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The use of photosystem II (PSII) in hybrid bio-photoelectrochemical cells for conversion of solar energy to electrical current is hampered by PSII's narrow absorption cross-section and the generally poor electrical connection between isolated complex and different anode materials. Here, we merge isolated market-grade spinach PSII with 25 nm cystamine-2,6-dichlorobenzoquinone (cys-DCBQ) modified Au-nanoparticles (PSII–AuNPCys-DCBQ) to obtain one of the highest reported photocurrent values to date (35 mA cm−2 mg−1 chlorophyll), retaining the native oxygen evolution properties of PSII. More than 80% of the PSII in solution assembles stably onto the AuNPCys-DCBQ. Spectroscopic studies show strong functional association in these hybrid particles. Mechanistic investigations reveal a dual role of the quinone-modified AuNPs, harvesting and transference of the excitation energy to PSII (resulting in ∼10-fold enhancement of anodic photocurrent in the 500–550 nm irradiation range) and simultaneously improving the electron transfer from PSII into the graphite anode (by almost 6-fold over the entire visible range of light).

The development of an intriguing concept using optical polymers for photonics is reported to enable modulation of refractive index (RI) in solution cast thin films with precise spatial control. While extensive efforts in polymer science have focused on methods to prepare optically transparent polymers with high RI, the creation of photoresponsive polymer systems to spatially adjust the refractive index upon irradiation is a distinct technical challenge requiring development of materials amenable to this process. The ability to create refractive index contrast (i.e., a difference in RI between two domains) is a critical capability required in photonics for the fabrication of integrated photonics devices, such as, polymer waveguides. In this report, we detail the synthesis of optical polymers tailored to this application, termed Refractive Index Contrast (RIC) polymers, in which the RI of the material can be photopatterned where UV exposure in the presence of a photoacid generator resulted in a permanent increase of RI in the exposed regions thus creating regions of high RIC. This process creates the high RI core of waveguides in a single step and lends itself to rapid fabrication of photonic devices via direct laser writing. Waveguides made from RIC polymers were found to have propagation losses of ∼2 dB/cm at 1550 nm.

The electrical double-layer plays a key role in important interfacial electrochemical processes from catalysis to energy stor-age and corrosion. Therefore, understanding its structure is crucial for the progress of sustainable technologies. We extract new physico-chemical information on the capacitance and structure of the electrical double-layer of platinum and gold nanoparticles at the molecular level, employing single nanoparticle electrochemistry. We reveal that the charge storage ability of the solid/liquid interface is larger by one order-of-magnitude than predicted by the traditional mean-field models of the double-layer such as the Gouy-Chapman-Stern-model. Performing Molecular Dynamics simulations, we investigate the possible relationship between the measured high capacitance and adsorption strength of the water adlayer formed at the metal surface. These insights may launch the active tuning of solid-solvent and solvent-solvent interactions as innovative design strategy to transform energy technologies towards superior performance and sustainability.

We report on a new strategy for preparing polymer–nanoparticle composite Faraday rotators for use in magnetic sensing and optical isolation. While most applications of Faraday rotators make use of inorganic garnet crystals, these are generally limited by low magneto-optical activity (low Verdet constants), high cost, and/or limited processing options. This has led to an interest in new materials with improved activity and processing characteristics. We have developed a new type of magneto-optical material based on polymer–nanoparticle composites that can be completely prepared by solution processing methods with tunable Verdet constants and device sensitivity. By exchanging native surface ligands on magneto-optically active CoFe2O4 nanocrystals with polymer compatible ligands, enhanced nanoparticle dispersion in processible polymer matrices was observed at up to 15 wt% inorganic loading. Employing a multilayer polymer film construct, functional Faraday rotator devices were prepared by simple sequential spin-coating of active nanocomposite and protective, barrier cellulose acetate layers. For these assemblies, magneto-optic activity and sensitivity are easily tuned through variation of nanoparticle feed and control of polymer film layers, respectively. These multilayered Faraday rotators show up to a 10-fold enhancement in Verdet constant compared to reference terbium gallium garnets at 1310 nm, opening new possibilities for the fabrication of “plastic garnets” as low cost alternatives to existing inorganic materials for use in the near-IR.

