20 research outputs found
Optoelectronics Meets Optoionics: Light Storing Carbon Nitrides and Beyond
Known for decades, Liebig's carbon nitrides have evolved into a burgeoning class of macromolecular semiconductors over the past 10+ years, front and center of many efforts revolving around the discovery of resourceâefficient and highâperformance photocatalysts for solar fuel generation. The recent discovery of a new class of âionicâ 2D carbon nitridesâpoly(heptazine imide) (PHI)âhas given new momentum to this field, driven both by unconventional properties and the prospect of new applications at the intersection between solar energy conversion and electrochemical energy storage. In this essay, key concepts of the emerging field of optoionics are delineated and the âlight storingâ ability of PHIâtype carbon nitrides is rationalized by an intricate interplay between their optoelectronic and optoionic properties. Based on these insights, key characteristics and general principles for the de novo design of optoionic materials across the periodic table are derived, opening up new research avenues such as âdark photocatalysisâ, direct solar batteries, lightâdriven autonomous systems, and photomemristive devices
A tunable azine covalent organic framework platform for visible light-induced hydrogen generation
Hydrogen evolution from photocatalytic reduction of water holds promise as a sustainable source of carbon-free energy. Covalent organic frameworks (COFs) present an interesting new class of photoactive materials, which combine three key features relevant to the photocatalytic process, namely crystallinity, porosity and tunability. Here we synthesize a series of water-and photostable 2D azine-linked COFs from hydrazine and triphenylarene aldehydes with varying number of nitrogen atoms. The electronic and steric variations in the precursors are transferred to the resulting frameworks, thus leading to a progressively enhanced light-induced hydrogen evolution with increasing nitrogen content in the frameworks. Our results demonstrate that by the rational design of COFs on a molecular level, it is possible to precisely adjust their structural and optoelectronic properties, thus resulting in enhanced photocatalytic activities. This is expected to spur further interest in these photofunctional frameworks where rational supramolecular engineering may lead to new material applications
Rational Strain Engineering in Delafossite Oxides for Highly Efficient Hydrogen Evolution Catalysis in Acidic Media
The rational design of hydrogen evolution reaction (HER) electrocatalysts
which are competitive with platinum is an outstanding challenge to make
power-to-gas technologies economically viable. Here, we introduce the
delafossites PdCrO, PdCoO and PtCoO as a new family of
electrocatalysts for the HER in acidic media. We show that in PdCoO the
inherently strained Pd metal sublattice acts as a pseudomorphic template for
the growth of a strained (by +2.3%) Pd rich capping layer under reductive
conditions. The surface modification continuously improves the electrocatalytic
activity by simultaneously increasing the exchange current density j from 2
to 5 mA/cm and by reducing the Tafel slope down to 38 mV/decade,
leading to overpotentials < 15 mV for 10 mA/cm, superior
to bulk platinum. The greatly improved activity is attributed to the in-situ
stabilization of a -palladium hydride phase with drastically enhanced
surface catalytic properties with respect to pure or nanostructured palladium.
