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Over the past several decades, extensive efforts have been undertaken to find methods to synthesize advanced electrocatalysts that possess rationally controllable sizes, shapes, crystallinities, compositions and structures for efficient energy conversion technologies. Of these methods, the one-pot seedless synthetic method in aqueous solution at ambient temperature has attracted extensive attention from researchers because it is a simple, inexpensive, energy-efficient, safe and less toxic method for the synthesis of electrocatalytic nanomaterials. In this review, recent developments in one-pot seedless synthetic strategies for the design of various structures of Au, Pt, Pd, Ag and multimetallic nanocrystals in aqueous solutions at ambient temperatures will be introduced, primarily focusing on the structure–electrocatalytic performance relationships of the as-prepared metal nanocrystals. Current challenges and outlooks for future research directions will also be provided in this promising research field.

Nonfiltered seawater electrolysis is promising for sustainable hydrogen gas. However, hydrogen production from seawater electrolysis faces many challenges, including corrosion caused by insoluble precipitates such as Cl−, Mg2+and Ca2+in alkaline seawater as well as marine pollutants can lead to blocking active sites, together with high energy consumption, resulting in low efficiency and poor stability of electrocatalyst, which hinders the application of seawater electrolysis technology. In this work, we report H2O enrichment of the Pt/hexagonal boron nitride (h‐BN) electrocatalyst. Electrochemical tests and in situ experiments both demonstrate that h‐BN as the support loaded Pt effectively prevents the corrosion of the cathode, the formation of fouling, and reduces energy consumption, resulting in prolonged operating stability at high current density. The electrocatalyst works stably for over 1000 h at a high current density of 500 mA cm−2in alkaline seawater electrolytes. Pt/h‐BN shows better hydrogen evolution performance than Pt/C under industrial production conditions and has good industrial application prospects. In this work, we construct a enriched H2O electrocatalyst through hexagonal boron nitride as a support loaded Pt in seawater splitting, which achieves anti‐corrosion, anti‐fouling and reduce energy consumption. This strategy of reactants enrichment can be used in other complex catalytic environments.

Developing a high-activity and antitoxic electrocatalyst is still a demanding task. Enhancing the enrichment of oxygen species on catalysts is beneficial for thorough oxidation of ethanol to generate CO2, but the role of oxygen radicals in the process of ethanol oxidation is still ambiguous. Herein, an artificial oxidase that can catalyze oxygen to generate reactive oxygen species (ROS) in-situhas been applied in EOR for the first time and the roles of •OH, •O2−, and 1O2in complete oxidation of ethanol were investigated. The mass activity of EOR is 18.2 A mgPt−1in 1 mol L−1KOH and the CO2selectivity is 98.7%. The research showed that Sn element could optimize coordination mode on catalyst surface, which enhanced oxidase activity of the catalyst. Explored the intermediates of the reaction and evaluated the performance of the catalyst using in-situinfrared testing technology. Theoretical calculations indicate that C–C bond breakage of *CH3CO to generate *CH3and *CO is potential determination steps in the C1 pathway. When singlet oxygen is present on the PtSn IM/C surface, the dissociation energy of C–C bond is –0.51 eV, which is lower than the 1.07 eV of hydroxyl radicals and –0.47 eV of superoxide anions.

The preparation of stable and efficient acidic overall water splitting catalysts is crucial to advance the progress of proton exchange membrane water electrolyzers. Herein, we successfully prepared IrPdRhMoW HEA metallene with rich amorphous and crystalline structures. In 0.5 mol L−1H2SO4, the extraordinary catalytic performance (the overpotentials for hydrogen evolution (HER) and oxygen evolution (OER) of IrPdRhMoW/C at 10 mA cm−2are 15 mV and 188 mV, respectively) is far stronger than that of commercial catalysts (HER: Pt/C, 47 mV and OER: RuO2, 305 mV) and even other reported noble metal-based catalysts. Using IrPdRhMoW/C for the overall water splitting, only a cell voltage of 1.48 V is required to achieve 10 mA cm−2and 1.59 V required to achieve 100 mA cm−2, which is the best voltage under high current density reported so far. More importantly, the IrPdRhMoW/C still maintains excellent electroactivity and structural stability after 100 h of water splitting at 100 mA cm−2. Theory calculations reveal the self-balanced effect of electronic structures in the HEA due to the co-existence of crystalline and amorphous lattice structures. The strong orbital couplings not only maximize the electroactivity towards both HER and OER but also stabilize the valence states of metal sites for durable electrocatalysis.

