Electrochemical reduction of CO2 to value-added chemicals and fuels is a promising approach to st... more Electrochemical reduction of CO2 to value-added chemicals and fuels is a promising approach to store renewable energy while closing the anthropogenic carbon cycle. Despite significant advances in developing new electrocatalysts, this system still lacks enough energy conversion efficiency to become a viable technology for industrial applications. To develop an active and selective electrocatalyst and engineer the reaction environment to achieve high energy conversion efficiency, we need to improve our knowledge of the reaction mechanism and material structure under reaction conditions. In situ spectroscopies are among the most powerful tools which enable measurements of the system under real conditions. These methods provide information about reaction intermediates and possible reaction pathways, electrocatalyst structure and active sites, as well as the effect of the reaction environment on products distribution. This review aims to highlight the utilization of in situ spectroscopic...
Quantum dot (QD) sensitized TiO 2 is considered as a highly promising photoanode material for pho... more Quantum dot (QD) sensitized TiO 2 is considered as a highly promising photoanode material for photo-electrochemical (PEC) solar hydrogen production. However, due to its limited stability, the photoanode suffers from degradation of its long-term PEC performance. Here, we report the design and characterization of a high-efficiency and long-term stable Pt-free PEC cell. The photoanode is composed of a mesoporous TiO 2 nanoparticle film sensitized with " giant " core@shell QDs for PEC solar hydrogen generation. The thick shell enhances light absorption in the visible range, increases the stability of the QDs and does not inhibit charge separation, injection and transport, needed for proper operation of the device. We prepared thin films of Cu 2 S nanoflakes through a simple and reproducible procedure, and used them as counter-electrodes replacing the standard Pt film, resulting in equivalent performances of the PEC cell. We obtained an unprecedented photocurrent density ($ 10 mA/cm 2) for " giant " QDs based PEC devices (and corresponding H 2 generation) and a very promising stability, indicating that the proposed cell architecture is a good candidate for long-term stable QD-based PEC solar hydrogen generation.
We report the fabrication and testing of dye sensitized solar cells (DSSC) based on tin oxide (Sn... more We report the fabrication and testing of dye sensitized solar cells (DSSC) based on tin oxide (SnO 2) particles of average size ~20 nm. Fluorine-doped tin oxide (FTO) conducting glass substrates were treated with TiO x or TiCl 4 precursor solutions to create a blocking layer before tape casting the SnO 2 mesoporous anode. In addition, SnO 2 photoelectrodes were treated with the same precursor solutions to deposit a TiO 2 passivating layer covering the SnO 2 particles. We found that the modification enhances the short circuit current, open-circuit voltage and fill factor, leading to nearly 2-fold increase in power conversion efficiency, from 1.48% without any treatment, to 2.85% achieved with TiCl 4 treatment. The superior photovoltaic performance of the DSSCs assembled with modified photoanode is attributed to enhanced electron lifetime and suppression of electron recombination to the electrolyte, as confirmed by electrochemical impedance spectroscopy (EIS) carried out under dark condition. These results indicate that modification of the FTO and SnO 2 anode by titania can play a major role in maximizing the photo conversion efficiency.
Electrophoretic deposition (EPD) is a simple technique for the uptake of nanoparticles into mesop... more Electrophoretic deposition (EPD) is a simple technique for the uptake of nanoparticles into mesoporous films, for example to graft semiconducting nanocrystals (quantum dots, QDs) on mesoporous oxide thick films acting as photoanodes in third generation solar cells. Here we study the uptake of colloidal QDs into mesoporous TiO 2 films using EPD. We examined PbS@CdS core@shell QDs, which are optically active in the near infrared (NIR) region of the solar spectrum and exhibit improved long-term stability toward oxidation compared to their pure PbS counterpart, as demonstrated by X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) spectroscopy. We applied Rutherford backscattering spectrometry (RBS) to obtain the Pb depth profile into the TiO 2 matrix. EPD duration in the range from 5 to 120 min and applied voltages from 50 to 200 V were considered. The applied electric field induces the fast anchoring of QDs to the oxide surface. Consequently, QD concentration in the solution contained in the mesoporous film drastically decreases, inducing a Fick-like diffusion of QDs. We modelled the entire process as a QD diffusion related to the formation of a QD concentration gradient, and a depth-independent QD anchoring, and were able to determine the electric field-induced diffusion coefficient D for QDs and the characteristic time for QD grafting, in very good agreement with the experiment. D increases from (1.5 AE 0.4) Â 10 À5 mm 2 s À1 at 50 V to (1.1 AE 0.3) Â 10 À3 mm 2 s À1 at 200 V. The dynamics of EPD may also be applied to other different colloidal QDs and quantum rod materials for the sensitization of mesoporous films. These results quantitatively describe the process of QD uptake during EPD, and can be used to tune the optical and optoelectronic properties of composite systems, which determine, for instance, the photoconversion efficiency in QD solar cells (QDSCs).