These findings illustrate how operando induced electrodissolution can be used
as a top-down design concept for rational surface and property engineering
through the strain-stabilized formation of catalytically active phases
Carbon nitride-based light-driven microswimmers with intrinsic photocharging ability
Controlling autonomous propulsion of microswimmers is essential for targeted drug delivery and applications of micro/nanomachines in environmental remediation and beyond. Herein, we report two-dimensional (2D) carbon nitride-based Janus particles as highly efficient, light-driven microswimmers in aqueous media. Due to the superior photocatalytic properties of poly(heptazine imide) (PHI), the microswimmers are activated by both visible and ultraviolet (UV) light in conjunction with different capping materials (Au, Pt, and SiO2) and fuels (H2O2 and alcohols). Assisted by photoelectrochemical analysis of the PHI surface photoreactions, we elucidate the dominantly diffusiophoretic propulsion mechanism and establish the oxygen reduction reaction (ORR) as the major surface reaction in ambient conditions on metal-capped PHI and even with TiO2-based systems, rather than the hydrogen evolution reaction (HER), which is generally invoked as the source of propulsion under ambient conditions with alcohols as fuels. Making use of the intrinsic solar energy storage ability of PHI, we establish the concept of photocapacitive Janus microswimmers that can be charged by solar energy, thus enabling persistent light-induced propulsion even in the absence of illuminationâa process we call âsolar battery swimmingââlasting half an hour and possibly beyond. We anticipate that this propulsion scheme significantly extends the capabilities in targeted cargo/drug delivery, environmental remediation, and other potential applications of micro/nanomachines, where the use of versatile earth-abundant materials is a key prerequisite
Dark Photocatalysis: Storage of Solar Energy in Carbon Nitride for Time-Delayed Hydrogen Generation
While natural photosynthesis serves as the model system for efficient charge separation and decoupling of redox reactions, bio-inspired artificial systems typically lack applicability owing to synthetic challenges and structural complexity. We present herein a simple and inexpensive system that, under solar irradiation, forms highly reductive radicals in the presence of an electron donor, with lifetimes exceeding the diurnal cycle. This radical species is formed within a cyanamide- functionalized polymeric network of heptazine units and can give off its trapped electrons in the dark to yield H-2, triggered by a co-catalyst, thus enabling the temporal decoupling of the light and dark reactions of photocatalytic hydrogen production through the radical's longevity. The system introduced here thus demonstrates a new approach for storing sunlight as long-lived radicals, and provides the structural basis for designing photocatalysts with long-lived photo-induced states
Structural Insights into Poly(Heptazine Imides): A Light-Storing Carbon Nitride Material for Dark Photocatalysis
Solving the structure of carbon nitrides has been a long-standing challenge due to the low crystallinity and complex structures observed within this class of earth-abundant photocatalysts. Herein, we report on two-dimensional layered potassium poly(heptazine imide) (K-PHI) and its proton-exchanged counterpart (H-PHI), obtained by ionothermal synthesis using a molecular precursor route. We present a comprehensive analysis of the in-plane and three-dimensional structure of PHI. Transmission electron microscopy and solid-state NMR spectroscopy, supported by quantum-chemical calculations, suggest a planar, imide-bridged heptazine backbone with trigonal symmetry in both K-PHI and H-PHI, whereas pair distribution function analyses and X-ray powder diffraction using recursive-like simulations of planar defects point to a structure-directing function of the pore content. While the out-of-plane structure of K-PHI exhibits a unidirectional layer offset, mediated by hydrated potassium ions, H-PHI is characterized by a high degree of stacking faults due to the weaker structure directing influence of pore water. Structureâproperty relationships in PHI reveal that a loss of in-plane coherence, materializing in smaller lateral platelet dimensions and increased terminal cyanamide groups, correlates with improved photocatalytic performance. Size-optimized H-PHI is highly active toward photocatalytic hydrogen evolution, with a rate of 3363 ÎŒmol/gh H2 placing it on par with the most active carbon nitrides. K- and H-PHI adopt a uniquely long-lived photoreduced polaronic state in which light-induced electrons are stored for more than 6 h in the dark and released upon addition of a Pt cocatalyst. This work highlights the importance of structureâproperty relationships in carbon nitrides for the rational design of highly active hydrogen evolution photocatalysts
Operando Insights on the Degradation Mechanisms of Rhenium doped Molybdenum Disulfide Nanocatalysts for Electrolyzer Applications
MoS2 nanostructures are promising catalysts for proton-exchange-membrane
(PEM) electrolyzers to replace expensive noble metals. Their broadscale
application demands high activity for the hydrogen evolution reaction (HER) as
