Stabilizing the oxidation state of catalysts for effective electrochemical carbon dioxide conversion.

In the electrocatalytic CO2 reduction reaction (CO2RR), metal catalysts with an oxidation state generally demonstrate more favorable catalytic activity and selectivity than their corresponding metallic counterparts. However, the persistence of oxidative metal sites under reductive potentials is challenging since the transition to metallic states inevitably leads to catalytic degradation. Herein, a thorough review of research on oxidation-state stabilization in the CO2RR is presented, starting from fundamental concepts and highlighting the importance of oxidation state stabilization while revealing the relevance of dynamic oxidation states in product distribution. Subsequently, the functional mechanisms of various oxidation-state protection strategies are explained in detail, and in situ detection techniques are discussed. Finally, the prevailing and prospective challenges associated with oxidation-state protection research are discussed, identifying innovative opportunities for mechanistic insights, technology upgrades, and industrial platforms to enable the commercialization of the CO2RR.

Regulating Au coverage for the direct oxidation of methane to methanol.

The direct oxidation of methane to methanol under mild conditions is challenging owing to its inadequate activity and low selectivity. A key objective is improving the selective oxidation of the first carbon-hydrogen bond of methane, while inhibiting the oxidation of the remaining carbon-hydrogen bonds to ensure high yield and selectivity of methanol. Here we design ultrathin PdxAuy nanosheets and revealed a volcano-type relationship between the binding strength of hydroxyl radical on the catalyst surface and catalytic performance using experimental and density functional theory results. Our investigations indicate a trade-off relationship between the reaction-triggering and reaction-conversion steps in the reaction process. The optimized Pd3Au1 nanosheets exhibits a methanol production rate of 147.8 millimoles per gram of Pd per hour, with a selectivity of 98% at 70 °C, representing one of the most efficient catalysts for the direct oxidation of methane to methanol.

Multimetallic Single-Atom Catalysts for Bifunctional Oxygen Electrocatalysis.

Multimetallic alloys have demonstrated promising performance for the application of metal-air batteries, while it remains a challenge to design multimetallic single-atom catalysts (MM-SACs). Herein, metal-C3N4 and nitrogen-doped carbon are employed as cornerstones to synthesize MM-SACs by a general two-step method, and the inherent features of atomic dispersion and the strong electronic reciprocity between the multimetallic sites have been verified. The trimetallic FeCoZn-SACs and quatermetallic FeCoCuZn-SACs are both found to deliver superior oxygen evolution reaction and oxygen reduction reaction activity, respectively, as well as outstanding bifunctional durability. Density functional theory calculations elucidate the crucial contribution of Co sites of FeCoCuZn-SACs to the efficient catalysis of both the ORR and the OER. More importantly, Zn-air batteries with FeCoCuZn-SACs as cathodic catalysts exhibit a high power density (252 mW cm-2), high specific capacity (817 mAh gZn-1), and considerable stability (over 225 h) for charging-discharging processes. This work provides a visual perspective for the advantages of MM-SACs toward oxygen electrocatalysis.

Advanced Catalyst Design and Reactor Configuration Upgrade in Electrochemical Carbon Dioxide Conversion.

Electrochemical carbon dioxide reduction reaction (CO2 RR) driven by renewable energy shows great promise in mitigating and potentially reversing the devastating effects of anthropogenic climate change and environmental degradation. The simultaneous synthesis of energy-dense chemicals can meet global energy demand while decoupling emissions from economic growth. However, the development of CO2 RR technology faces challenges in catalyst discovery and device optimization that hinder their industrial implementation. In this contribution, a comprehensive overview of the current state of CO2 RR research is provided, starting with the background and motivation for this technology, followed by the fundamentals and evaluated metrics. Then the underlying design principles of electrocatalysts are discussed, emphasizing their structure-performance correlations and advanced electrochemical assembly cells that can increase CO2 RR selectivity and throughput. Finally, the review looks to the future and identifies opportunities for innovation in mechanism discovery, material screening strategies, and device assemblies to move toward a carbon-neutral society.

Understanding the Bifunctional Trends of Fe-Based Binary Single-Atom Catalysts.

Binary single-atom catalysts (BSACs) have demonstrated fascinating activities compared to single atom catalysts (SACs) for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Notably, Fe SACs is one of the most promising ORR electrocatalysts, and further revealing the synergistic effects between Fe and other 3d transition metals (M) for FeM BSACs are very important to enhance bifunctional performance. Herein, density functional theory (DFT) calculations are first adapted to demonstrate the role of various transition metals on the bifunctional activity of Fe sites, and a notable volcano relationship is established through the generally accepted adsorption free energy that ΔG* OH for ORR, and ΔG* O -ΔG* OH for OER, respectively. Further, ten of the atomically dispersed FeM anchored on nitrogen-carbon support (FeM-NC) are successfully synthesized with typical atomic dispersion by a facile movable type printing method. The experimental data confirms the bifunctional activity diversity of FeM-NC between the early- and late- transition metals, agrees very well with the DFT results. More importantly, the optimal FeCu-NC shows the expected performance with high ORR and OER activity, thereby, the assembled rechargeable zinc-air battery delivers a high power density of 231 mW cm-2 , and an impressive stability that can be stably operated over 300 h.

