Online citations, reference lists, and bibliographies.
Please confirm you are human
(Sign Up for free to never see this)
← Back to Search

Quantum Confinement Controls Photocatalysis: A Free Energy Analysis For Photocatalytic Proton Reduction At CdSe Nanocrystals.

J. Zhao, M. A. Holmes, Frank E Osterloh
Published 2013 · Chemistry, Medicine

Save to my Library
Download PDF
Analyze on Scholarcy
Share
The ability to adjust the mechanical, optical, magnetic, electric, and chemical properties of materials via the quantum confinement effect is well-understood. Here, we provide the first quantitative analysis of quantum-size-controlled photocatalytic H2 evolution at the semiconductor-solution interface. Specifically, it is found that the hydrogen evolution rate from illuminated suspended CdSe quantum dots in aqueous sodium sulfite solution depends on nanocrystal size. Photoelectrochemical measurements on CdSe nanocrystal films reveal that the observed reactivity is controlled by the free energy change of the system, as determined by the proton reduction potential and the quasi-Fermi energy of the dots. The corresponding free energy change can be fitted to the photocatalytic activity using a modified Butler-Volmer equation for reaction kinetics. These findings establish a quantitative experimental basis for quantum-confinement-controlled proton reduction with semiconductor nanocrystals. Electrochemical data further indicate that proton reduction occurs at cadmium sites on the dots, and that charge separation in these nanocrystals is controlled by surface effects, not by space charge layers.
This paper references
10.1021/JA070099A
Size-dependent electron injection from excited CdSe quantum dots into TiO2 nanoparticles.
István Robel (2007)
10.1016/0927-0248(92)90091-3
Photoelectrochemical studies of colloidal TiO2-films : the charge separation process studied by means of action spectra in the UV region
A. Hagfeldt (1992)
10.1557/MRS.2010.5
Recent developments in solar water-splitting photocatalysis
Frank E Osterloh (2011)
10.1002/CHIN.199443314
Principles and Applications of Semiconductor Photoelectrochemistry.
M. Tan (1994)
10.1007/S10008-008-0670-8
Tafel slopes from first principles
S. Fletcher (2009)
10.1103/PHYSREVB.49.17072
Quantum-dot quantum well CdS/HgS/CdS: Theory and experiment.
Schooss (1994)
10.1103/PHYSREVB.53.16338
Measurement and assignment of the size-dependent optical spectrum in CdSe quantum dots.
Norris (1996)
10.1021/JP030334L
Band-Edge Tuning in Self-Assembled Layers of Bi2S3 Nanoparticles Used To Photosensitize Nanocrystalline TiO2
L. Peter (2003)
10.1021/J100072A023
Theoretical Models for the Action Spectrum and the Current-Voltage Characteristics of Microporous Semiconductor Films in Photoelectrochemical Cells
S. Soedergren (1994)
Inorganic Materials as Catalysts for Photochemical Splitting of Water
B. Viswanathan (2009)
10.1002/BBPC.19840881010
Photo-Chemistry of Colloidal Metal Sulfides 8. Photo-Physics of Extremely Small CdS Particles: Q-State CdS and Magic Agglomeration Numbers
A. Fojtík (1984)
10.1017/cbo9780511524141
Optical properties of semiconductor nanocrystals
S. Gaponenko (1998)
10.1007/978-94-009-3073-5_13
Quantum States of Confined Carriers in Very Thin AlxGa1-x As-GaAs-AlxGa1-xAs Heterostructures
R. Dingle (1974)
Photochemical and Photoelectrochemical Conversion and Storage of Solar Energy (Proc
G. Hodes (1993)
10.1002/CHIN.199927259
Synthesis and Characterization of a Size Series of Extremely Small Thiol-Stabilized CdSe Nanocrystals.
A. Rogach (1999)
10.1126/science.1191462
Multiple Exciton Collection in a Sensitized Photovoltaic System
J. Sambur (2010)
Recent Developments in SolarWater - SplittingPhotocatalysis
F. E. Osterloh (2011)
10.1149/1.2119676
Electrochemical Studies of Photocorrosion of n ‐ CdSe
K. W. Frese (1983)
10.1073/pnas.1011972107
Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles
K. Tvrdy (2010)
10.1103/PHYSREVB.38.9797
Quantum-size effects of interacting electrons and holes in semiconductor microcrystals with spherical shape.
