Enhanced Performance of Porphyrin-Modified CuO-Co3O4 Heterojunction as a Photoelectrocatalyst for Methanol Oxidation.

It is desirable to improve the methanol oxidation ability of heterojunction catalysts because of their potential in the field of electrocatalysis. In this article, we have integrated CuO/Co3O4 heterojunction with porphyrin (TCPP) for TCPP/Cu2Co1. The results demonstrate that the specific surface area and electrochemical active surface area (ECSA) are enhanced, and the unblocked separation and transfer of photogenerated charges are guaranteed by the matched band energy of CuO, Co3O4, and TCPP. As such, the photocatalytic methanol oxidation reaction (MOR) performance and stability of TCPP/Cu2Co1 are significantly enhanced compared with those of Cu2Co1. This study provides a promising pathway for the design of MOR catalysts with high MOR activity.

Engineering Lattice Planes of NiCo-LDH Ultrathin Sheets for Boosting Methanol/Ethanol Oxidation Performance.

Alcohol oxidation reactions are known to be significant in the advancement of sustainable, renewable energy sources. Searching for catalytic materials with powerful, reliable, and economic performance is of great importance. Due to their excellent intrinsic performance, outstanding stability, and inexpensiveness, ultrathin layered double hydroxides (LDHs) are considered to be competitive electrocatalysts. However, the electrocatalytic property of ultrathin LDHs is still confined by the predominant exposure of the (003) basal plane. Hence, we have engineered active edge facets in ultrathin NiCo-LDHs, which possess abundant oxygen vacancies (VO), by a facile one-step strategy. Experimental results show that NiCo-LDH-E synthesized in ethanol demonstrates an ultrathin structure, rich oxygen vacancies, and more active facets, exhibiting a higher electrochemical active area of 3.25 cm2, which is 1.18 times that of NiCo-LDH-W (2.75 cm2). In addition, the current density of NiCo-LDH-E in methanol and ethanol oxidation reactions could reach 159.5 and 136.3 mA cm-2, which are 2.8 and 1.7 times that of NiCo-LDH-W, respectively.

Enhancement of photoelectrocatalytic performance of copper cobaltate nanoflowers modified with 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin for methanol oxidation under light.

With the continuously increasing global energy demand, there is an urgent requirement to find efficient methanol oxidation reaction (MOR) catalysts that can replace precious metals. In this work, we have elaborately integrated 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin (H2TCPP) with copper cobaltate (CuCo2O4), which possesses efficient separation of photogenerated charges and increased active sites. The mass activity of H2TCPP/CuCo2O4 (534.75 mA mg-1) toward MOR is higher than that of pure CuCo2O4 (291.75 mA mg-1) under light. In addition, H2TCPP/CuCo2O4 can catalyze the oxidation of other alcohols, such as ethanol, ethanediol, isopropanol, and glycerol. This study demonstrates that it is feasible to enhance the MOR activity by the modification of bimetallic transition metal oxides with porphyrins.

Unveiling the influence of 5,10,15,20-tetrakis (4-carboxyl phenyl) porphyrin on the photogenerated charge behavior and photoelectrochemical water oxidation of hematite photoanode.

Coupling porphyrins with semiconductors is demonstrated as one of effective means to facilitate the separation of photogenerated charge in dye-sensitized solar cells as well as photocatalytic hydrogen production. However, there are limited reports about exploring the effect of porphyrin on the behavior of photogenerated charges and photoelectrochemical (PEC) water oxidation performance. Herein, we have built a hybrid photoanode containing Ti doped α-Fe2O3 (Ti-Fe2O3), 5,10,15,20-tetrakis (4-carboxyl phenyl) porphyrin (H2TCPP) and cobalt phosphate (CoPi) cocatalyst. Because of the appropriate band alignment of Ti-Fe2O3, H2TCPP and CoPi, the photogenerated holes are transferred directionally from Ti-Fe2O3 to CoPi across H2TCPP, which boosts the separation efficiency of CoPi/H2TCPP/Ti-Fe2O3 in turn. Meanwhile, CoPi/H2TCPP/Ti-Fe2O3 possesses higher injection efficiency as well. Under the double guarantee of high separation efficiency and injection efficiency, CoPi/H2TCPP/Ti-Fe2O3 yields an impressive photocurrent density of 1.84 mA/cm2 at 1.23 V vs. reversible hydrogen electrode (RHE), which is much higher than that of CoPi/Ti-Fe2O3. This structure design describes an appealing maneuver to facilitate the directed migration of photogenerated charges and then enhance the PEC water oxidation performance.

Enhancement Strategy of Photoelectrocatalytic Activity of Cobalt-Copper Layer Double Hydroxide toward Methanol Oxidation: Cerium Doping and Modification with Porphyrin.

