A titanium carbide (Ti3C2Tx) MXene is employed as an efficient solid support to host a nitrogen (N) and sulfur (S) coordinated ruthenium single atom (RuSA) catalyst, which displays superior activity ...toward the hydrogen evolution reaction (HER). X‐ray absorption fine structure spectroscopy and aberration corrected scanning transmission electron microscopy reveal the atomic dispersion of Ru on the Ti3C2Tx MXene support and the successful coordination of RuSA with the N and S species on the Ti3C2Tx MXene. The resultant RuSA‐N‐S‐Ti3C2Tx catalyst exhibits a low overpotential of 76 mV to achieve the current density of 10 mA cm−2. Furthermore, it is shown that integrating the RuSA‐N‐S‐Ti3C2Tx catalyst on n+np+‐Si photocathode enables photoelectrochemical hydrogen production with exceptionally high photocurrent density of 37.6 mA cm−2 that is higher than the reported precious Pt and other noble metals catalysts coupled to Si photocathodes. Density functional theory calculations suggest that RuSA coordinated with N and S sites on the Ti3C2Tx MXene support is the origin of this enhanced HER activity. This work would extend the possibility of using the MXene family as a solid support for the rational design of various single atom catalysts.
Ti3C2Tx MXene is demonstrated as a 2D solid support to host a ruthenium single atom (RuSA) catalyst for water splitting. The resultant RuSA‐N‐S‐Ti3C2Tx catalyst coupled with n+np+‐Si photocathode enables photoelectrochemical H2 production with exceptionally high photocurrent density of 37.6 mA cm−2 under AM 1.5G illumination.
MXene, a new class of 2D materials, has gained significant attention owing to its attractive electrical conductivity, tunable work function, and metallic nature for wide range of applications. ...Herein, delaminated few layered Ti3C2Tx MXene contacted Si solar cells with a maximum power conversion efficiency (PCE) of ≈11.5% under AM1.5G illumination are demonstrated. The formation of an Ohmic junction of the metallic MXene to n+‐Si surface efficiently extracts the photogenerated electrons from n+np+‐Si, decreases the contact resistance, and suppresses the charge carrier recombination, giving rise to excellent open‐circuit voltage and short‐circuit current density. The rapid thermal annealing process further improves the electrical contact between Ti3C2Tx MXene and n+‐Si surface by reducing sheet resistance, increasing electrical conductivity, and decreasing cell series resistance, thus leading to a remarkable improvement in fill factor and overall PCE. The work demonstrated here can be extended to other MXene compositions as potential electrodes for developing highly performing solar cells.
Delaminated few layered Ti3C2Tx MXene contacted Si solar cells with a maximum power conversion efficiency of ≈11.5% under AM1.5G illumination are achieved. The work demonstrated here can be extended to other members of the MXene family as potential electrodes for developing high performance solar cells.
Despite III-V semiconductors demonstrating extraordinary solar-to-hydrogen (STH) conversion efficiencies, high cost and poor stability greatly impede their practical implementation in ...photoelectrochemical (PEC) water splitting applications. Here, we present a simple and efficient strategy for III-V-based photoelectrodes that functionally and spatially decouples the light harvesting component of the device from the electrolysis part that eliminates parasitic light absorption, reduces the cost, and enhances the stability without any compromise in efficiency. The monolithically integrated PEC cell was fabricated by an epitaxial lift-off and transfer of inversely grown InGaP/GaAs to a robust Ni-substrate and the resultant photoanode exhibits an STH efficiency of ~9% with stability ~150 h. Moreover, with the ability to access both sides of the device, we constructed a fully-integrated, unassisted-wireless "artificial leaf" system with an STH efficiency of ~6%. The excellent efficiency and stability achieved herein are attributed to the light harvesting/catalysis decoupling scheme, which concurrently improves the optical, electrical, and electrocatalytic characteristics.