Kayanuma (1988)
10.1149/1.2115568
The Transport and Kinetics of Photogenerated Carriers in Colloidal Semiconductor Electrode Particles
W. J. Albery (1984)
10.1021/ja8003683
Photoinduced ultrafast electron transfer from CdSe quantum dots to Re-bipyridyl complexes.
J. Huang (2008)
10.1002/cphc.201100120
Ultrafast electron transfer from photoexcited CdSe quantum dots to methylviologen.
F. Scholz (2011)
10.1073/pnas.0603395103
Powering the planet: Chemical challenges in solar energy utilization
N. Lewis (2006)
Interfacial electron-transfer reactions in colloidal semiconductors
M. Graetzel (1992)
10.1021/J150659A025
Photochemical hydrogen production with cadmium sulfide suspensions
N. Buehler (1984)
10.1103/PHYSREVLETT.98.146803
Experimental observation of quantum confinement in the conduction band of CdSe quantum dots.
J. Lee (2007)
V.Optical Properties of Semiconductor Nanocrystals
S. Gaponenki (1998)
10.1039/B508268B
Size and ligand effects on the electrochemical and spectroelectrochemical responses of CdSe nanocrystals.
Claudia Querner (2005)
10.1021/CM203293J
Single-Crystal Tungsten Oxide Nanosheets: Photochemical Water Oxidation in the Quantum Confinement Regime
Mollie Waller (2012)
10.1149/1.2069045
Nanocrystalline photoelectrochemical cells : a new concept in photovoltaic cells
G. Hodes (1992)
10.1103/PHYSREVLETT.80.1501
Magnetic edge states in a magnetic quantum dot
Heung-Sun Sim (1998)
10.1146/ANNUREV.MATSCI.30.1.475
The Electronic Structure of Semiconductor Nanocrystals1
A. L. Efros (2000)
10.5860/choice.33-4512
Electrochemistry for Chemists
D. T. Sawyer (1995)
10.1002/ijch.201200073
Recent Progress in Photocatalysis Mediated by Colloidal II-VI Nanocrystals
M. Wilker (2012)
The Electrochemical Society Proceedings Series. In Photoelectrochemistry and Electrosynthesis on Semiconducting Materials (The Electrochemical Society Proceedings Series, PV
G. Hodes (1988)
10.1007/3-540-57565-0_75
Photoinduced charge transfer processes at semiconductor electrodes and particles
R. Memming (1994)
10.1103/PHYSREVB.58.7120
Quantum size level structure of narrow-gap semiconductor nanocrystals: Effect of band coupling
A. L. Efros (1998)
10.1002/BBPC.19820860409
Photo‐Degradation and Fluorescence of Colloidal‐Cadmium Sulfide in Aqueous Solution
A. Henglein (1982)
10.1103/PhysRevLett.87.146601
Magnetic quantum dot: a magnetic transmission barrier and resonator.
H. S. Sim (2001)
10.1021/JP200197D
Current and Voltage Limiting Processes in Thin Film Hematite Electrodes
Benjamin M. Klahr (2011)
10.1108/acmm.2003.12850eae.001
Electrochemical Methods: Fundamentals and Applications
Allen J. Bard (1980)
10.1021/J100212A031
Interfacial electron-transfer reactions in colloidal semiconductor dispersions. Kinetic analysis
M. Graetzel (1982)
10.1021/NL0256210
Size-Dependent Photoconductivity in CdSe Nanoparticles as Measured by Time-Resolved Terahertz Spectroscopy
M. C. Beard (2002)
10.1063/1.445676
A simple model for the ionization potential, electron affinity, and aqueous redox potentials of small semiconductor crystallites
L. Brus (1983)
The Electrochemical Society Proceedings Series
G. Hodes
10.1108/ACMM.2003.12850EAE.001
Electrochemical Methods: Fundamentals and Applications
M. Rooij (2003)
Photoelectrochemical cells : Materials for clean energy
M. Graetzel (2001)
10.1039/b800489g
Heterogeneous photocatalyst materials for water splitting.
