Chlorophyll derivatives/MXene hybrids for photocatalytic hydrogen evolution: Dependence of performance on the central coordinating metals

Development of efficient photocatalytic hydrogen evolution reaction (HER) with illumination of visible light is challenging. In this work, five chlorophyll derivatives (M-Chls; M = H2/Cu/Ni/Co/Zn) with different central ions in its cyclic tetrapyrrole ring including free base, copper, nickel, cobalt, and zinc were synthesized and employed as the effective visible-light harvester for efficient HER. In addition, two-dimensional (2D) noble metal-free co-catalyst Ti3C2Tx MXene was used as an excellent electron capturer due to its outstanding conductivity property. These M-Chls are modified on the surface of Ti3C2Tx MXene with 2D accordion-like morphology by means of a simple deposition process to form noble metal-free Chl/Ti3C2Tx-based photocatalysts for HER. It is found that the best HER performance as high as 49 μmol/h/gcat was achieved with the Co-Chl@Ti3C2Tx hybrid, which was much higher than those of other M-Chl@Ti3C2Tx composites. This research provides a specific way to synthesize low-cost and environmentally friendly natural Chls for developing highly efficient photocatalytic HER through molecular engineering

Aggregate-forming semi-synthetic chlorophyll derivatives / Ti₃C₂Tₓ MXene hybrids for photocatalytic hydrogen evolution

Chlorophylls (Chls) are the most abundant natural pigments having excellent opt-electrical and semi-conductive properties. Ti3C2Tx MXene, one of the most extensively studied 2D noble metal-free co-catalyst, features outstanding electrochemical properties. This work compares three aggregate-forming chlorophyll derivatives (Chl-n; n = 1–3), namely, zinc methyl 3-devinyl-3-hydroxymethyl-pyropheophorbide-a (Chl-1), zinc dodecyl 3-devinyl-3-hydroxymethyl-pyropheophorbide-a (Chl-2) and zinc dodecyl 131-deoxo-3-devinyl-131-dicyanomethylene-3-hydroxymethyl-pyropheophorbide-a (Chl-3), as light-harvesting antenna pigments in the MXene-based photocatalytic system for hydrogen evolution under the white light illumination (λ > 420 nm). The hydrogen evolution reaction (HER) of these Chls depends on the peripheral substituent groups at the C13- and/or C17-positions of the chlorin macrocyclic π-system. Differences among these Chl-n sensitized Ti3C2Tx MXene (Chl-n@Ti3C2Tx) are compared in terms of their light-harvesting ability, morphology, charge transfer efficiency and photocatalytic performance. The best HER performance is found to be as high as 122 μmol/h/gcat with the Chl-3@Ti3C2Tx composite. This work leads the direction in synthesizing Chls in Chl/MXene hybrid structure suitable for highly efficient photocatalytic HER

Effect of the Fabrication Method of Chlorophyll-Ti3C2Tx-Based Photocatalysts on Noble Metal-Free Hydrogen Evolution

Composites composed of a chlorophyll-a derivative and Ti3C2Tx MXene recently showed promising results as photocatalysts for the hydrogen evolution reaction. Herein, this type of composites is prepared by using a layered Ti3C2Tx material via an HCl@LiF etching technique, instead of the previously adopted HF etching technique. The performance of H2 evolution, therefore, showed a fourfold increase in this photocatalytic system, compared with the reported data in our previous works. The underlying reason for such a large improvement of the chlorophyll-MXene photocatalyst performance would be attributed to a more suitable surface chemistry, higher conductivity, fewer defects, higher surface area, and larger interlayer space of Ti3C2Tx introduced by the Li+ ions from LiF in the etching process. Herein, it is revealed that the preparation method of MXenes used as the cocatalysts is key to improve the H2 evolution efficiency in photocatalytic water splitting

Chlorophyll based organic heterojunction on Ti3C2Tx MXenes nano‐sheets for efficient hydrogen production

Z‐scheme process is a photo‐induced electron transfer pathway in natural oxygenic photosynthesis involving the electron transport from photosystem II (PSII) to PSI. Inspired by the interesting Z‐scheme process, here we demonstrated a photocatalytic hydrogen evolution reaction (HER) employing chlorophyll derivatives, Chl‐1 and Chl‐2, on the surface of Ti3C2Tx MXenes with two‐dimensional accordion‐like morphology forming Chl‐1@Chl‐2@Ti3C2Tx composite. Due to the frontier molecular orbital energy alignments of Chl‐1 and Chl‐2, the sublayer Chl‐1 is a simulation of PSI whereas the upper layer Chl‐2 is equivalent to PSII, and the resultant electron transport can take place from Chl‐2 to Chl‐1. Under the illumination of visible light (> 420 nm), the HER performance of Chl‐1@Chl‐2@Ti3C2Tx photocatalysts was found to be as high as 143 μmol/h/gcat , which was substantially higher than that of photocatalysts of either Chl‐1@Ti3C2Tx (20 μmol/h/g) or Chl‐2@Ti3C2Tx (15 μmol/h/g)

Chlorosome‐Like Molecular Aggregation of Chlorophyll Derivative on Ti₃C₂Tₓ MXene Nanosheets for Efficient Noble Metal‐Free Photocatalytic Hydrogen Evolution