[2Fe–2S] organometallic complexes are effective electrocatalysts for the reduction of weak acids in acetonitrile to generate molecular hydrogen (H2) (hydrogen evolution reaction, HER). Inco...

Lead-free double perovskites are studied as an optional replacement to lead halide perovskites in optoelectronic applications. Recently, double-perovskite materials in which two divalent lead cations are replaced with an Ag+ and a trivalent cation have been demonstrated. The presence of a reactive silver cation and observations of metallic silver nanodecorations raised concerns regarding the stability and applicability of these materials. To better understand the nucleation and crystal growth of lead-free double perovskites, we explore the origin and role that metallic silver nanoparticles (NPs) play in the Ag-based Pb-free double-perovskite nanocrystal (NC) systems such as Cs2AgInCl6, Cs2AgSbCl6, Cs2AgBiCl6, and Cs2AgBiBr6. With major focus on Cs2AgInCl6 NCs, we show evidence supporting growth of the NCs through heterogeneous nucleation on preexisting metallic silver seeds. The silver seeds nucleate prior to injection of halide through reduction of the Ag+ ion by the aminic ligand. The presence of preexisting silver NPs is supported by a localized surface plasmon resonance (LSPR). The injection of halide precursor into the reaction mixture step initiates a fast nucleation and growth of the perovskite NC on the silver seed. The change in the dielectric medium at the interface of the silver NP results in a quantifiable red shift of the LSPR peak. In addition, we demonstrate charge transfer from the perovskite to the silver NP through photoinduced electrochemical Ostwald ripening of the silver NPs via UV irradiation. The ripened perovskite-metal hybrid nanocrystal exhibits modified optical properties in the form of quenched emission and enhanced plasmonic absorption. Future development of Ag-based double-perovskite NC applications depends on the ability to control Ag+ reduction at all synthetic stages. This understanding is critical for delivering stability and functionality for silver-based lead-free perovskite nanocrystals.

Shape-controlled nanomaterials have been in the spotlight of photocatalysis for nearly two decades as they afford a unique level of energetic and structural tunability while possessing many desirable characteristics of both homogeneous and heterogeneous catalysts, such as solution stability, high turnover number, and facile catalyst isolation. However, they come with their own set of challenges. Fundamentally, photocatalysis can be thought of as an analog to electrocatalysis, wherein thermodynamic driving force is provided by photosensitizer-originated excited charge carriers as opposed to an external circuit. In this minireview, recent advances and challenges in the development of shape-controlled nanomaterials for photocatalysis are highlighted, drawing attention to emerging areas of research and development such as nontoxic heavy metal–free photocatalysts, nanocrystal–ligand–solution interface engineering, and biohybrid systems for improved activity in challenging redox reactions.

We report on noble metal tipping of heterostructured nanocrystals (NCs) of CdSe@CdS tetrapods (TPs) as a chemical reaction to manifest energetic differences between type I and quasi-type II heterojunctions. The energetics between zincblende (ZB) CdSe seed and wurtzite CdS TP arms has previously been probed primarily using ultrafast spectroscopic methods. However, to interrogate the energetics of CdSe@CdS TPs from both larger and very small ZB CdSe seeds (i.e., effective diameters (Deff) 6.2 to 1.8 nm) we utilize the photodeposition of gold nanoparticles as a facile and selective chemical reaction to correlate reaction rates with tetrapod energetics. We observe a 20-fold enhancement in the rate of selective photodeposition of a single AuNP tip onto this series of TPs, which were attributed to straddling of type I vs. quasi-type II energetics as a direct consequence of varying ZB CdSe seed size. Synthetic access to type I and quasi-type II TPs enabled the synthesis of singly tipped AuNP-CdSe@CdS TPs in gram quantities, which is the largest scale synthesis of metal–semiconductor Janus nanoparticles to date.

