An official website of the United States government
Abstract Solar-thermal technologies for converting chemicals using thermochemistry require extreme light concentration. Exploiting plasmonic nanostructures can dramatically increase the reaction rates by providing more efficient solar-to-heat conversion by broadband light absorption. Moreover, hot-carrier and local field enhancement effects can alter the reaction pathways. Such discoveries have boosted the field of photothermal catalysis, which aims at driving industrially-relevant chemical reactions using solar illumination rather than conventional heat sources. Nevertheless, only large arrays of plasmonic nano-units on a substrate, i.e., plasmonic metasurfaces, allow a quasi-unitary and broadband solar light absorption within a limited thickness (hundreds of nanometers) for practical applications. Through moderate light concentration (∼10 Suns), metasurfaces reach the same temperatures as conventional thermochemical reactors, or plasmonic nanoparticle bed reactors reach under ∼100 Suns. Plasmonic metasurfaces, however, have been mostly neglected so far for applications in the field of photothermal catalysis. In this Perspective, we discuss the potentialities of plasmonic metasurfaces in this emerging area of research. We present numerical simulations and experimental case studies illustrating how broadband absorption can be achieved within a limited thickness of these nanostructured materials. The approach highlights the synergy among different enhancement effects related to the ordered array of plasmonic units and the efficient heat transfer promoting faster dynamics than thicker structures (such as powdered catalysts). We foresee that plasmonic metasurfaces can play an important role in developing modular-like structures for the conversion of chemical feedstock into fuels without requiring extreme light concentrations. Customized metasurface-based systems could lead to small-scale and low-cost decentralized reactors instead of large-scale, infrastructure-intensive power plants.
more »
« less
Broadband Plasmonic Photocatalysis Enhanced by Photothermal Light Absorbers
Plasmonic photocatalysis is an emerging research field that holds promise for sustainable energy applications, particularly in solar energy conversion. In this study, we focus on the enhancement of broadband light absorption capabilities for plasmonic photocatalyst under white light illumination. By replacing parts of the catalyst with solar absorber, we can significantly improve the total reaction rate under mild heating conditions with less catalyst. Through careful comparison of reaction conditions and systematic optimization of the contributions from photothermal and non-thermal effects, we demonstrate a substantial enhancement in broadband light absorption capacity and overall light effectiveness, paving the way for advanced plasmonic photocatalysts with greater efficiency and practical applicability using solar light as the energy source.
more »
« less
- Award ID(s):
- 1954838
- PAR ID:
- 10512300
- Publisher / Repository:
- ACS
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry C
- Volume:
- 127
- Issue:
- 36
- ISSN:
- 1932-7447
- Page Range / eLocation ID:
- 17723 to 17731
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Plasmonic photocatalysis presents a promising method for light-to-matter conversion. However, most current studies focused on understanding the relative importance of thermal and nonthermal effects while their synergistic effects remained less studied. Here, we propose an index, termed Overall Light Effectiveness (OLE), to capture the combined impact of these light effects on reactions. By systematically varying the thickness of catalyst layers, we isolated thermal and nonthermal contributions and optimized them to achieve maximum light enhancement. We demonstrate the approach using carbon dioxide hydrogenation reaction on titania-supported rhodium nanoparticles as a model reaction system. It shows a generalizable potential in designing catalyst systems with optimum combinations of heating and light illumination, especially with broadband light illumination such as sunlight, for achieving the most economical light-to-matter conversion in plasmonic catalysis.more » « less
-
Solar water splitting using photoelectrochemical cells (PEC's) is a promising pathway toward clean and sustainable storage of renewable energy. Practical realization of solar-driven synthesis of hydrogen and oxygen integrating light absorption and electrolysis of water has been challenging because of (1) the limited stability of good photovoltaic materials under the required electrochemical conditions, and (2) photovoltaic efficiency losses due to light absorption by catalysts, the electrolyte, and generated bubbles, or reflection at their various interfaces. Herein, we evaluate a novel integrated solar water splitting architecture using efficient silicon heterojunction photovoltaic cells that avoids such losses and exhibits a solar-to-hydrogen (STH) efficiency in excess of 10%. Series-connected silicon Heterojunction with Intrinsic Thin layer (HIT) cells generate sufficient photovoltage for unassisted water splitting, with one of the cells acting as the photocathode. Platinum is deposited on the back (dark) junction of this HIT cell as the catalyst for the hydrogen evolution reaction (HER). The photocathode is protected from corrosion by a TiO 2 layer deposited by atomic layer deposition (ALD) interposed between the HIT cell and the Pt, enabling stable operation for >120 hours. Combined with oxygen evolution reaction (OER) catalysts deposited on a porous metal dark anode, these PEC's achieve stable water splitting with a record high STH efficiency for an integrated silicon photosynthesis device.more » « less
-
Plasmonic photocatalysis uses the light-induced resonant oscillation of free electrons in a metal nanoparticle to concentrate optical energy for driving chemical reactions. By altering the joint electronic structure of the catalyst and reactants, plasmonic catalysis enables reaction pathways with improved selectivity, activity, and catalyst stability. However, designing an optimal catalyst still requires a fundamental understanding of the underlying plasmonic mechanisms at the spatial scales of single particles, at the temporal scales of electron transfer, and in conditions analogous to those under which real reactions will operate. Thus, in this review, we provide an overview of several of the available and developing nanoscale and ultrafast experimental approaches, emphasizing those that can be performed in situ. Specifically, we discuss high spatial resolution optical, tip-based, and electron microscopy techniques; high temporal resolution optical and x-ray techniques; and emerging ultrafast optical, x-ray, tip-based, and electron microscopy techniques that simultaneously achieve high spatial and temporal resolution. Ab initio and classical continuum theoretical models play an essential role in guiding and interpreting experimental exploration, and thus, these are also reviewed and several notable theoretical insights are discussed.more » « less
-
We demonstrate a way to coherently control light at the nanoscale and achieve coherent perfect absorption (CPA) by using epsilon-near-zero (ENZ) plasmonic waveguides. The presented waveguides support an effective ENZ response at their cut-off frequency, combined with strong and homogeneous field enhancement along their nanochannels. The CPA conditions are perfectly satisfied at the ENZ frequency, surprisingly by a subwavelength plasmonic structure, resulting in strong CPA under the illumination of two counter-propagating plane waves with appropriate amplitudes and phases. In addition, we investigate the nonlinear response of the proposed ENZ plasmonic configuration as we increase the input intensity of the incident waves. We demonstrate that the CPA phenomenon can become both intensity- and phasedependent in this case leading to new tunable all-optical switching and absorption devices.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.jpcc.3c03639