A. Kudo (2009)
10.1021/JP035395Y
Interpretation of the Time Constants Measured by Kinetic Techniques in Nanostructured Semiconductor Electrodes and Dye-Sensitized Solar Cells
J. Bisquert (2004)
10.1103/PHYSREVB.69.153302
First principle thousand atom quantum dot calculations
L. Wang (2004)
10.1016/0013-4686(90)87067-C
The impact of semiconductors on the concepts of electrochemistry
H. Gerischer (1990)
10.1016/0022-0728(94)03622-A
Photoelectrochemical studies of colloidal TiO2 films: The effect of oxygen studied by photocurrent transients
A. Hagfeldt (1995)
10.1021/JA060292P
Translucent thin film Fe2O3 photoanodes for efficient water splitting by sunlight: nanostructure-directing effect of Si-doping.
I. Cesar (2006)
10.1021/ja0782706
Quantum dot solar cells. Tuning photoresponse through size and shape control of CdSe-TiO2 architecture.
Anusorn Kongkanand (2008)
10.1080/00018737500101431
Structural and electrical properties of granular metal films
B. Abeles (1975)
10.1021/JA003598J
Size-dependent optical spectroscopy of a homologous series of CdSe cluster molecules.
V. N. Soloviev (2001)
10.1146/ANNUREV.PC.15.100164.001103
Chemical and Electrochemical Electron-Transfer Theory
R. Marcus (1964)
CdSe-MoS 2 : A Quantum Size-Confined Photocatalyst for Hydrogen Evolution from Water under Visible Light
F. Frame (2010)
10.1016/0022-0728(86)80520-4
A particle size effect in the sensitization of TiO2 electrodes by a CdS deposit
H. Gerischer (1986)
10.1039/b718796c
First demonstration of CdSe as a photocatalyst for hydrogen evolution from water under UV and visible light.
F. Andrew Frame (2008)
10.17877/DE290R-2790
Magnetic Quantum Dot
K. Chang (2001)
10.1039/c2cp23801b
The hydrogen evolution reaction in a room temperature ionic liquid: mechanism and electrocatalyst trends.
Y. Meng (2012)
10.1039/c1cc16082f
Quantum confinement controlled photocatalytic water splitting by suspended CdSe nanocrystals.
M. A. Holmes (2012)
10.1103/PHYSREVB.41.6079
Comparison between calculated and experimental values of the lowest excited electronic state of small CdSe crystallites.
Lippens (1990)
10.1021/JP809060P
Influence of Feature Size, Film Thickness, and Silicon Doping on the Performance of Nanostructured Hematite Photoanodes for Solar Water Splitting
I. Cesar (2009)
10.1021/ja200144w
Photocatalytic water oxidation with nonsensitized IrO2 nanocrystals under visible and UV light.
F. Frame (2011)
10.1021/JP046445H
Size and Structure-Dependent Photocatalytic Activity of Jingle-Bell-Shaped Silica-Coated Cadmium Sulfide Nanoparticles for Methanol Dehydrogenation
B. Pal (2004)
10.1021/J100387A017
Vectorial electron injection into transparent semiconductor membranes and electric field effects on the dynamics of light-induced charge separation
B. O'Regan (1990)
10.1021/J100082A044
CdS Nanoclusters: Synthesis, Characterization, Size Dependent Oscillator Strength, Temperature Shift of the Excitonic Transition Energy, and Reversible Absorbance Shift
T. Vossmeyer (1994)
10.1002/BBPC.19961001104
Synthesis and characterization of thiol-stabilized CdTe nanocrystals
A. Rogach (1996)
10.1149/1.1838552
Surface States and Photovoltaic Effects in CdSe Quantum Dot Films
L. Kronik (1998)
10.1126/science.1227775
Robust Photogeneration of H2 in Water Using Semiconductor Nanocrystals and a Nickel Catalyst
Z. Han (2012)
10.1126/SCIENCE.281.5383.1647
Onset of catalytic activity of gold clusters on titania with the appearance of nonmetallic properties
Valden (1998)
10.1021/jz201629p
Manipulation of Charge Transfer Across Semiconductor Interface. A Criterion That Cannot Be Ignored in Photocatalyst Design.
P. Kamat (2012)
10.1039/C1EE02110A
Photocatalytic water oxidation with suspended alpha-Fe2O3 particles-effects of nanoscaling
T. Townsend (2011)
10.1002/CHIN.199304012
Nanocrystalline Photoelectrochemical Cells. A New Concept in Photovoltaic Cells.
G. Hodes (1993)
10.1021/nn204350w
CdSe quantum dot-fullerene hybrid nanocomposite for solar energy conversion: electron transfer and photoelectrochemistry.
