Electrocatalytic Nitrate and Nitrite Reduction toward Ammonia Using Cu2O Nanocubes: Active Species and Reaction Mechanisms.

The electrochemical reduction of nitrate (NO3-) and nitrite (NO2-) enables sustainable, carbon-neutral, and decentralized routes to produce ammonia (NH3). Copper-based materials are promising electrocatalysts for NOx- conversion to NH3. However, the underlying reaction mechanisms and the role of different Cu species during the catalytic process are still poorly understood. Herein, by combining quasi in situ X-ray photoelectron spectroscopy (XPS) and operando X-ray absorption spectroscopy (XAS), we unveiled that Cu is mostly in metallic form during the highly selective reduction of NO3-/NO2- to NH3. On the contrary, Cu(I) species are predominant in a potential region where the two-electron reduction of NO3- to NO2- is the major reaction. Electrokinetic analysis and in situ Raman spectroscopy was also used to propose possible steps and intermediates leading to NO2- and NH3, respectively. This work establishes a correlation between the catalytic performance and the dynamic changes of the chemical state of Cu, and provides crucial mechanistic insights into the pathways for NO3-/NO2- electrocatalytic reduction.

Enhancing Devulcanizing Degree and Efficiency of Reclaimed Rubber by Using Alcoholic Amines as the Devulcanizing Agent in Low-Temperature Mechano-Chemical Process.

Low-temperature mechanical chemical devulcanization is a process that can produce reclaimed rubber with exceptional mechanical properties. However, the inadequacy and low efficiency of the devulcanization have significantly restricted its application. To address the issues, alcoholic amines, including hydroxyethyl ethylenediamine (AEEA), ethanolamine (ETA), and diethanol amine (DEA), are utilized as devulcanizing agents to promote the devulcanization process. Careful characterizations are conducted to reveal the devulcanizing mechanism and to depict the performances of reclaimed rubbers. Results show that the amine groups in the devulcanizing agents can react with sulfur after the crosslink bonds are broken by mechanical shear force, thus blocking the activity of sulfur and introducing hydroxyl groups into the rubber chains. The incorporation of alcoholic amines can enhance the devulcanizing degree and devulcanizing efficiency, reduce the Mooney viscosity, and improve the mechanical and anti-aging performance. When using DEA as the devulcanizing agent, the sol content of reclaimed rubber increases from 13.1% to 22.4%, the devulcanization ratio increases from 82.1% to 89.0%, the Mooney viscosity decreases from 135.5 to 83.6, the tensile strength improves from 14.7 MPa to 16.3 MPa, the retention rate of tensile strength raises from 55.2% to 82.6% after aging for 72 h, while the devulcanization time is shortened from 21 min to 9.5 min, compared with that without using alcoholic amines. Therefore, alcoholic amines exhibit remarkable advantages in the devulcanization of waste rubber, thus indicating a promising direction for the advancement of research in the area of waste rubber reclamation.

Improving Dispersion of Carbon Nanotubes in Natural Rubber by Using Waterjet-Produced Rubber Powder as a Carrier.

Carbon nanotube (CNT), as reinforcing agents in natural rubber (NR), has gained a large amount of consideration due to their excellent properties. Uniform dispersion of CNT is the key to obtaining high-performance NR nanocomposites. In this contribution, a novel ultrasonic grinding dispersion method of CNT with waterjet-produced rubber powder (WPRP) as a carrier is proposed. Microscopic morphologies show that a Xanthium-like structure with WPRP as the core and CNTs as the spikes is formed, which significantly improves the dispersion of CNT in the NR matrix and simultaneously strengthens the bonding of the WPRP and NR matrix. With the increase in the WPRP loading, the Payne effect of CNT/WPRP/NR composites decreases, indicating the effectiveness of the dispersion method. The vulcanization MH and ML value and crosslinking density increase with the increase in the WPRP loading, whereas the scorch time and cure time exhibit a decreasing trend when the WPRP loading is less than 15 phr. It is found that the CNT/WPRP/NR composites filled with 5 phr WPRP have a 4% increase in 300% modulus, a 3% increase in tensile strength, while a 5% decrease in Akron abrasion loss, compared to CNT/NR composites.

Modulating the Site Density of Mo Single Atoms to Catch Adventitious O Atoms for Efficient H2 O2 Oxidation with Light.

