Tuning Product Selectivity Through Surficial Vacancy Engineering on CZTS/CdS for Photoelectrochemical CO₂ Reduction