Search

Nanocarbon can promote robust and efficient electrocatalytic water oxidation through active surface oxygen moieties. The recent mechanistic understandings (e.g., active sites) of metal-free carbon catalysts in oxygen evolution reaction (OER), however, are still rife with controversies. In this work, we describe a facile protocol in which eight kinds of aromatic molecules with designated single oxygen species were used as model structures to investigate the explicit roles of each common oxygen group in OER at a molecular level. These model structures were decorated onto typical nanocarbon surfaces like onion-like carbons (OLC) or multiwalled carbon nanotubes (MWCNT) to build aromatic molecule-modified carbon systems. We show that edge (including zigzag and armchair) quinones in a conjugated π network are the true active centers, and the roles of ether and carboxyl groups are excluded in the OER process. The plausible rate-determining step could be singled out by H/D kinetic isotope effects. The turnover frequency per C═O (∼0.323 s -1 at η = 340 mV) in 0.1 M KOH and the optimized current density (10 mA/cm 2 at 1.58 V vs RHE) of quinone-modified carbon systems are comparable to those of promising metal-based catalysts.

The mechanism on interfacial synergistic catalysis for supported metal catalysts has long been explored and investigated in several important heterogeneous catalytic processes (e.g., water-gas shift (WGS) reaction). The modulation of metal-support interactions imposes a substantial influence on activity and selectivity of catalytic reaction, as a result of the geometric/electronic structure of interfacial sites. Although great efforts have validated the key role of interfacial sites in WGS over metal catalysts supported on reducible oxides, direct evidence at the atomic level is lacking and the mechanism of interfacial synergistic catalysis is still ambiguous. Herein, Ni nanoparticles supported on TiO 2- x (denoted as Ni@TiO 2- x ) were fabricated via a structure topotactic transformation of NiTi-layered double hydroxide (NiTi-LDHs) precursor, which showed excellent catalytic performance for WGS reaction. In situ microscopy was carried out to reveal the partially encapsulated structure of Ni@TiO 2- x catalyst. A combination study including in situ and operando EXAFS, in situ DRIFTS spectra combined with TPSR measurements substantiates a new redox mechanism based on interfacial synergistic catalysis. Notably, interfacial Ni species (electron-enriched Ni δ- site) participates in the dissociation of H 2 O molecule to generate H 2 , accompanied by the oxidation of Ni δ- -O v -Ti 3+ (O v : oxygen vacancy) to Ni δ+ -O-Ti 4+ structure. Density functional theory calculations further verify that the interfacial sites of Ni@TiO 2- x catalyst serve as the optimal active site with the lowest activation energy barrier (∼0.35 eV) for water dissociation. This work provides a fundamental understanding on interfacial synergistic catalysis toward WGS reaction, which is constructive for the rational design and fabrication of high activity heterogeneous catalysts.

Transition metal phosphides (TMPs) have recently emerged as a new class of pre-catalysts that can efficiently catalyze the oxygen evolution reaction (OER). However, how the OER activity of TMPs varies with the catalyst composition has not been systematically explored. Here, we report the alkaline OER electrolysis of a series of nanoparticulate phosphides containing different equimolar metal (M = Fe, Co, Ni) components. Notable trends in OER activity are observed, following the order of FeP < NiP < CoP < FeNiP < FeCoP < CoNiP < FeCoNiP, which indicate that the introduction of a secondary metal(s) to a mono-metallic TMP substantially boosts the OER performance. We ascribe the promotional effect to the enhanced oxidizing power of bi- and tri-metallic TMPs that can facilitate the formation of MOH and chemical adsorption of OH - groups, which are the rate-limiting steps for these catalysts according to our Tafel analysis. Remarkably, the tri-metallic FeCoNiP pre-catalyst exhibits exceptionally high apparent and intrinsic OER activities, requiring only 200 mV to deliver 10 mA cm -2 and showing a high turnover frequency (TOF) of ≥0.94 s -1 at the overpotential of 350 mV.