Coordination environment and site density have great impacts on the catalytic performance for single atoms (SAs). Herein, the site density of Mo-SAs on red polymeric carbon nitrides (RPCN) is modulated via a local carbonization strategy to controllably catch adventitious O atoms from open environment. The addition of melamine derivants with hydrocarbyl chains induces local carbonization during RPCN pyrolysis. These local carbonization regions bring abundant graphitic N3C to anchor Mo-SAs, and most of Mo-SAs catch the O atoms in air, forming the O2 -covered Mo-N3 coordination. The dopants of carbon source with different structures and amounts can modulate the site density of Mo-SAs, therefore controlling the amounts of coordinated O atoms. Furthermore, coordinated O atoms around Mo-SAs construct the catalytic environment with Lewis base and gather photo-generated electrons under light. Such O-covered Mo-SAs endow RPCN materials (Mo-RPCN) with a strong ability for hydrogen abstraction, leading to the 99.51% ratio (28.8 mmol min-1  g-1 ) rate for thioanisole conversion with H2 O2 assisted advance oxidation technology. This work brings a new sight on the coordinated atoms dominant oxidation process.

Recycling of Flexible Polyurethane Foams by Regrinding Scraps into Powder to Replace Polyol for Re-Foaming.

In the context of protecting the ecological environment and carbon neutrality, high-value recycling of flexible polyurethane foam (F-PUF) scraps, generated in the production process, is of great significance to save petroleum raw materials and reduce energy consumption. In the present study, F-PUF scraps were ground into powder by strong shear regrinding using two-roll mill and then reused as a partial replacement of polyol for re-foaming. A series of characterizations were employed to investigate the effect of milling cycles, roller temperatures, and content of the powder on the properties of the powder and F-PUF containing powder. It was revealed that the mechanochemical effect induced breaking of the cross-linking structure and increased activity of the powder. The volume mean diameter (VMD) of powder prepared with 7 milling cycles, at room temperature, is about 97.73 µm. The microstructure and density of the F-PUF containing powder prepared in the above-mentioned manner to replace up to 15 wt.% polyol, is similar to the original F-PUF, with resilience 49.08% and compression set 7.8%, which indicates that the recycling method will play an important role in industrial applications.

Efficient Electrochemical Nitrate Reduction to Ammonia with Copper-Supported Rhodium Cluster and Single-Atom Catalysts.

The electrochemical nitrate reduction reaction (NITRR) provides a promising solution for restoring the imbalance in the global nitrogen cycle while enabling a sustainable and decentralized route to source ammonia. Here, we demonstrate a novel electrocatalyst for NITRR consisting of Rh clusters and single-atoms dispersed onto Cu nanowires (NWs), which delivers a partial current density of 162 mA cm-2 for NH3 production and a Faradaic efficiency (FE) of 93 % at -0.2 V vs. RHE. The highest ammonia yield rate reached a record value of 1.27 mmol h-1 cm-2 . Detailed investigations by electron paramagnetic resonance, in situ infrared spectroscopy, differential electrochemical mass spectrometry and density functional theory modeling suggest that the high activity originates from the synergistic catalytic cooperation between Rh and Cu sites, whereby adsorbed hydrogen on Rh site transfers to vicinal *NO intermediate species adsorbed on Cu promoting the hydrogenation and ammonia formation.

Spectroscopic and Electrokinetic Evidence for a Bifunctional Mechanism of the Oxygen Evolution Reaction*.

A bifunctional oxygen evolution reaction (OER) mechanism, in which the energetically demanding step of the attack of hydroxide on a metal oxo unit is facilitated by a hydrogen atom transfer to a second site, has the potential to circumvent the scaling relationship. However, the bifunctional mechanism has hitherto only been supported by theoretical computations. Here we describe an operando Raman spectroscopic and electrokinetic study of two highly active OER catalysts, FeOOH-NiOOH and NiFe layered double hydroxide (LDH). The data support two distinct mechanisms for the two catalysts: FeOOH-NiOOH operates by a bifunctional mechanism where the rate-determining O-O bond forming step is the OH- attack on a Fe=O coupled with a hydrogen atom transfer to a NiIII -O site, whereas NiFe LDH operates by a conventional mechanism of four consecutive proton-coupled electron transfer steps. The experimental validation of the bifunctional mechanism enhances the understanding of OER catalysts.

Strategies for Semiconductor/Electrocatalyst Coupling toward Solar-Driven Water Splitting.

Hydrogen (H2) has a significant potential to enable the global energy transition from the current fossil-dominant system to a clean, sustainable, and low-carbon energy system. While presently global H2 production is predominated by fossil-fuel feedstocks, for future widespread utilization it is of paramount importance to produce H2 in a decarbonized manner. To this end, photoelectrochemical (PEC) water splitting has been proposed to be a highly desirable approach with minimal negative impact on the environment. Both semiconductor light-absorbers and hydrogen/oxygen evolution reaction (HER/OER) catalysts are essential components of an efficient PEC cell. It is well documented that loading electrocatalysts on semiconductor photoelectrodes plays significant roles in accelerating the HER/OER kinetics, suppressing surface recombination, reducing overpotentials needed to accomplish HER/OER, and extending the operational lifetime of semiconductors. Herein, how electrocatalyst coupling influences the PEC performance of semiconductor photoelectrodes is outlined. The focus is then placed on the major strategies developed so far for semiconductor/electrocatalyst coupling, including a variety of dry processes and wet chemical approaches. This Review provides a comprehensive account of advanced methodologies adopted for semiconductor/electrocatalyst coupling and can serve as a guideline for the design of efficient and stable semiconductor photoelectrodes for use in water splitting.