Ultrathin Nitrogen-Doped Carbon Encapsulated Ni Nanoparticles for Highly Efficient Electrochemical CO2 Reduction and Aqueous Zn-CO2 Batteries.

Electrochemical CO2 reduction reaction (CO2 RR), powered by renewable electricity, has attracted great attention for producing high value-added fuels and chemicals, as well as feasibly mitigating CO2 emission problem. Here, this work reports a facile hard template strategy to prepare the Ni@N-C catalyst with core-shell structure, where nickel nanoparticles (Ni NPs) are encapsulated by thin nitrogen-doped carbon shells (N-C shells). The Ni@N-C catalyst has demonstrated a promising industrial current density of 236.7 mA cm-2 with the superb FECO of 97% at -1.1 V versus RHE. Moreover, Ni@N-C can drive the reversible Zn-CO2 battery with the largest power density of 1.64 mW cm-2 , and endure a tough cycling durability. These excellent performances are ascribed to the synergistic effect of Ni@N-C that Ni NPs can regulate the electronic microenvironment of N-doped carbon shells, which favor to enhance the CO2 adsorption capacity and the electron transfer capacity. Density functional theory calculations prove that the binding configuration of N-C located on the top of Ni slabs (Top-Ni@N-C) is the most thermodynamically stable and possess a lowest thermodynamic barrier for the formation of COOH* and the desorption of CO. This work may pioneer a new method on seeking high-efficiency and worthwhile electrocatalysts for CO2 RR and Zn-CO2 battery.

Simultaneous Prediction of Wrist and Hand Motions via Wearable Ultrasound Sensing for Natural Control of Hand Prostheses.

Simultaneous prediction of wrist and hand motions is essential for the natural interaction with hand prostheses. In this paper, we propose a novel multi-out Gaussian process (MOGP) model and a multi-task deep learning (MTDL) algorithm to achieve simultaneous prediction of wrist rotation (pronation/supination) and finger gestures for transradial amputees via a wearable ultrasound array. We target six finger gestures with concurrent wrist rotation in four transradial amputees. Results show that MOGP outperforms previously reported subclass discriminant analysis for both predictions of discrete finger gestures and continuous wrist rotation. Moreover, we find that MTDL has the potential to improve the accuracy of finger gesture prediction compared to MOGP and classification-specific deep learning, albeit at the expense of reducing the accuracy of wrist rotation prediction. Extended comparative analysis shows the superiority of ultrasound over surface electromyography. This paper prioritizes exploring the performance of wearable ultrasound on the simultaneous prediction of wrist and hand motions for transradial amputees, demonstrating the potential of ultrasound in future prosthetic control. Our ultrasound-based adaptive prosthetic control dataset (Ultra-Pro) will be released to promote the development of the prosthetic community.

Ultrathin Pd3 Pt1 Rh0.1 Nanorings with Strong C-C Bond Breaking Ability for the Ethanol Oxidation Reaction.

Ethanol as a fuel for direct ethanol fuel cells (DEFCs) has the advantages of being highly energetic, environmentally friendly, and low-cost, while the slow anodic ethanol oxidation reaction (EOR), intermediate poisoning effect, and incomplete oxidation of ethanol became obstacles to the development of DEFCs. Herein, a 2D ternary cyclic Pd3 Pt1 Rh0.1 nanorings (NRs) catalyst with efficient EOR performance is prepared via a facile one-pot solvothermal approach, and systematic studies are carried out to reveal the mechanisms of the enhanced performance and C-C bond selectivity. In particular, the optimized catalyst exhibits impressive mass activity, stability, toxicity resistance, and C-C bond cleavage ability. It's proposed that the considerable performance is attributed to the unique hollow structure, providing abundant active sites. The high toxicity resistance is not only attributed to the electronic modulation of the catalyst material by Rh atoms, but also depends on the excellent water activation properties of Rh, which contribute to the removal of intermediates, such as CO. In addition, the density functional theory calculations showed that the introduction of Rh significantly enhances the C-C bond cleavage ability of the catalyst, further improving the EOR activity.

Movable type printing method to synthesize high-entropy single-atom catalysts.