The emergence of van der Waals (vdW) heterostructures of 2D materials has opened new avenues for fundamental scientific research and technological applications. However, the current concepts and strategies of material engineering lack feasibilities to comprehensively regulate the as-obtained extrinsic physicochemical characters together with intrinsic properties and activities for optimal performances. A 3D mesoporous vdW heterostructure of graphene and nitrogen-doped MoS 2 via a two-step sequential chemical vapor deposition method is constructed. Such strategy is demonstrated to offer an all-round engineering of 2D materials including the morphology, edge, defect, interface, and electronic structure, thereby leading to robustly modified properties and greatly enhanced electrochemical activities. The hydrogen evolution is substantially accelerated on MoS 2 , while the oxygen reduction and evolution are significantly improved on graphene. This work provides a powerful overall engineering strategy of 2D materials for electrocatalysis, which is also enlightening for other nanomaterials and energy-related applications., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Water oxidation represents the core process of many sustainable energy systems, such as fuel cells, rechargeable metal-air batteries, and water splitting. Material surface defects with high-energy hanging bonds possess superb intrinsic reactivity, whose actual performance is limited by the dimension and conductivity of the electrocatalyst. Herein we propose a surface defect-rich perovskite electrocatalyst through a p-block metal regulation concept to achieve high performance for oxygen evolution. As a typical p-metal, Sn 4+ dissolves from the solid phase from model SnNiFe perovskite nanodots, resulting in abundant surface defects with superior water oxidation performance. An oxygen pool model and a fusion-evolution mechanism are therefore proposed for the in-depth understanding of p-block metal regulation and the oxygen evolution reaction. The energy chemistry unveiled herein provides insights into water oxidation and helps to tackle critical issues in multi-electron oxygen electrocatalysis.Electrocatalysts that possess high densities of surface defects show great promise for efficient water oxidation. Here the authors demonstrate that regulating the p-block metal content in perovskite nanodots imparts these materials with abundant surface defects and excellent electrocatalytic activity.

Although nanosized Au clusters have been well developed for many applications, fundamental understanding of their adsorption/activation behaviors in catalytic applications is still lacking, especially when other elements provide promotion or hybridization functions. Au hybridized with Cu element is a highly investigated system; Cu is in the same element group as Au and thus displays similar physicochemical properties. However, their hybrids are not well understood in terms of their chemical states and adsorption/activation properties. In this work, typical γ-Al 2 O 3 -supported Au and CuO as well as Au-CuO nanoparticles were prepared and characterized to explore their adsorption/activation properties in depth using CO as a probe molecule using advanced techniques, such as XPS, HR-TEM, temperature programmed experiments and operando DRIFT combined with mass spectra. It was found that gold and copper can both act as active sites during CO adsorption and activation. The CO-TPD and operando DRIFT results also revealed that CO molecules were able to react with surface oxygenated species, resulting in the direct formation of CO 2 over the three samples in the absence of gaseous O 2 . The gold step sites (Au step ) participated more readily in the reaction, especially under gaseous O 2 -free conditions. During adsorption, CO molecules were more preferentially adsorbed on Au 0 sites at lower temperature comparing with those on the Cu 0 sites. However, competitive adsorption occurred between CO adsorbed on Au 0 and Cu 0 with increased reaction temperature, and the synergy between the Au and Cu compositions was too strong to suppress the adsorption and activation of the CO molecules. The dynamic adsorption equilibrium over 120 °C to 200 °C resulted in the appearance of a hysteresis performance platform.

Developing highly selective and stable catalysts for acetylene hydrogenation is an imperative task in the chemical industry. Herein, core-shell Pd@carbon nanoparticles supported on carbon nanotubes (Pd@C/CNTs) were synthesized. During the hydrogenation of acetylene, the selectivity of Pd@C/CNTs to ethylene was distinctly improved. Moreover, Pd@C/CNTs showed excellent stability during the hydrogenation reaction.