Designing durable, high-active, and low-cost noble-metal-free photoelectrocatalysts for methanol electrooxidation is highly demanded but remains a challenge. Herein, the photoelectrocatalytic activity of cobalt-copper layer double hydroxide (CoCu-LDH) for methanol oxidation reaction (MOR) in the alkaline media under light was remarkably enhanced by cerium (Ce) doping and further by 5,10,15,20-tetrakis(4-carboxylphenyl)porphyrin (TCPP) modification. TCPP/Ce-CoCu-LDH exhibits a remarkable mass activity of 1788.2 mA mg-1 in 1 mol L-1 KOH with 1 mol L-1 methanol under light, which is 2.3 and 1.8 times higher than that of CoCu-LDH (782.2 mA mg-1) and Ce-CoCu-LDH (987.4 mA mg-1). The UV-vis diffuse reflectance spectra and photoluminescence emission spectra reveal that TCPP/Ce-CoCu-LDH can effectively utilize the visible light and inhibit the electron-hole pairs' recombination because of the introduction of porphyrin. Furthermore, more active sites and the greater electrical conductivity of TCPP/Ce-CoCu-LDH also contributed to the high photoelectrocatalytic activity. Thus, TCPP/Ce-CoCu-LDH can be used as a low-cost alternative for Pt-based catalyst toward MOR.

Boosting Photocatalytic Hydrogen Production by Modulating Recombination Modes and Proton Adsorption Energy.

Solar-driven production of renewable energy (e.g., H2) has been investigated for decades. To date, the applications are limited by low efficiency due to rapid charge recombination (both radiative and nonradiative modes) and slow reaction rates. Tremendous efforts have been focused on reducing the radiative recombination and enhancing the interfacial charge transfer by engineering the geometric and electronic structure of the photocatalysts. However, fine-tuning of nonradiative recombination processes and optimization of target reaction paths still lack effective control. Here we show that minimizing the nonradiative relaxation and the adsorption energy of photogenerated surface-adsorbed hydrogen atoms are essential to achieve a longer lifetime of the charge carriers and a faster reaction rate, respectively. Such control results in a 16-fold enhancement in photocatalytic H2 evolution and a 15-fold increase in photocurrent of the crystalline g-C3N4 compared to that of the amorphous g-C3N4.

Ferrihydrite-Modified Ti-Fe2 O3 as an Effective Photoanode: The Role of Interface Interactions in Enhancing the Photocatalytic Activity of Water Oxidation.

Semiconductor electrodes integrated with cocatalysts are key components of photoelectrochemistry (PEC)-based solar-energy conversion. However, efforts to optimize the PEC device have been limited by an inadequate understanding of the interface interactions between the semiconductor-cocatalyst (sem|cat) and cocatalyst-electrolyte (cat|ele) interface. In our work, we used ferrihydrite (Fh)-modified Ti-Fe2 O3 as a model to explore the transfer process of photogenerated charge carriers between the Ti-Fe2 O3 -Fh (Ti-Fe2 O3 |Fh) interface and Fh-electrolyte (Fh|ele) interface. The results demonstrate that the biphasic structure (Fh/Ti-Fe2 O3 ) possesses the advantage that the minority hole transfer from Ti-Fe2 O3 to Fh is driven by the interfacial electric field at the Ti-Fe2 O3 |Fh interface; meanwhile, the holes reached at the surface of Fh can rapidly inject into the electrolyte across the Fh|ele interface. As a benefit from the improved charge transfer at the Ti-Fe2 O3 |Fh and Fh|ele interface, the photocurrent density obtained by Fh/Ti-Fe2 O3 can reach 2.32 mA cm-2 at 1.23 V versus RHE, which is three times higher than that of Ti-Fe2 O3 .

A Ni2P modified Ti4+ doped Fe2O3 photoanode for efficient solar water oxidation by promoting hole injection.

Nickel phosphide (Ni2P) was used as an excellent water oxidation cocatalyst for photoelectrochemical (PEC) water splitting, which could significantly promote the hole injection efficiency and suppress the back reaction of water oxidation over a Ti4+ doped Fe2O3 photoanode.

Electron acceptor of Ni decorated porous carbon nitride applied in photocatalytic hydrogen production.

Nickel, a non-noble metal, is one of the most promising candidates for photocatalysis because it is inexpensive and an earth-abundant metal. Herein, Ni/CM-C3N4 nanocomposites with Ni as a cocatalyst were synthesized by a simple solvothermal method. Field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) confirmed that Ni nanoparticles were loaded onto the surface of CM-C3N4. The prepared Ni/CM-C3N4 nanocomposites exhibited an enhanced hydrogen evolution activity. The most active catalyst contained 10% Ni and produced H2 at a rate of 313.2 µmol h-1 g-1, which was obviously higher than that of pure CM-C3N4. The results of photoluminescence (PL) and photoacoustics (PA) studies indicated that the recombination efficiency of photo-induced electron-hole pairs was decreased for CM-Ni10 as compared to that for unmodified CM-C3N4. The transient photovoltage (TPV) measurements directly demonstrated that the recombination time of electron-hole pairs in CM-Ni10 was prolonged. More importantly, the reversed surface photovoltage (SPV) and the declined surface photocurrent (SPC) response of CM-Ni10 revealed that the photogenerated electrons could be trapped by Ni, leading to a better separation efficiency and a superior hydrogen production. Finally, the possible mechanism is proposed to illuminate the photogenerated charge behavior between CM-C3N4 and Ni, which might provide a theoretical basis to develop efficient cocatalysts for photocatalytic water splitting.