The controllable anchoring of multiple isolated metal atoms into a single support exhibits scientific and technological opportunities, while the synthesis of catalysts with multiple single metal atoms remains a challenge and has been rarely reported. Herein, we present a general route for anchoring up to eleven metals as highly dispersed single-atom centers on porous nitride-doped carbon supports with the developed movable type printing method, and label them as high-entropy single-atom catalysts. Various high-entropy single-atom catalysts with tunable multicomponent are successfully synthesized with the same method by adjusting only the printing templates and carbonization parameters. To prove utility, quinary high-entropy single-atom catalysts (FeCoNiCuMn) is investigated as oxygen reduction reaction catalyst with much more positive activity and durability than commercial Pt/C catalyst. This work broadens the family of single-atom catalysts and opens a way to investigate highly efficient single-atom catalysts with multiple compositions.

Enhanced Photocatalytic Hydrolysis Performance of Chiral Molecule Loaded Titanium Disulfide Nanosheets.

The photoelectrochemical (PEC) water decomposition is a promising method to produce hydrogen from water. To improve the water decomposition efficiency of the PEC process, it is necessary to inhibit the generation of H2 O2 byproducts and reduce the overpotential required by cheap catalysts and a high current density. Studies have shown that coating the electrode with chiral molecules or chiral films can increase the hydrogen production and reduce the generation of H2 O2 byproducts. This is interpreted as the result of a chiral induced spin selectivity (CISS) effect, which induces a spin correlation between the electrons that are transferred to the anode. Here, we report the adsorption of chiral molecules onto titanium disulfide nanosheets. Firstly, titanium disulfide nanosheets were synthesized via thermal injection and then dispersed through ultrasonic crushing. This strategy combines the CISS with the plasma effect caused by the narrow bandgap of two-dimensional sulfur compounds to promote the PEC water decomposition with a high current density.

General Method for Synthesizing Effective and Durable Electrocatalysts Derived from Cellulose for Microbial Fuel Cells.

Microbial fuel cells (MFCs) can be capable of both wastewater treatment and electricity generation, which necessarily depends on the increasing cathodic performances and stability at low cost to realize industrialization. Herein, cellulose, a commercially available and sustainable material, was oxidized as a carbon precursor to produce the oxygen species synergizing the nitrogen-doped carbon (CON-900) catalyst by a facile in situ nitrogen doping method. The incorporation of nitrogen and oxygen with a high content creates more active centers. Meanwhile, the hierarchical porosity of CON-900 contributes to a high specific surface area (652 m2 g-1) and the exposure of accessible active sites. As expected, CON-900 exhibits considerable activity for the oxygen reduction reaction, excellent operating stability, and high poisoning resistance. In addition, the MFC fabricated with CON-900 as a cathode catalyst demonstrates a maximum power density of 1014 ± 23 mW m-2, which is comparable with that of the Pt/C cathode (1062 ± 14 mW m-2). This work offers a facile and versatile strategy for various biomass materials to develop low-cost and high-efficiency carbon-based catalysts for MFCs and beyond.

Progress in the development of heteroatom-doped nickel phosphates for electrocatalytic water splitting.

Hydrogen energy is expected to replace fossil fuels as a mainstream energy source in the future. Currently, hydrogen production via water electrolysis yields high hydrogen purity with easy operation and without producing polluting side products. Presently, platinum group metals and their oxides are the most effective catalysts for water splitting; however, their low abundance and high cost hinder large-scale hydrogen production, especially in alkaline and neutral media. Therefore, the development of high-efficiency, durable, and low-cost electrocatalysts is crucial to improving the overpotential and lowering the electrical energy consumption. As a solution, Ni2P has attracted particular attention, owing to its desirable electrical conductivity, high corrosion resistance, and remarkable catalytic activity for overall water splitting, and thus, is a promising substitute for platinum-group catalysts. However, the catalytic performance and durability of raw Ni2P are still inferior to those of noble metal-based catalysts. Heteroatom doping is a universal strategy for enhancing the performance of Ni2P for water electrolysis over a wide pH range, because the electronic structure and crystal structure of the catalyst can be modulated, and the adsorption energy of the reaction intermediates can be adjusted via doping, thus optimizing the reaction performance. In this review, first, the reaction mechanisms of water electrolysis, including the cathodic hydrogen evolution reaction and anodic oxygen evolution reaction, are briefly introduced. Then, progress into heteroatom-doped nickel phosphide research in recent years is assessed, and a discussion of each representative work is given. Finally, the opportunities and challenges for developing advanced Ni2P based electrocatalysts are proposed and discussed.

Synthesis and Design of a Highly Stable Platinum Nickel Electrocatalyst for the Oxygen Reduction Reaction.