The preparation of photocatalysts with high activities under visible-light illumination is challenging. We report the rational design and construction of a zirconium-doped anatase catalyst (S-Zr-TiO 2 ) with Brønsted acidity and photoactivity as an efficient catalyst for the degradation of phenol under visible light. Electron microscopy images demonstrate that the zirconium sites are uniformly distributed on the sub-10 nm anatase crystals. UV-visible spectrometry indicates that the S-Zr-TiO 2 is a visible-light-responsive catalyst with narrower band gap than conventional anatase. Pyridine-adsorption infrared and acetone-adsorption 13 C NMR spectra confirm the presence of Brønsted acidic sites on the S-Zr-TiO 2 sample. Interestingly, the S-Zr-TiO 2 catalyst exhibits high catalytic activity in the degradation of phenol under visible-light illumination, owing to a synergistic effect of the Brønsted acidity and photoactivity. Importantly, the S-Zr-TiO 2 shows good recyclability., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A bifunctional graphene catalyst with abundant topological defects is achieved via the carbonization of natural gelatinized sticky rice to probe the underlying oxygen electrocatalytic mechanism. A nitrogen-free configuration with adjacent pentagon and heptagon carbon rings is revealed to exhibit the lowest overpotential for both oxygen reduction and evolution catalysis. The versatile synthetic strategy and novel insights on the activity origin facilitate the development of advanced metal-free carbocatalysts for a wide range of electrocatalytic applications., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Carbon nanotubes (CNTs) are functionalized with nitrogen atoms for reduction of carbon dioxide (CO2 ). The investigation explores the origin of the catalyst's activity and the role of nitrogen chemical states therein. The catalysts show excellent performances, with about 90 % current efficiency for CO formation and stability over 60 hours. The Tafel analyses and density functional theory calculations suggest that the reduction of CO2 proceeds through an initial rate-determining transfer of one electron to CO2 , which leads to the formation of carbon dioxide radical anion (CO2 (.-) ). The initial reduction barrier is too high on pristine CNTs, resulting in a very high overpotentials at which the hydrogen evolution reaction dominates over CO2 reduction. The doped nitrogen atoms stabilize the radical anion, thereby lowering the initial reduction barrier and improving the intrinsic activity. The most efficient nitrogen chemical state for this reaction is quaternary nitrogen, followed by pyridinic and pyrrolic nitrogen., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The structures of PtNix nanoalloy particles were modified through thermal annealing in different atmospheres. The evolution of surface structures was uncovered by advanced transmission electron microscopy, and the structure-function correlation in methanol electro-oxidation was probed. It provided new insights into the design and synthesis of highly efficient electrocatalysts.

