Suljo Linic

Bio: Suljo Linic is an academic researcher from University of Michigan. The author has contributed to research in topics: Catalysis & Oxide. The author has an hindex of 48, co-authored 101 publications receiving 14454 citations. Previous affiliations of Suljo Linic include Max Planck Society & University of Delaware.

Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy

Abstract: Recent years have seen a renewed interest in the harvesting and conversion of solar energy. Among various technologies, the direct conversion of solar to chemical energy using photocatalysts has received significant attention. Although heterogeneous photocatalysts are almost exclusively semiconductors, it has been demonstrated recently that plasmonic nanostructures of noble metals (mainly silver and gold) also show significant promise. Here we review recent progress in using plasmonic metallic nanostructures in the field of photocatalysis. We focus on plasmon-enhanced water splitting on composite photocatalysts containing semiconductor and plasmonic-metal building blocks, and recently reported plasmon-mediated photocatalytic reactions on plasmonic nanostructures of noble metals. We also discuss the areas where major advancements are needed to move the field of plasmon-mediated photocatalysis forward.

Visible-light-enhanced catalytic oxidation reactions on plasmonic silver nanostructures

Abstract: Catalysis plays a critical role in chemical conversion, energy production and pollution mitigation. High activation barriers associated with rate-limiting elementary steps require most commercial heterogeneous catalytic reactions to be run at relatively high temperatures, which compromises energy efficiency and the long-term stability of the catalyst. Here we show that plasmonic nanostructures of silver can concurrently use low-intensity visible light (on the order of solar intensity) and thermal energy to drive catalytic oxidation reactions--such as ethylene epoxidation, CO oxidation, and NH₃ oxidation--at lower temperatures than their conventional counterparts that use only thermal stimulus. Based on kinetic isotope experiments and density functional calculations, we postulate that excited plasmons on the silver surface act to populate O₂ antibonding orbitals and so form a transient negative-ion state, which thereby facilitates the rate-limiting O₂-dissociation reaction. The results could assist the design of catalytic processes that are more energy efficient and robust than current processes.

Photochemical transformations on plasmonic metal nanoparticles

Abstract: Optically excited plasmonic nanoparticles can activate chemical reactions on their surfaces. The underlying physical mechanisms responsible for the chemical activity and advances in photocatalysis on plasmonic metallic nanostructures are discussed. The strong interaction of electromagnetic fields with plasmonic nanomaterials offers opportunities in various technologies that take advantage of photophysical processes amplified by this light–matter interaction. Recently, it has been shown that in addition to photophysical processes, optically excited plasmonic nanoparticles can also activate chemical transformations directly on their surfaces. This potentially offers a number of opportunities in the field of selective chemical synthesis. In this Review we summarize recent progress in the field of photochemical catalysis on plasmonic metallic nanostructures. We discuss the underlying physical mechanisms responsible for the observed chemical activity, and the issues that must be better understood to see progress in the field of plasmon-mediated photocatalysis.

Water Splitting on Composite Plasmonic-Metal/Semiconductor Photoelectrodes: Evidence for Selective Plasmon-Induced Formation of Charge Carriers near the Semiconductor Surface

Abstract: A critical factor limiting the rates of photocatalytic reactions, including water splitting, on oxide semiconductors is the high rate of charge-carrier recombination. In this contribution, we demonstrate that this issue can be alleviated significantly by combining a semiconductor photocatalyst with tailored plasmonic-metal nanostructures. Plasmonic nanostructures support the formation of resonant surface plasmons in response to a photon flux, localizing electromagnetic energy close to their surfaces. We present evidence that the interaction of localized electric fields with the neighboring semiconductor allows for the selective formation of electron/hole (e−/h+) pairs in the near-surface region of the semiconductor. The advantage of the formation of e−/h+ pairs near the semiconductor surface is that these charge carriers are readily separated from each other and easily migrate to the surface, where they can perform photocatalytic transformations.

Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures

Abstract: It is now shown that, unlike most semiconductors, plasmonic metal nanostructures constructively couple the energy of photons and thermal energy, with the reaction rate positively responding to both stimuli. These unique characteristics suggest that these photocatalysts could prove useful for heterogeneous catalytic processes that cannot be activated using conventional thermal processes on metals or photocatalytic processes on semiconductors.

Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer To Achieving Sustainability?

Abstract: As a fascinating conjugated polymer, graphitic carbon nitride (g-C3N4) has become a new research hotspot and drawn broad interdisciplinary attention as a metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability, and “earth-abundant” nature. This critical review summarizes a panorama of the latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites, including (1) nanoarchitecture design of bare g-C3N4, such as hard and soft templating approaches, supramolecular preorganization assembly, exfoliation, and template-free synthesis routes, (2) functionalization of g-C3N4 at an atomic level (elemental doping) and molecular level (copolymerization), and (3) modification of g-C3N4 with well-matched energy levels of another semiconductor or a metal as a cocatalyst to form heterojunction nanostructures. The constructi...

Understanding TiO2 photocatalysis: mechanisms and materials.

Abstract: Jenny Schneider,*,† Masaya Matsuoka,‡ Masato Takeuchi,‡ Jinlong Zhang, Yu Horiuchi,‡ Masakazu Anpo,‡ and Detlef W. Bahnemann*,† †Institut fur Technische Chemie, Leibniz Universitaẗ Hannover, Callinstrasse 3, D-30167 Hannover, Germany ‡Faculty of Engineering, Osaka Prefecture University, 1 Gakuen-cho, Sakai Osaka 599-8531, Japan Key Lab for Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology, Shanghai 200237, China

Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy

Abstract: Recent years have seen a renewed interest in the harvesting and conversion of solar energy. Among various technologies, the direct conversion of solar to chemical energy using photocatalysts has received significant attention. Although heterogeneous photocatalysts are almost exclusively semiconductors, it has been demonstrated recently that plasmonic nanostructures of noble metals (mainly silver and gold) also show significant promise. Here we review recent progress in using plasmonic metallic nanostructures in the field of photocatalysis. We focus on plasmon-enhanced water splitting on composite photocatalysts containing semiconductor and plasmonic-metal building blocks, and recently reported plasmon-mediated photocatalytic reactions on plasmonic nanostructures of noble metals. We also discuss the areas where major advancements are needed to move the field of plasmon-mediated photocatalysis forward.

Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions

Abstract: A fundamental change has been achieved in understanding surface electrochemistry due to the profound knowledge of the nature of electrocatalytic processes accumulated over the past several decades and to the recent technological advances in spectroscopy and high resolution imaging. Nowadays one can preferably design electrocatalysts based on the deep theoretical knowledge of electronic structures, via computer-guided engineering of the surface and (electro)chemical properties of materials, followed by the synthesis of practical materials with high performance for specific reactions. This review provides insights into both theoretical and experimental electrochemistry toward a better understanding of a series of key clean energy conversion reactions including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The emphasis of this review is on the origin of the electrocatalytic activity of nanostructured catalysts toward the aforementioned reactions by correlating the apparent electrode performance with their intrinsic electrochemical properties. Also, a rational design of electrocatalysts is proposed starting from the most fundamental aspects of the electronic structure engineering to a more practical level of nanotechnological fabrication.

Computational high-throughput screening of electrocatalytic materials for hydrogen evolution

Abstract: The pace of materials discovery for heterogeneous catalysts and electrocatalysts could, in principle, be accelerated by the development of efficient computational screening methods. This would require an integrated approach, where the catalytic activity and stability of new materials are evaluated and where predictions are benchmarked by careful synthesis and experimental tests. In this contribution, we present a density functional theory-based, high-throughput screening scheme that successfully uses these strategies to identify a new electrocatalyst for the hydrogen evolution reaction (HER). The activity of over 700 binary surface alloys is evaluated theoretically; the stability of each alloy in electrochemical environments is also estimated. BiPt is found to have a predicted activity comparable to, or even better than, pure Pt, the archetypical HER catalyst. This alloy is synthesized and tested experimentally and shows improved HER performance compared with pure Pt, in agreement with the computational screening results.