Molybdenum disulfide (MoS2) has become a competitive candidate for efficient and economical hydrogen evolution reaction (HER). Compared with 1T-MoS2, 2H-MoS2possesses exceptional thermodynamic stability but still suffers from low active site density, poor conductivity, and weak hydrogen bonding in the wide pH range. Herein, 2H-MoS2nanoflowers with phosphorus doping, sulfur vacancies and crystalline-amorphous heterojunction were synthesized viaphosphorus-assisted rapid calcination method. Benefiting from the cooperative interaction of multiple strategies, the prepared 2H-MoS2nanoflowers firstly achieve efficient pH-universal HER at high current densities. Experimental results show that in alkaline, acidic, and neutral media, MoS2-P2 requires only 332, 302, and 417 mV to drive the current density of 500 mA cm−2and obtains 932, 1100, and 472 mA cm−2at the potential of −0.4 V vs. RHE, respectively. Moreover, MoS2-P2 shows excellent stability of low and high current density in the full pH range.

A series of MPX/CNT with ultra-small metastable crystalline phase-controlled are rapidly synthesized in a household microwave oven by an ultra-fast synthesis method. By altering the phosphorus source to synthesize different metastable crystalline phase Pd phosphides.

In electrocatalysis, the stability issue between catalyst and support still needs great attention. Here, a series of high-entropy alloy nanoparticles (HEA-NPs) embedded in carbon cloth (CC) were synthesized by using the scalable strategy-microwave heating. Among them, PtRhCoNiCu/CC exhibits outstanding hydrogen evolution reaction (HER) activity (19 and 170 mV overpotential at 10 and 1000 mA cm−2) and stability (150 h), outperforming other recently reported HEAs catalysts. IrRuCoNiCu/CC displays superior oxygen evolution reaction (OER) activity (166 and 354 mV overpotential at 10 and 1000 mA cm−2) and stability (150 h), and shows a lower overpotential than recently reported HEA catalysts. In water splitting, IrRuCoNiCu/CC(+)//PtRhCoNiCu/CC(-) electrolyzer achieves 500 mA cm−2(1000 mA cm−2) high current density at 1.76 V (1.88 V) and exhibits excellent stability, which is one of the best catalysts currently. Therefore, the novel supported HEA catalyst with high stability is expected to be a promising candidate material for industrialized water splitting.

In this study, an ultra-fast and simple solvent-free microwave method was successfully demonstrated using a series of ultra-small (~2.5 nm) surfactant-free Ru2P@Ru/CNT heterostructures for the first time. The structure has a high-density Ru component and Ru2P component interface, which accelerates the hydrogen evolution reaction (HER). The prepared Ru2P@Ru/CNT demonstrated excellent catalytic effects for the HER in alkaline media and real seawater. The experimental results indicate that ratio-optimized Ru2P@Ru/CNT (Ru2P:Ru = 66:34) requires only 23 and 29 mV to reach 10 mA cm–2in 1.0 mol/L KOH and real seawater, respectively. These values are 10 and 24 mV lower than those of commercial Pt/C in 1.0 mol/L KOH (33 mV) and real seawater (53 mV), respectively, making it among the best non-Pt HER reported in the literature. Additionally, the TOF of Ru2P@Ru/CNT in alkaline freshwater and seawater were 13.1 and 8.5 s–1, respectively. These exceed the corresponding values for Pt/C, indicating that the catalyst has excellent intrinsic activity. The high current activity of Ru2P@Ru/CNT in 1.0 mol/L KOH was explored, and only 77 and 104 mV were required to reach 500 and 1000 mA cm–2, respectively. After 100 h of durability testing, the catalyst retained excellent catalytic and structural stability in low current density, high current density, and seawater.