N-type metal oxide solar cells sensitized by infrared absorbing PbS quantum dots (QDs) represent ... more N-type metal oxide solar cells sensitized by infrared absorbing PbS quantum dots (QDs) represent a promising alternative to traditional photovoltaic devices. However, colloidal PbS QDs capped with pure organic ligand shells suffer from surface oxidation that affects the long term stability of the cells. Application of a passivating CdS shell guarantees the increased long term stability of PbS QDs, but can negatively affect photoinduced charge transfer from the QD to the oxide and the resulting photoconversion efficiency (PCE). For this reason, the characterization of electron injection rates in these systems is very important, yet has never been reported. Here we investigate the photoelectron transfer rate from PbS@CdS core@shell QDs to wide bandgap semiconducting mesoporous films using photoluminescence (PL) lifetime spectroscopy. The different electron affinity of the oxides (SiO 2 , TiO 2 and SnO 2), the core size and the shell thickness allow us to fine tune the electron injection rate by determining the width and height of the energy barrier for tunneling from the core to the oxide. Theoretical modeling using the semi-classical approximation provides an estimate for the escape time of an electron from the QD 1S state, in good agreement with experiments. The results demonstrate the possibility of obtaining fast charge injection in near infrared (NIR) QDs stabilized by an external shell (injection rates in the range of 110–250 ns for TiO 2 films and in the range of 100–170 ns for SnO 2 films for PbS cores with diameters in the 3–4.2 nm range and shell thickness around 0.3 nm), with the aim of providing viable solutions to the stability issues typical of NIR QDs capped with pure organic ligand shells.
Electrochemical reduction of CO2 to value-added chemicals and fuels is a promising approach to st... more Electrochemical reduction of CO2 to value-added chemicals and fuels is a promising approach to store renewable energy while closing the anthropogenic carbon cycle. Despite significant advances in developing new electrocatalysts, this system still lacks enough energy conversion efficiency to become a viable technology for industrial applications. To develop an active and selective electrocatalyst and engineer the reaction environment to achieve high energy conversion efficiency, we need to improve our knowledge of the reaction mechanism and material structure under reaction conditions. In situ spectroscopies are among the most powerful tools which enable measurements of the system under real conditions. These methods provide information about reaction intermediates and possible reaction pathways, electrocatalyst structure and active sites, as well as the effect of the reaction environment on products distribution. This review aims to highlight the utilization of in situ spectroscopic...
Quantum dot (QD) sensitized TiO 2 is considered as a highly promising photoanode material for pho... more Quantum dot (QD) sensitized TiO 2 is considered as a highly promising photoanode material for photo-electrochemical (PEC) solar hydrogen production. However, due to its limited stability, the photoanode suffers from degradation of its long-term PEC performance. Here, we report the design and characterization of a high-efficiency and long-term stable Pt-free PEC cell. The photoanode is composed of a mesoporous TiO 2 nanoparticle film sensitized with " giant " core@shell QDs for PEC solar hydrogen generation. The thick shell enhances light absorption in the visible range, increases the stability of the QDs and does not inhibit charge separation, injection and transport, needed for proper operation of the device. We prepared thin films of Cu 2 S nanoflakes through a simple and reproducible procedure, and used them as counter-electrodes replacing the standard Pt film, resulting in equivalent performances of the PEC cell. We obtained an unprecedented photocurrent density ($ 10 mA/cm 2) for " giant " QDs based PEC devices (and corresponding H 2 generation) and a very promising stability, indicating that the proposed cell architecture is a good candidate for long-term stable QD-based PEC solar hydrogen generation.