J. Bang (2011)
10.1038/35104607
Photoelectrochemical cells
M. Graetzel (2001)
10.1002/CHIN.200126012
Size-Dependent Optical Spectroscopy of a Homologous Series of CdSe Cluster Molecules.
V. N. Soloviev (2001)
10.1021/JP0754583
Energetics of Photoinduced Electron-Transfer Reactions Decided by Quantum Confinement
G. Scholes (2007)
10.1021/JA00155A017
Monolayers in Three Dimensions: NMR, SAXS, Thermal, and Electron Hopping Studies of Alkanethiol Stabilized Gold Clusters
R. Terrill (1995)
10.1021/nn201788f
Measuring electron and hole transfer in core/shell nanoheterostructures.
Chi-Hung Chuang (2011)
10.1021/J150668A032
Photochemical production of hydrogen with zinc sulfide suspensions
J. F. Reber (1984)
10.1021/CM7024203
Inorganic Materials as Catalysts for Photochemical Splitting of Water
Frank E Osterloh (2008)
10.1021/JA056494N
Quantum dot solar cells. harvesting light energy with CdSe nanocrystals molecularly linked to mesoscopic TiO2 films.
István Robel (2006)
10.1021/JP044127C
Visible light-induced water oxidation on mesoscopic α-Fe2O3 films made by ultrasonic spray pyrolysis
Alexis Duret (2005)
10.1063/1.447228
Size effects in the excited electronic states of small colloidal CdS crystallites
R. Rossetti (1984)
10.1039/c2cs35266d
Inorganic nanostructures for photoelectrochemical and photocatalytic water splitting.
Frank E Osterloh (2013)
10.1021/JZ1007966
Photocatalytic Water Splitting: Recent Progress and Future Challenges
K. Maeda (2010)
10.1039/c0cc00540a
Enhanced photocatalytic activity of quantum-confined tungsten trioxide nanoparticles in mesoporous silica.
D. Tanaka (2010)
10.2172/899136
Basic Research Needs for Solar Energy Utilization: report of the Basic Energy Sciences Workshop on Solar Energy Utilization, April 18-21, 2005
N. Lewis (2005)
10.1246/BCSJ.68.752
Semiconductor Photocatalysis : Size Control of Surface-Capped CdS Nanocrystallites and the Quantum Size Effect in Their Photocatalysis
S. Yanagida (1995)
10.1021/JP0460801
Size-dependent electrochemical behavior of thiol-capped CdTe nanocrystals in aqueous solution.
S. Poznyak (2005)
10.1021/CR00033A003
Light-Induced Redox Reactions in Nanocrystalline Systems
A. Hagfeldt (1995)



This paper is referenced by
10.1039/C7TA01670K
Direct synthesis of all-inorganic heterostructured CdSe/CdS QDs in aqueous solution for improved photocatalytic hydrogen generation
Zhi-jun Li (2017)
10.1021/jacs.6b06548
Selenium Redox Reactivity on Colloidal CdSe Quantum Dot Surfaces
E. Tsui (2016)
10.1021/acs.joc.8b01651
Visible-Light Photocatalytic Synthesis of Amines from Imines via Transfer Hydrogenation Using Quantum Dots as Catalysts.
Zi-wei Xi (2018)
10.1016/j.apsusc.2019.144065
Direct Z-scheme photocatalytic removal of ammonia via the narrow band gap MoS2/N-doped graphene hybrid catalyst upon near-infrared irradiation
H. Zhang (2020)
10.1016/J.NANOEN.2017.10.031
Intermediate-mediated strategy to horn-like hollow mesoporous ultrathin g-C3N4 tube with spatial anisotropic charge separation for superior photocatalytic H2 evolution
C. Liu (2017)
10.1021/ACSENERGYLETT.6B00665
Photocatalysis versus Photosynthesis: A Sensitivity Analysis of Devices for Solar Energy Conversion and Chemical Transformations
Frank E Osterloh (2017)
10.1007/s10853-016-9888-5
Enhanced photocatalytic capability of zinc ferrite nanotube arrays decorated with gold nanoparticles for visible light-driven photodegradation of rhodamine B
H. Liu (2016)
10.1016/J.CHEMPR.2019.06.019
Efficient and Selective CO2 Reduction Integrated with Organic Synthesis by Solar Energy
Qing Guo (2019)
10.1021/ja501489h
Efficient and limiting reactions in aqueous light-induced hydrogen evolution systems using molecular catalysts and quantum dots.