We report on a versatile synthetic method of preparing colloidal copolymers and terpolymers composed of dipolar Au@Co core-shell nanoparticles (NPs) in the backbone, along with semiconductor CdSe@CdS nanorod (NR), or tetrapod (TP) side chain groups. A seven-step colloidal total synthesis enabled the synthesis of well-defined colloidal comonomers composed of a dipolar Au@CoNP attached to a single CdSe@CdS NR, or TP, where magnetic dipolar associations between Au@CoNP units promoted the formation of colloidal co- or terpolymers. The key step in this synthesis was the ability to photodeposit a single AuNP tip onto CdSe@CdS NR or TP that enables selective seeding of a dipolar CoNP onto the AuNP seed. We show that the variation of the AuNP size directly controlled the size and dipolar character of the CoNP tip, where the size modulation of the Au and Au@CoNP tips is analogous to control of comonomer reactivity ratios in classical copolymerization processes.

Electrocatalytic [FeFe]-hydrogenase mimics for the hydrogen evolution reaction (HER) generally suffer from low activity, high overpotential, aggregation, oxygen sensitivity, and low solubility in water. By using atom-transfer radical polymerization (ATRP), a new class of [FeFe]-metallopolymers with precise molar mass, defined composition, and low polydispersity, has been prepared. The synthetic methodology introduced here allows facile variation of polymer composition to optimize the [FeFe] solubility, activity, and long-term chemical and aerobic stability. Water soluble functional metallopolymers facilitate electrocatalytic hydrogen production in neutral water with loadings as low as 2 ppm and operate at rates an order of magnitude faster than hydrogenases (2.5×105 s-1 ), and with low overpotential requirement. Furthermore, unlike the hydrogenases, these systems are insensitive to oxygen during catalysis, with turnover numbers on the order of 40 000 under both anaerobic and aerobic conditions.

We report on the first synthesis of a heterostructured semiconductor tetrapod from CdSe@CdS that carries a single dipolar nanoparticle tip from a core-shell colloid of Au@Co. A four-step colloidal total synthesis was developed, where the key step in the synthesis was the selective deposition of a single AuNP tip onto a CdSe@CdS tetrapod under UV-irradiation. Synthetic accessibility to this dipolar heterostructured tetrapod enabled the use of these as colloidal monomers to form colloidal polymers that carry the semiconductor tetrapod as a side chain group attached to the CoNP colloidal polymer main chain. The current report details a number of novel discoveries on the selective synthesis of an asymmetric heterostructured tetrapod that is capable of 1D dipolar assembly into colloidal polymers that carry tetrapods as side chain groups that mimic "giant tert-butyl groups".

Conduction and valence band energies (ECB, EVB) for CdSe nanorods (NRs) functionalized with Au nanoparticle (NP) tips are reported here, referenced to the vacuum scale. We use (a) UV photoemission spectroscopy (UPS) to measure EVB for NR films, utilizing advanced approaches to secondary electron background correction, satellite removal to enhance spectral contrast, and correction for shifts in local vacuum levels; and (b) waveguide-based spectroelectrochemistry to measure ECB from onset potentials for electron injection into NR films tethered to ITO. For untipped CdSe NRs, both approaches show EVB = 5.9-6.1 eV and ECB = 4.1-4.3 eV. Addition of Au tips alters the NR band edge energies and introduces midgap states, in ways that are predicted to influence the efficiency of these nanomaterials as photoelectrocatalysts. UPS results show that Au tipping shifts EVB closer to vacuum by up to 0.4 eV, shifts the apparent Fermi energy toward the middle of the band gap, and introduces additional states above EVB. Spectroelectrochemical results confirm these trends: Au tipping shifts ECB closer to vacuum, by 0.4-0.6 eV, and introduces midgap states below ECB, which are assigned as metal-semiconductor interface (MSI) states. Characterization of these band edge energies and understanding the origins of MSI states is needed to design energy conversion systems with proper band alignment between the light absorbing NR, the NP catalyst, and solution electron donors and acceptors. The complementary characterization protocols presented here should be applicable to a wide variety of thin films of heterogeneous photoactive nanomaterials, aiding in the identification of the most promising material combinations for photoelectrochemical energy conversion.