We report the fabrication and testing of dye sensitized solar cells (DSSC) based on tin oxide (Sn... more We report the fabrication and testing of dye sensitized solar cells (DSSC) based on tin oxide (SnO 2) particles of average size ~20 nm. Fluorine-doped tin oxide (FTO) conducting glass substrates were treated with TiO x or TiCl 4 precursor solutions to create a blocking layer before tape casting the SnO 2 mesoporous anode. In addition, SnO 2 photoelectrodes were treated with the same precursor solutions to deposit a TiO 2 passivating layer covering the SnO 2 particles. We found that the modification enhances the short circuit current, open-circuit voltage and fill factor, leading to nearly 2-fold increase in power conversion efficiency, from 1.48% without any treatment, to 2.85% achieved with TiCl 4 treatment. The superior photovoltaic performance of the DSSCs assembled with modified photoanode is attributed to enhanced electron lifetime and suppression of electron recombination to the electrolyte, as confirmed by electrochemical impedance spectroscopy (EIS) carried out under dark condition. These results indicate that modification of the FTO and SnO 2 anode by titania can play a major role in maximizing the photo conversion efficiency.
Electrophoretic deposition (EPD) is a simple technique for the uptake of nanoparticles into mesop... more Electrophoretic deposition (EPD) is a simple technique for the uptake of nanoparticles into mesoporous films, for example to graft semiconducting nanocrystals (quantum dots, QDs) on mesoporous oxide thick films acting as photoanodes in third generation solar cells. Here we study the uptake of colloidal QDs into mesoporous TiO 2 films using EPD. We examined PbS@CdS core@shell QDs, which are optically active in the near infrared (NIR) region of the solar spectrum and exhibit improved long-term stability toward oxidation compared to their pure PbS counterpart, as demonstrated by X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) spectroscopy. We applied Rutherford backscattering spectrometry (RBS) to obtain the Pb depth profile into the TiO 2 matrix. EPD duration in the range from 5 to 120 min and applied voltages from 50 to 200 V were considered. The applied electric field induces the fast anchoring of QDs to the oxide surface. Consequently, QD concentration in the solution contained in the mesoporous film drastically decreases, inducing a Fick-like diffusion of QDs. We modelled the entire process as a QD diffusion related to the formation of a QD concentration gradient, and a depth-independent QD anchoring, and were able to determine the electric field-induced diffusion coefficient D for QDs and the characteristic time for QD grafting, in very good agreement with the experiment. D increases from (1.5 AE 0.4) Â 10 À5 mm 2 s À1 at 50 V to (1.1 AE 0.3) Â 10 À3 mm 2 s À1 at 200 V. The dynamics of EPD may also be applied to other different colloidal QDs and quantum rod materials for the sensitization of mesoporous films. These results quantitatively describe the process of QD uptake during EPD, and can be used to tune the optical and optoelectronic properties of composite systems, which determine, for instance, the photoconversion efficiency in QD solar cells (QDSCs).
N-type metal oxide solar cells sensitized by infrared absorbing PbS quantum dots (QDs) represent ... more N-type metal oxide solar cells sensitized by infrared absorbing PbS quantum dots (QDs) represent a promising alternative to traditional photovoltaic devices. However, colloidal PbS QDs capped with pure organic ligand shells suffer from surface oxidation that affects the long term stability of the cells. Application of a passivating CdS shell guarantees the increased long term stability of PbS QDs, but can negatively affect photoinduced charge transfer from the QD to the oxide and the resulting photoconversion efficiency (PCE). For this reason, the characterization of electron injection rates in these systems is very important, yet has never been reported. Here we investigate the photoelectron transfer rate from PbS@CdS core@shell QDs to wide bandgap semiconducting mesoporous films using photoluminescence (PL) lifetime spectroscopy. The different electron affinity of the oxides (SiO 2 , TiO 2 and SnO 2), the core size and the shell thickness allow us to fine tune the electron injection rate by determining the width and height of the energy barrier for tunneling from the core to the oxide. Theoretical modeling using the semi-classical approximation provides an estimate for the escape time of an electron from the QD 1S state, in good agreement with experiments. The results demonstrate the possibility of obtaining fast charge injection in near infrared (NIR) QDs stabilized by an external shell (injection rates in the range of 110–250 ns for TiO 2 films and in the range of 100–170 ns for SnO 2 films for PbS cores with diameters in the 3–4.2 nm range and shell thickness around 0.3 nm), with the aim of providing viable solutions to the stability issues typical of NIR QDs capped with pure organic ligand shells.
Uploads