Deciphering Iron-Dependent Activity in Oxygen Evolution Catalyzed by Nickel-Iron Layered Double Hydroxide.

Nickel iron oxyhydroxide is the benchmark catalyst for the oxygen evolution reaction (OER) in alkaline medium. Whereas the presence of Fe ions is essential to the high activity, the functions of Fe are currently under debate. Using oxygen isotope labeling and operando Raman spectroscopic experiments, we obtain turnover frequencies (TOFs) of both Ni and Fe sites for a series of Ni and NiFe layered double hydroxides (LDHs), which are structurally defined samples of the corresponding oxyhydroxides. The Fe sites have TOFs 20-200 times higher than the Ni sites such that at an Fe content of 4.7 % and above the Fe sites dominate the catalysis. Higher Fe contents lead to larger structural disorder of the NiOOH host. A volcano-type correlation was found between the TOFs of Fe sites and the structural disorder of NiOOH. Our work elucidates the origin of the Fe-dependent activity of NiFe LDH, and suggests structural ordering as a strategy to improve OER catalysts.

A Cobalt-Iron Double-Atom Catalyst for the Oxygen Evolution Reaction.

Single-atom catalysts exhibit well-defined active sites and potentially maximum atomic efficiency. However, they are unsuitable for reactions that benefit from bimetallic promotion such as the oxygen evolution reaction (OER) in an alkaline medium. Here we show that a single-atom Co precatalyst can be in situ transformed into a Co-Fe double-atom catalyst for the OER. This catalyst exhibits one of the highest turnover frequencies among metal oxides. Electrochemical, microscopic, and spectroscopic data, including those from operando X-ray absorption spectroscopy, reveal a dimeric Co-Fe moiety as the active site of the catalyst. This work demonstrates double-atom catalysis as a promising approach for the development of defined and highly active OER catalysts.

Atomically dispersed Fe3+ sites catalyze efficient CO2 electroreduction to CO.

Currently, the most active electrocatalysts for the conversion of CO2 to CO are gold-based nanomaterials, whereas non-precious metal catalysts have shown low to modest activity. Here, we report a catalyst of dispersed single-atom iron sites that produces CO at an overpotential as low as 80 millivolts. Partial current density reaches 94 milliamperes per square centimeter at an overpotential of 340 millivolts. Operando x-ray absorption spectroscopy revealed the active sites to be discrete Fe3+ ions, coordinated to pyrrolic nitrogen (N) atoms of the N-doped carbon support, that maintain their +3 oxidation state during electrocatalysis, probably through electronic coupling to the conductive carbon support. Electrochemical data suggest that the Fe3+ sites derive their superior activity from faster CO2 adsorption and weaker CO absorption than that of conventional Fe2+ sites.

Metal-Sulfide Catalysts Derived from Lignosulfonate and their Efficient Use in Hydrogenolysis.

Catalytic lignosulfonate valorization is hampered by the in situ liberation of sulfur that ultimately poisons the catalyst. To overcome this limitation, metal sulfide catalysts were developed that are able to cleave the C-O bonds of lignosulfonate and are resistant to sulfur poisoning. The catalysts were prepared by using the lignosulfonate substrate as a precursor to form well-dispersed carbon-supported metal (Co, Ni, Mo, CoMo, NiMo) sulfide catalysts. Following optimization of the reaction conditions employing a model substrate, the catalysts were used to generate guaiacyl monomers from lignosulfonate. The Co catalyst was able to produce 23.7 mg of 4-propylguaiacol per gram of lignosulfonate with a selectivity of 84 %. The catalysts operated in water and could be recycled and reused multiple times. Thus, it was demonstrated that an inexpensive, sulfur-tolerant catalyst based on an earth-abundant metal and lignosulfonate efficiently catalyzed the selective hydrogenolysis of lignosulfonate in water in the absence of additives.

Alkene hydrosilylation catalyzed by easily assembled Ni(ii)-carboxylate MOFs.

We report the first Ni MOF catalysts for anti-Markovnikov hydrosilylation of alkenes. These catalysts are bench-stable and easily-assembled from simple Ni salts and carboxylic acids. The best catalyst gives turnover numbers up to 9500 and is robust even after 10 recycling runs. The catalyst can be applied for the hydrosilylation of a wide range of alkenes, achieving good synthetic utility and functional group tolerance.

Transition Metal Oxides as Electrocatalysts for the Oxygen Evolution Reaction in Alkaline Solutions: An Application-Inspired Renaissance.