P-type Cu2 O has been long considered as an attractive photocatalyst for photocatalytic water reduction, but few successful examples has been reported. Here, we report the synthesis of TiO2 (core)/Cu2 O (ultrathin film shell) nanorods by a redox reaction between Cu(2+) and in-situ generated Ti(3+) when Cu(2+) -exchanged H-titanate nanotubes are calcined in air. Owing to the strong TiO2 -Cu2 O interfacial interaction, TiO2 (core)/Cu2 O (ultrathin film shell) nanorods are highly active and stable in photocatalytic water reduction. The TiO2 core and Cu2 O ultrathin film shell respectively act as the photosensitizer and cocatalyst, and both the photoexcited electrons in the conduction band and the holes in the valence band of TiO2 respectively transfer to the conduction band and valence band of the Cu2 O ultrathin film shell. Our results unambiguously show that Cu2 O itself can act as the highly active and stable cocatalyst for photocatalytic water reduction., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The lithium-oxygen (Li-O2 ) battery is a very appealing candidate for advanced high energy applications owing to its exceptionally high specific energy. However, its poor energy efficiency, rate capability, and cyclability remain key barriers to its practical application. In this work, using a rationally designed cathode based on a bimodal mesoporous nitrogen-doped graphene/carbon nanotube (NGC) composite, we have developed a Li-O2 battery demonstrating enhanced round-trip efficiency (ca. 85 %) and excellent cyclability over 400 cycles under a high current rate of 500 mA g(-1) . The excellent cyclability and rate capability are attributed to improved stability of the aggressive LiO2 intermediate on the nitrogen-doped carbon surface in addition to the favorable hierarchical architecture of NGC. These results demonstrate a valuable research direction to achieve highly stable and reversible Li-O2 batteries through tuning the surface chemistry of the cathode in addition to finding a stable electrolyte solvent., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In alkaline medium, it seems that both metal-free and iron-containing carbon-based catalysts, such as nitrogen-doped nanocarbon materials, FeOx -doped carbon, and Fe/N/C catalysts, are active for the oxygen reduction reaction (ORR). However, the order of activity of these different active compositions has not been clearly determined. Herein, we synthesized nitrogen-doped carbon black (NCB), Fe3 O4 /CB, Fe3 O4 /NCB, and FeN4 /CB. Through the systematic study of the ORR catalytic activity of these four catalysts in alkaline solution, we confirmed the difference in the catalytic activity and catalytic mechanism for nitrogen, iron oxides, and Fe-N complexes, respectively. In metal-free NCB, nitrogen can improve the ORR catalytic activity with a four-electron pathway. Fe3 O4 /CB catalyst did not exhibit improved activity over that of NCB owing to the poor conductivity and spinel structure of Fe3 O4 . However, FeN4 coordination compounds as the active sites showed excellent ORR catalytic activity., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Non-precious metal oxide/carbon hybrid electrocatalysts are of increasing importance for the oxygen reduction reaction (ORR). A synergistic effect is commonly used to explain the superior ORR activity exerted by metal oxide/nanocarbon hybrids, and this effect is attributed to covalently coupled interfaces between the two materials. However, the origin of the high activity, the structure, and the electrocatalytic nature of the interface remain unclear. By combining X-ray photoelectron spectroscopy with synchrotron far-infrared spectroscopy, we resolved the interface structure between spinel manganese oxide nanocrystals and graphene oxide nanoribbons, and the role of this interface in the promoted ORR. Moreover, we demonstrated the excellent ORR activity by a functional synergism of the hybrid constituents through a series of comparative electrochemical experiments., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Two kinds of phosphorus-modified onion-like carbons dominated by C-O-P bonds and C-P bonds were fabricated and further used as catalysts in the oxygen reduction reaction (ORR). The results show that the bonding state of phosphorus has a significant effect on the ORR catalytic activity. The formation of C-O-P bonds improves ORR activity, whereas C-P bonds play an adverse role in stabilizing the key intermediates during the ORR owing to the distorted graphitic structure, as confirmed by the work function value., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Non-precious Fe/N co-modified carbon electrocatalysts have attracted great attention due to their high activity and stability in oxygen reduction reaction (ORR). Compared to iron-free N-doped carbon electrocatalysts, Fe/N-modified electrocatalysts show four-electron selectivity with better activity in acid electrolytes. This is believed relevant to the unique Fe-N complexes, however, the Fe-N structure remains unknown. We used o,m,p-phenylenediamine as nitrogen precursors to tailor the Fe-N structures in heterogeneous electrocatalysts which contain FeS and Fe3 C phases. The electrocatalysts have been operated for 5000 cycles with a small 39 mV shift in half-wave potential. By combining advanced electron microscopy and Mössbauer spectroscopy, we have identified the electrocatalytically active Fe-N6 complexes (FeN6, [Fe(III)(porphyrin)(pyridine)2]). We expect the understanding of the FeN6 structure will pave the way towards new advanced Fe-N based electrocatalysts., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Hybrid nanocarbon, comprised of a diamond core and a graphitic shell with a variable sp(2)-/sp(3)-carbon ratio, is controllably obtained through sequential annealing treatment (550-1300 °C) of nanodiamond. The formation of sp(2) carbon increases with annealing temperature and the nanodiamond surface is reconstructed from amorphous into a well-ordered, onion-like carbon structure via an intermediate composite structure--a diamond core covered by a defective, curved graphene outer shell. Direct dehydrogenation of propane shows that the sp(2)-/sp(3)-nanocomposite exhibits superior catalytic performance to that of individual nanodiamond and graphitic nanocarbon. The optimum catalytic activity of the diamond/graphene composite depends on the maximum structural defectiveness and high chemical reactivity of the ketone groups. Ketone-type functional groups anchored on the defects/vacancies are active for propene formation; nevertheless, once the oxygen functional groups are desorbed, the defects/vacancies alone might be active sites responsible for the C-H bond activation of propane., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Palladium dynamics: Under hydrogenation conditions, saturating over-active palladium by carbon diffusion leads to a stable and selective particle surface. By choosing supports with suitable geometric structures and establishing a strong interaction between supports and metal particles, accumulated species can be regularly rearranged and reaction-selective phases can be exposed (see figure)., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A family of photocatalysts for water splitting into hydrogen was prepared by distributing TiO(6) units in an MTi-layered double hydroxide matrix (M = Ni, Zn, Mg) that displays largely enhanced photocatalytic activity with an H(2)-production rate of 31.4 μmol  h(-1) as well as excellent recyclable performance. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) mapping and XPS measurement reveal that a high dispersion of TiO(6) octahedra in the layered doubled hydroxide (LDH) matrix was obtained by the formation of an M(2+)-O-Ti network, rather different from the aggregation state of TiO(6) in the inorganic layered material K(2)Ti(4)O(9). Both transient absorption and photoluminescence spectra demonstrate that the electron-hole recombination process was significantly depressed in the Ti-containing LDH materials relative to bulk Ti oxide, which is attributed to the abundant surface defects that serve as trapping sites for photogenerated electrons verified by positron annihilation and extended X-ray absorption fine structure (EXAFS) techniques. In addition, a theoretical study on the basis of DFT calculations demonstrates that the electronic structure of the TiO(6) units was modified by the adjacent MO(6) octahedron by means of covalent interactions, with a much decreased bandgap of 2.1 eV, which accounts for its superior water-splitting behavior. Therefore, the dispersion strategy for TiO(6) units within a 2D inorganic matrix can be extended to fabricate other oxide or hydroxide catalysts with greatly enhanced performance in photocatalysis and energy conversion., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)