Carolina Gimbert-Suriñach (2014)
10.1039/c8nr04344b
Size-controlled electron transfer rates determine hydrogen generation efficiency in colloidal Pt-decorated CdS quantum dots.
W. Li (2018)
10.1021/ACS.CHEMREV.6B00102
Electronic Processes within Quantum Dot-Molecule Complexes.
R. Harris (2016)
10.1021/nn504561v
Diameter dependent electron transfer kinetics in semiconductor-enzyme complexes.
K. A. Brown (2014)
10.1038/s41467-020-14756-5
Electrochemically-stable ligands bridge the photoluminescence-electroluminescence gap of quantum dots
Chaodan Pu (2020)
10.1021/acsami.7b06980
Aqueous Exfoliation of Graphite into Graphene Assisted by Sulfonyl Graphene Quantum Dots for Photonic Crystal Applications.
Minxiang Zeng (2017)
10.1002/cssc.201402885
Vectorial electron transfer for improved hydrogen evolution by mercaptopropionic-acid-regulated CdSe quantum-dots-TiO2 -Ni(OH)2 assembly.
S. Yu (2015)
10.1039/C3EE42993H
Use of potential determining ions to control energetics and photochemical charge transfer of a nanoscale water splitting photocatalyst
Rachel L. Chamousis (2014)
10.1007/978-3-319-68879-4_2
Semiconductor-Based Photocatalytic Systems for the Solar-Light-Driven Water Splitting and Hydrogen Evolution
O. Stroyuk (2018)
10.1007/128_2015_633
Nanoscale Effects in Water Splitting Photocatalysis.
Frank E Osterloh (2016)
10.1021/jacs.8b03316
Ultrathin WO3·0.33H2O Nanotubes for CO2 Photoreduction to Acetate with High Selectivity.
Songmei Sun (2018)
10.1021/ACS.CHEMMATER.5B04521
Investigating the Control by Quantum Confinement and Surface Ligand Coating of Photocatalytic Efficiency in Chalcopyrite Copper Indium Diselenide Nanocrystals
A. Jana (2016)
10.1039/C3TC32049A
Cation exchange synthesis and optoelectronic properties of type II CdTe–Cu2−xTe nano-heterostructures
Ilka Kriegel (2014)
10.1016/J.NANTOD.2016.04.005
Charge transfer and separation in photoexcited quantum dot-based systems
K. V. Vokhmintcev (2016)
10.1021/ACSENERGYLETT.7B00061
Designing the Surfaces of Semiconductor Quantum Dots for Colloidal Photocatalysis
E. Weiss (2017)
10.1021/ACSCATAL.6B00418
Atomic Layer Deposited (ALD) TiO2 on Fibrous Nano-Silica (KCC-1) for Photocatalysis: Nanoparticle Formation and Size Quantization Effect
R. Singh (2016)
10.1016/j.ijleo.2020.164480
Light formation mechanisms induced by well-aligned sub-20-nm Ag quantum dots produced alongside patterned porous Si walls and bottoms
J. H. Bang (2020)
10.1063/1.5125000
Size dependence of photocatalytic hydrogen generation for CdTe quantum dots.
Jiajia Yin (2019)
10.1021/ACS.JPCC.5B12380
Photocatalytic Reduction of Fumarate to Succinate on ZnS Mineral Surfaces
Ruixin Zhou (2016)
10.1007/s11164-019-03904-2
Low-dimensional II–VI semiconductors for photocatalytic hydrogen generation
M. Zhukovskyi (2019)
10.1016/j.jphotochem.2020.112580
Interaction of CdTe-MPA quantum dots with meso-tetra methyl pyridyl porphyrin. Charge transfer complex formation
G. G. Parra (2020)
10.1016/J.IJHYDENE.2017.06.153
Efficient and robust visible light photocatalytic H2 production based on CdSe quantum dots sensitized titania
Guan Zhang (2017)
10.1002/adma.201605646
0D-2D Quantum Dot: Metal Dichalcogenide Nanocomposite Photocatalyst Achieves Efficient Hydrogen Generation.
X. Liu (2017)
10.1201/B18066-8
Photoelectrochemistry with Nanostructured Semiconductors
W. Wen (2015)
See more
Semantic Scholar Logo Some data provided by SemanticScholar