The fast penetration of electrification in rural areas calls for the development of competitive decentralized approaches. A promising solution is represented by low-cost and compact integrated solar ...flow batteries; however, obtaining high energy conversion performance and long device lifetime simultaneously in these systems has been challenging. Here, we use high-efficiency perovskite/silicon tandem solar cells and redox flow batteries based on robust BTMAP-Vi/N
-TEMPO redox couples to realize a high-performance and stable solar flow battery device. Numerical analysis methods enable the rational design of both components, achieving an optimal voltage match. These efforts led to a solar-to-output electricity efficiency of 20.1% for solar flow batteries, as well as improved device lifetime, solar power conversion utilization ratio and capacity utilization rate. The conceptual design strategy presented here also suggests general future optimization approaches for integrated solar energy conversion and storage systems.
The photoelectrochemical (PEC) approach is attractive as a promising route for the nitrogen reduction reaction (NRR) toward ammonia (NH3) synthesis. However, the challenges in synergistic management ...of optical, electrical, and catalytic properties have limited the efficiency of PEC NRR devices. Herein, to enhance light‐harvesting, carrier separation/transport, and the catalytic reactions, a concept of decoupling light‐harvesting and electrocatalysis by employing a cascade n+np+‐Si photocathode is implemented. Such a decoupling design not only abolishes the parasitic light blocking but also concurrently improves the optical and electrical properties of the n+np+‐Si photocathode without compromising the efficiency. Experimental and density functional theory studies reveal that the porous architecture and N‐vacancies promote N2 adsorption of the Au/porous carbon nitride (PCN) catalyst. Impressively, an n+np+‐Si photocathode integrating the Au/PCN catalyst exhibits an outstanding PEC NRR performance with maximum Faradaic efficiency (FE) of 61.8% and NH3 production yield of 13.8 µg h–1 cm–2 at −0.10 V versus reversible hydrogen electrode (RHE), which is the highest FE at low applied potential ever reported for the PEC NRR.
A Si photocathode with a unique design, in which the light‐harvesting and electrocatalysis components in the monolithic device are spatially decoupled, exhibits outstanding photoelectrochemical nitrogen reduction activity with maximum Faradaic efficiency of 61.8% and NH3 yield of 13.8 µg h−1 cm−2 at a low applied potential of −0.10 V versus reversible hydrogen electrode.
Abstract
Converting sunlight into a storable form of energy by spontaneous water splitting is of great interest but the difficulty in simultaneous management of optical, electrical, and catalytic ...properties has limited the efficiency of photoelectrochemical (PEC) devices. Herein, we implemented a decoupling scheme of light harvesting and electrocatalysis by employing a back-buried junction (BBJ) PEC cell design, which enables >95% front side light-harvesting, whereas the electrochemical reaction in conjunction with carrier separation/transport/collection occurs on the back side of the PEC cell. The resultant silicon BBJ-PEC half-cell produces a current density of 40.51 mA cm
−2
for hydrogen evolution by minimizing optical, electrical, and catalytic losses (as low as 6.11, 1.76, and 1.67 mA cm
−2
, respectively). Monolithic fabrication also enables three BBJ-PEC cells to be connected in series as a single module, enabling unassisted solar water-splitting with a solar-to-hydrogen conversion efficiency of 15.62% and a hydrogen generation rate of 240 μg cm
−2
h
−1
.
3D organic–inorganic hybrid halide perovskites have attracted great interest due to their impressive optoelectronic properties. Recently, the emergence of 2D layered hybrid perovskites, with their ...excellent and tunable optoelectronic behavior, has encouraged researchers to develop the next generation of optoelectronics based on these 2D materials. However, device fabrication methods of scalable patterning on both types of hybrid perovskites are still lacking as these materials are readily damaged by the organic solvents in standard lithographic processes. We conceived the orthogonal processing and patterning method: Chlorobenzene and hexane, which are orthogonal to hybrid perovskites, are utilized in modified electron beam lithography (EBL) processes to fabricate perovskite-based devices without compromising their electronic or optical characteristics. As a proof-of-concept, we used the orthogonal EBL technique to fabricate a 2D layered single-crystal (C6H5C2H4NH3)2PbI4 photodetector featuring nanoscale patterned electrodes and superior photodetection ability with responsivity of 5.4 mA/W and detectivity of 1.07 × 1013 cm Hz1/2/W. Such orthogonal processing and patterning methods are believed to fully enable the high-resolution, high-throughput fabrication of complex perovskite-based electronics in the near future.