Efficient photocatalytic hydrogen evolution reaction (HER) in the visible‐to‐near infrared region at a low cost remains a challenging issue. This work demonstrates the fabrication of organic‐inorganic composites by deposition of supramolecular aggregates of a chlorophyll derivative, namely, zinc methyl 3‐devinyl‐3‐hydroxymethyl‐pyropheophorbide a (Chl) on the surface of Ti3C2Tx MXene with 2D accordion‐like morphology. This composite material is employed as noble metal‐free catalyst in photocatalytic HER under the white light illumination, where Chl serves as a small molecule organic semiconductor component instead of ordinary inorganic and polymer organic semiconductors such as TiO2 and g‐C3N4, and Ti3C2Tx serves as a co‐catalyst. Different composition ratios of Chl/Ti3C2Tx are compared for their light‐harvesting ability, morphology, charge transfer efficiency, and photocatalytic performance. The best HER performance is found to be as high as 52 ± 5 µmol h−1 gcat−1 after optimization. Such a large HER activity is attributed to the efficient light harvesting followed by exciton transfer in Chl aggregates and the resultant charge separation at the interface of Chl/Ti3C2Tx

T-Duality Transformation and Universal Structure of Non-Critical String Field Theory

We discuss a T-duality transformation for the c=1/2 matrix model for the purpose of studying duality transformations in a possible toy example of nonperturbative frameworks of string theory. Our approach is to first investigate the scaling limit of the Schwinger-Dyson equations and the stochastic Hamiltonian in terms of the dual variables and then compare the results with those using the original spin variables. It is shown that the c=1/2 model in the scaling limit is T-duality symmetric in the sphere approximation. The duality symmetry is however violated when the higher-genus effects are taken into account, owing to the existence of global Z_2 vector fields corresponding to nontrivial homology cycles. Some universal properties of the stochastic Hamiltonians which play an important role in discussing the scaling limit and have been discussed in a previous work by the last two authors are refined in both the original and dual formulations. We also report a number of new explicit results for various amplitudes containing macroscopic loop operators.Comment: RevTex, 46 pages, 5 eps figure

Stochastic Hamiltonian for Non-Critical String Field Theories from Double-Scaled Matrix Models

We present detailed discussions on the stochastic Hamiltonians for non-critical string field theories on the basis of matrix models. Beginning from the simplest $c=0$ case, we derive the explicit forms of the Hamiltonians for the higher critical case $k=3$ (which corresponds to $c=-22/5$) and for the case $c=1/2$, directly from the double-scaled matrix models. In particular, for the two-matrix case, we do not put any restrictions on the spin configurations of the string fields. The properties of the resulting infinite algebras of Schwinger-Dyson operators associated with the Hamiltonians and the derivation of the Virasoro and $W_3$ algebras therefrom are also investigated. Our results suggest certain universal structure of the stochastic Hamiltonians, which might be useful for an attempt towards a background independent string field theory.Comment: 70 pages, LaTeX, typographical errors are corrected, to be published in Phys. Rev.

Extended Fermion Representation of Multi-Charge 1/2-BPS Operators in AdS/CFT -- Towards Field Theory of D-Branes --

We extend the fermion representation of single-charge 1/2-BPS operators in the four-dimensional N=4 super Yang-Mills theory to general (multi-charge) 1/2-BPS operators such that all six directions of scalar fields play roles on an equal footing. This enables us to construct a field-theorectic representation for a second-quantized system of spherical D3-branes in the 1/2-BPS sector. The Fock space of D3-branes is characterized by a novel exclusion principle (called `Dexclusion' principle), and also by a nonlocality which is consistent with the spacetime uncertainty relation. The Dexclusion principle is realized by composites of two operators, obeying the usual canonical anticommutation relation and the Cuntz algebra, respectively. The nonlocality appears as a consequence of a superselction rule associated with a symmetry which is related to the scale invariance of the super Yang-Mills theory. The entropy of the so-called superstars, with multiple charges, which have been proposed to be geometries corresponding to the condensation of giant gravitons is discussed from our viewpoint and is argued to be consistent with the Dexclusion principle. Our construction may be regarded as a first step towards a possible new framework of general D-brane field theory.Comment: 43 pages, 4 figures; version 2, corrected typos and added reference

1/2-BPS Correlators as c=1 S-matrix

We argue from two complementary viewpoints of Holography that the 2-point correlation functions of 1/2-BPS multi-trace operators in the large-N (planar) limit are nothing but the (Wick-rotated) S-matrix elements of c=1 matrix model. On the bulk side, we consider an Euclideanized version of the so-called bubbling geometries and show that the corresponding droplets reach the conformal boundary. Then the scattering matrix of fluctuations of the droplets gives directly the two-point correlators through the GKPW prescription. On the Yang-Mills side, we show that the two-point correlators of holomorphic and anti-holomorphic operators are essentially equivalent with the transformation functions between asymptotic in- and out-states of c=1 matrix model. Extension to non-planar case is also discussed.Comment: 28 pages, 3 figures, corrected typos, version to appear in JHE