Water splitting is the essential chemical reaction to enable the storage of intermittent energies such as solar and wind in the form of hydrogen fuel. The oxygen evolution reaction (OER) is often considered as the bottleneck in water splitting. Though metal oxides had been reported as OER electrocatalysts more than half a century ago, the recent interest in renewable energy storage has spurred a renaissance of the studies of transition metal oxides as Earth-abundant and nonprecious OER catalysts. This Perspective presents major progress in several key areas of the field such as theoretical understanding, activity trend, in situ and operando characterization, active site determination, and novel materials. A personal overview of the past achievements and future challenges is also provided.

Highly Efficient Photoelectrochemical Water Splitting with an Immobilized Molecular Co4 O4 Cubane Catalyst.

Molecular Co4 O4 cubane water oxidation catalysts were combined with BiVO4 electrodes for photoelectrochemical (PEC) water splitting. The results show that tuning the substituent groups on cobalt cubane allows the PEC properties of the final molecular catalyst/BiVO4 hybrid photoanodes to be tailored. Upon loading a new cubane complex featuring alkoxy carboxylato bridging ligands (1 h) on BiVO4 , an AM 1.5G photocurrent density of 5 mA cm-2 at 1.23 V vs. RHE for water oxidation was obtained, the highest photocurrent for undoped BiVO4 photoanodes. A high solar-energy conversion efficiency of 1.84 % was obtained for the integrated photoanode, a sixfold enhancement over that of unmodified BiVO4 . These results and the high surface charge separation efficiency support the role of surface-modified molecular catalysts in improving PEC performance and demonstrate the potential of molecule/semiconductor hybrids for efficient artificial photosynthesis.

Electrocatalytic water oxidation by a macrocyclic Cu(ii) complex in neutral phosphate buffer.

A single-site copper complex, [Cu(TMC)(H2O)](NO3)2 (1, TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), was found to be the most active copper-based catalyst towards electrocatalytic water oxidation in neutral aqueous solution. Complex 1 leads to a cathodic shift of approximately 200 mV in potential to reach a current density of 1 mA cm(-2) in comparison with that of the previously reported dinuclear copper complex under the same conditions. Upon immobilization of complex 1 on carbon cloth, it shows greatly improved activity than other copper-based WOCs including CuOx and Cu(2+).

Visible-light-driven selective oxidation of benzyl alcohol and thioanisole by molecular ruthenium catalyst modified hematite.

Molecular ruthenium catalysts were found to selectively catalyze the oxidation of thioanisole to sulfoxide with a yield up to 100% in the presence of visible light and sacrificial reagents when they were anchored onto hematite powder. The composite photocatalysts also showed about 5 times higher efficiencies in benzyl alcohol oxidation than the system composed of dispersed molecular catalysts and hematite particles in aqueous solution. A photoelectrochemical cell based on a molecular catalyst modified hematite photoanode was further fabricated, which exhibited high activity towards the oxidation of organic substrates.

An iron-based thin film as a highly efficient catalyst for electrochemical water oxidation in a carbonate electrolyte.

A highly active iron-based water-oxidation catalyst was electrodeposited from a CO2 saturated bicarbonate solution containing Fe(2+). This catalyst (Fe-Ci) produces a current density of 10 mA cm(-2) at an overpotential of 560 mV and the activity remains constant over 18 h in the environmentally benign HCO3(-)/CO3(2-) buffer (pH 9.75). A Tafel slope of 34 mV dec(-1) was obtained for Fe-Ci, which is lower than other reported values for iron-based catalysts.

Photocatalytic water oxidation via combination of BiVO4-RGO and molecular cobalt catalysts.

A BiVO4-reduced graphene oxide (RGO) composite in conjugation with the cubic molecular complex Co4O4(O2CMe)4(py)4 (py = pyridine) has been found to be highly efficient towards visible light-driven water oxidation. A 4-fold enhancement in the average oxygen evolution rate and 100% yield based on the consumption of the sacrificial electron acceptor were obtained upon the addition of molecular cocatalysts to BiVO4-RGO in pure water.

Visible-Light-Driven Water Oxidation on a Photoanode by Supramolecular Assembly of Photosensitizer and Catalyst.

A ruthenium water oxidation catalyst (WOC) bearing hydrophobic ligands was incorporated on the surface of a dye-sensitized nanostructured TiO2 film by formation of a host-guest adduct with the dye. This provides a new strategy for constructing photocatalytically active electrodes for water oxidation. The resultant photoanode exhibits a photocurrent of 800 µA cm-2 under visible-light illumination (λ>400 nm, 300 mW cm-2 ) and 240 µA cm-2 under simulated sunlight illumination (AM 1.5G, 100 mW cm-2 ) with an applied bias of 0.2 V vs. NHE in neutral phosphate buffer.