Hydrogen production via photoelectrochemical water-splitting is a key source of clean and sustainable energy. The use of one-dimensional nanostructures as photoelectrodes is desirable for ...photoelectrochemical water-splitting applications due to the ultralarge surface areas, lateral carrier extraction schemes, and superior light-harvesting capabilities. However, the unavoidable surface states of nanostructured materials create additional charge carrier trapping centers and energy barriers at the semiconductor–electrolyte interface, which severely reduce the solar-to-hydrogen conversion efficiency. In this work, we address the issue of surface states in GaN nanowire photoelectrodes by employing a simple and low-cost surface treatment method, which utilizes an organic thiol compound (i.e., 1,2-ethanedithiol). The surface-treated photocathode showed an enhanced photocurrent density of −31 mA/cm2 at −0.2 V versus RHE with an incident photon-to-current conversion efficiency of 18.3%, whereas untreated nanowires yielded only 8.1% efficiency. Furthermore, the surface passivation provides enhanced photoelectrochemical stability as surface-treated nanowires retained ∼80% of their initial photocurrent value and produced 8000 μmol of gas molecules over 55 h at acidic conditions (pH ∼ 0), whereas the untreated nanowires demonstrated only <4 h of photoelectrochemical stability. These findings shed new light on the importance of surface passivation of nanostructured photoelectrodes for photoelectrochemical applications.
Building on regenerative photoelectrochemical solar cells and emerging electrochemical redox flow batteries (RFBs), more efficient, scalable, compact, and cost‐effective hybrid energy conversion and ...storage devices could be realized. An integrated photoelectrochemical solar energy conversion and electrochemical storage device is developed by integrating regenerative silicon solar cells and 9,10‐anthraquinone‐2,7‐disulfonic acid (AQDS)/1,2‐benzoquinone‐3,5‐disulfonic acid (BQDS) RFBs. The device can be directly charged by solar light without external bias, and discharged like normal RFBs with an energy storage density of 1.15 Wh L−1 and a solar‐to‐output electricity efficiency (SOEE) of 1.7 % over many cycles. The concept exploits a previously undeveloped design connecting two major energy technologies and promises a general approach for storing solar energy electrochemically with high theoretical storage capacity and efficiency.
Even flow: An integrated solar‐charged storage device is developed that builds on regenerative silicon solar cells and organic redox flow batteries. This prototype device utilizes a p+nn+‐Si/TiO2/Pt photocathode and an n+np+‐Si/TiO2/Pt photoanode. The excellent device performance promises a general, efficient, and cost‐effective approach for storing the intermittent solar energy electrochemically.
Organic semiconductors demonstrate several advantages over conventional inorganic materials for novel electronic and optoelectronic applications, including molecularly tunable properties, ...flexibility, low‐cost, and facile device integration. However, before organic semiconductors can be used for the next‐generation devices, such as ultrafast photodetectors (PDs), it is necessary to develop new materials that feature both high mobility and ambient stability. Toward this goal, a highly stable PD based on the organic single crystal PtBr2(5,5′‐bis(CF3CH2OCH2)‐2,2′‐bpy) (or “Pt complex (1o)”) is demonstrated as the active semiconductor channel—a material that features a lamellar molecular structure and high‐quality, intraligand charge transfer. Benefitting from its unique crystal structure, the Pt‐complex (1o) device exhibits a field‐effect mobility of ≈0.45 cm2 V−1 s−1 without loss of significant performance under ambient conditions even after 40 days without encapsulation, as well as immersion in distilled water for a period of 24 h. Furthermore, the device features a maximum photoresponsivity of 1 × 103 A W−1, a detectivity of 1.1 × 1012 cm Hz1/2 W−1, and a record fast response/recovery time of 80/90 µs, which has never been previously achieved in other organic PDs. These findings strongly support and promote the use of the single‐crystal Pt complex (1o) in next‐generation organic optoelectronic devices.
A Pt‐complex‐based organic semiconductor is developed as the active channel and/or photoabsorption layer for high‐performance organic device applications. The Pt‐complex device displays a stable mobility (0.45 cm2 V−1 s−1), a remarkable photoresponsivity (1000 A W−1), and a record fast response/fall time (80/90 µs), demonstrating the highest combined efficiency and stability reported for an organic semiconductor.
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