well as good durability. Doping in MoS2 is commonly applied to enhance the HER
activity of MoS2-based nanocatalysts, but the effect of dopants in the
electrochemical and structural stability is yet to be discussed. Herein, we
correlate operando electrochemical measurements to the structural evolution of
the materials down to the nanometric scale by identical location electron
microscopy and spectroscopy. Different degradation mechanisms at first
electrolyte contact, open circuit stabilization and HER conditions are
identified for MoS2 nanocatalysts with and without Rhenium doping. Our results
demonstrate that doping in MoS2 nanocatalysts can not only improve their HER
activity, but also their stability. Doping of MoS2-based nanocatalysts is
validated as a promising strategy to follow for the continuous improvement of
high performance and durable PEM electrolyzers
IrOOH nanosheets as acid stable electrocatalysts for the oxygen evolution reaction
In solids, heterogeneous catalysis is inherently bound to reactions on the surface. Yet, atomically efficient preparation of specific surfaces and the characterization of their properties are impeding its applications towards a clean energy future. Here, we present the synthesis of single layered IrOOH nanosheets and investigations of their structure as well as their electrochemical properties towards oxygen evolution under aqueous acidic conditions. The nanosheets are synthesized by treating bulk IrOOH with a tetrabutylammonium hydroxide solution and subsequent washing. Electron diffraction shows that the triangular arrangement of the edge sharing Ir(O,OH)(6) octahedra found in the layers of bulk IrOOH is retained after exfoliation into single layers. When incorporated as an active component in Ti electrodes, the nanosheets exhibit a Tafel slope of 58(3) mV dec(-1) and an overpotential of eta(-2)(10 mA cm) = 344(7) mV in 0.1 M HClO4, while retaining the trivalent oxidation state of iridium. They outperform bulk rutile-IrO2 and bulk IrOOH as electrocatalytic water oxidation catalysts under the same conditions. The results of this study on the structure-property relationships of low valence IrOOH nanosheets offer new pathways for the development of atom efficient, robust and highly active oxygen evolution catalysts
Bottom-up Formation of Carbon-Based Structures with Multilevel Hierarchy from MOF-Guest Polyhedra.
Three-dimensional carbon-based structures have proven useful for tailoring material properties in structural mechanical and energy storage applications. One approach to obtain them has been by carbonization of selected metal-organic frameworks (MOFs) with catalytic metals, but this is not applicable to most common MOF structures. Here, we present a strategy to transform common MOFs, by guest inclusions and high-temperature MOF-guest interactions, into complex carbon-based, diatom-like, hierarchical structures (named for the morphological similarities with the naturally existing diatomaceous species). As an example, we introduce metal salt guests into HKUST-1-type MOFs to generate a family of carbon-based nano-diatoms with two to four levels of structural hierarchy. We report control of the morphology by simple changes in the chemistry of the MOF and guest, with implications for the formation mechanisms. We demonstrate that one of these structures has unique advantages as a fast-charging lithium-ion battery anode. The tunability of composition should enable further studies of reaction mechanisms and result in the growth of a myriad of unprecedented carbon-based structures from the enormous variety of currently available MOF-guest candidates.The project was funded through a European Research Council (ERC) grant to S.K.S. (grant number: EMATTER 280078). A.K.C. and Y.W. thank the Ras Al Khaimah Center for Advanced Materials (RAK-CAM). T.W. thanks the China Scholarship Council (CSC) for funding and EPSRC Centre for Doctoral Training in Sensor Technologies and Applications (EP/L015889/1 and 1566990) for support. W.L. acknowledges the EPSRC grants (EP/L011700/1 and EP/N004272/1). Financial support by the Max Planck Society is gratefully acknowledged. K.D.F. acknowledges support from the Winston Churchill Foundation of the United States. C.Y. thanks the Cambridge Commonwealth, European and International Trust for funding
Polymer photocatalysts for solar-to-chemical energy conversion
Solar-to-chemical energy conversion for the generation of high-energy chemicals is one of the most viable solutions to the quest for sustainable energy resources. Although long dominated by inorganic semiconductors, organic polymeric photocatalysts offer the advantage of a broad, molecular-level design space of their optoelectronic and surface catalytic properties, owing to their molecularly precise backbone. In this Review, we discuss the fundamental concepts of polymeric photocatalysis and examine different polymeric photocatalysts, including carbon nitrides, conjugated polymers, covalent triazine frameworks and covalent organic frameworks. We analyse the photophysical and physico-chemical concepts that govern the photocatalytic performance of these materials, and derive design principles and possible future research directions in this emerging field of âsoft photocatalysisâ