Exploring effective, stable, and affordable oxygen reduction reaction (ORR) catalysts is very significant for the practical application of proton-exchange membrane fuel cells. In this work, a facile and expandable method is developed to prepare ultrathin PtNi nanowires (NWs) with various Pt/Ni contents, and the ORR performance of the synthesized samples is thoroughly investigated. Pt3.2Ni NWs show the best ORR performance among the studied samples and, notably, exhibit much better ORR activity and stability than those of the Pt/C catalyst even after a 300,000-continuous cycling test. This work confirms that the initial Pt/Ni ratio plays a critical role in the ORR activity and stability of PtNi NWs, and the structure of the PtNi NWs can be well retained after the durability test. Additionally, the structure and performance of Pt3.2Ni NWs are investigated in detail during various cycles, and the performance decay is attributed to the dealloying of Ni and the corrosion of the one-dimensional structure after a prolonged durability test. This work provides a desirable method for rationally synthesizing a highly efficient ORR electrocatalyst with remarkable stability.

Engineering Ruthenium-Based Electrocatalysts for Effective Hydrogen Evolution Reaction.

The investigation of highly effective, durable, and cost-effective electrocatalysts for the hydrogen evolution reaction (HER) is a prerequisite for the upcoming hydrogen energy society. To establish a new hydrogen energy system and gradually replace the traditional fossil-based energy, electrochemical water-splitting is considered the most promising, environmentally friendly, and efficient way to produce pure hydrogen. Compared with the commonly used platinum (Pt)-based catalysts, ruthenium (Ru) is expected to be a good alternative because of its similar hydrogen bonding energy, lower water decomposition barrier, and considerably lower price. Analyzing and revealing the HER mechanisms, as well as identifying a rational design of Ru-based HER catalysts with desirable activity and stability is indispensable. In this review, the research progress on HER electrocatalysts and the relevant describing parameters for HER performance are briefly introduced. Moreover, four major strategies to improve the performance of Ru-based electrocatalysts, including electronic effect modulation, support engineering, structure design, and maximum utilization (single atom) are discussed. Finally, the challenges, solutions and prospects are highlighted to prompt the practical applications of Ru-based electrocatalysts for HER.

Effect of kinesio taping on hemiplegic shoulder pain: A systematic review and meta-analysis of randomized controlled trials.

OBJECTIVE: The aim of this study was to evaluate the effectiveness of kinesio taping for the management of hemiplegic shoulder pain. DATA SOURCES: MEDLINE, EMBASE, Web of Science, CENTRAL, CNKI, Wan Fang databases and the grey literature research were searched from inception to July 2020. METHODS: We considered randomized controlled trials in English or Chinese that used kinesio taping for the treatment of hemiplegic shoulder pain. Two reviewers independently screened the articles, scored the methodological quality using the PEDro scale, assessed risk of bias using the Cochrane's risk of bias tool and extracted the data. The outcomes included pain, motor function of the upper limb, magnitude of shoulder subluxation and activities of daily living post-intervention. RESULTS: A total of nine studies (n = 424) met the inclusion criteria. A meta-analysis demonstrated a significant effect of kinesio taping on pain (mean difference(MD)= -1.45, 95% confidence interval(CI): -1.98 to-0.92 cm, p < 0.0001), motor function of upper limb (MD = 4.22,95%CI: 3.49 to 4.95, p < 0.00001), magnitude of shoulder subluxation (standardized mean difference(SMD) = -0.65, 95%CI: -0.95 to -0.35, p < 0.0001) and activities of daily living (MD = 6.86, 95% CI: 3.99 to 9.73, p < 0.00001) post-intervention. CONCLUSION: This meta-analysis suggests a beneficial effect of kinesio taping for reducing shoulder subluxation, improving motor function of the upper limb and activities of daily living in patients with hemiplegic shoulder pain post-intervention, which could not be interpreted simply as a placebo effect. And it was associated with reduced pain for patients with chronic stroke.

Metal-Organic Framework-Derived Carbon Nanorods Encapsulating Bismuth Oxides for Rapid and Selective CO2 Electroreduction to Formate.

Carbon dioxide (CO2 ) conversion is promising in alleviating the excessive CO2 level and simultaneously producing valuables. This work reports the preparation of carbon nanorods encapsulated bismuth oxides for the efficient CO2 electroconversion toward formate production. This resultant catalyst exhibits a small onset potential of -0.28 V vs. RHE and partial current density of over 200 mA cm-2 with a stable and high Faradaic efficiency of 93 % for formate generation in a flow cell configuration. Electrochemical results demonstrate the synergistic effect in the Bi2 O3 @C promotes the rapid and selective CO2 reduction in which the Bi2 O3 is beneficial for improving the reaction kinetics and formate selectivity, while the carbon matrix would be helpful for enhancing the activity and current density of formate production. This work provides effective bismuth-based MOF derivatives for efficient formate production and offers insights in promoting practical CO2 conversion technology.