Noble metal aerogels (NMAs), belonging to the porous material, have exhibited excellent catalytic performance. Although the synthesis method continues to improve, it still exists some problems which hindered the experimental process, such as high concentration of noble metal precursors, long synthesis cycle, expensive production cost, and uncontrollable ligament length. In this work, ultrasonic wave and reducing agent NaBH4were simultaneously applied to gelation process. With the cavitation of ultrasound, it can generate huge energy with heating and stirring, thus gelation reaction proceeded quickly, and even completed the process in only a few seconds, that is much faster than the recorded. A wide concentration range was successfully expanded from 0.02 mmol/L to 62.5 mmol/L. Further, we extended this method to a variety of noble metal elements (Au, Ru, Rh, Ag, Pt, Pd), and this method is adaptive for the synthesis of single metal aerogels (Au, Ag, Ru, Rh, Pd), bimetal and trimetal aerogels (Au-Ag, Au-Rh, Au-Ru, Au-Pt, Au-Pd, Au-Pt-Pd). In addition, the ligament size of alloy aerogels are 10 nm or less. Moreover, their brilliant properties were demonstrated in hydrogen evolution reaction (HER) and ethanol oxidation reaction (EOR).

Titanium alloys are excellent structural materials in engineering fields, but their poor tribological properties limit their further applications. Electroless plating is an effective method to enhance the tribological performance of alloys, but it is difficult to efficiently apply to titanium alloys, due to titanium alloy’s strong chemical activity. In this work, the electroless Nickel-Boron (Ni-B) coating was successfully deposited on the surface of titanium alloy (Ti-6AL-4V) via a new pre-treatment process. Then, linearly reciprocating sliding wear tests were performed to evaluate the tribological behaviors of titanium alloy and its electroless Ni-B coatings. It was found that the Ni-B coatings can decrease the wear rate of the titanium alloy from 19.89×10−3mm3to 0.41×10−3mm3, which attributes to the much higher hardness of Ni-B coatings. After heat treatment, the hardness of Ni-B coating further increases corresponding to coating crystallization and hard phase formation. However, heat treatment does not improve the tribological performance of Ni-B coating, due to the fact that higher brittleness and more severe oxidative wear exacerbate the damage of heat-treated coatings. Furthermore, the Ni-B coatings heat-treated both in air and nitrogen almost present the same tribological performance. The finding of this work on electroless coating would further extend the practical applications of titanium alloys in the engineering fields.

Large-scale production of unconventional phase-controlled telluride catalysts in a simple and fast manner still poses a great challenge. Herein, we develop a superfast tellurizing synthesis method that can quickly prepare unconventional phase-controlled palladium telluride nanoparticles (Pd-Te NPs) on carbon nanotubes (CNTs) (i.e., PdTe/CNT, Pd20Te7/CNT) in 60 s. By merely tuning the mass of the tellurium precursors under the same conditions, fine (about 5.5 nm) and high-yield (about 90%) hexagonal structured PdTe/CNT and rhombohedral structured Pd20Te7/CNT can be precisely synthesized. The hexagonal structured PdTe/CNT exhibits excellent performance for glycerol oxidation reaction (GOR) and ethylene glycol oxidation reaction (EGOR). Specifically, the highest current density for GOR is 2.72 A mgPd−1, which is 1.9-fold higher than that of rhombohedral structured Pd20Te7/CNT, and 2.8-fold higher than that of Pd/CNT. It also outperforms most catalysts reported in GOR. Meanwhile, the specific activity for EGOR is 3.65 A mgPd−1, which is 2.1 and 3.9 times higher than those of rhombohedral structured Pd20Te7/CNT and Pd/CNT. We hope that this work can provide guidance for the preparation of crystalline phase-controlled telluride catalysts vianew tellurization and inspire the application of crystalline phase-controlled materials.

Defect engineering has become one of the important considerations in today’s electrocatalyst design. However, the vacancies in the ordered crystal structure (especially body-centered cubic (bcc) and the effect of ordered vacancies (OVs) on the electronic fabric have not been researched yet. In this work, we report the inaugural time of the generation of OVs in the bcc architecture and discuss the insight of the modulation system of the material and its part in the electrochemical N2reduction reaction (NRR). OV-PdCu-2 achieves the highest Faradaic efficiency value of 21.5% at 0.05 V versus RHE. When the potential increases to 0 V versus RHE, the highest ammonia yield is 55.54 μg h–1mgcat–1, which is significantly better than the unetched PdCu nanoparticles (12.83 μg h–1mgcat–1). It is the latest reported catalyst to date in the NRR process at 0 V versus RHE (see Supporting Information).

[Display omitted] • A high-throughput approach is used to establish a database of crystalline and amorphous alloys. • The amorphous alloys exhibit a weaker compositional dependence in plasticity parameters. • Different deformation mechanisms are responsible for respective plasticity behavior. • A composition-dependent atomic model is proposed to elucidate structure-property relationships. A high-throughput approach based on magnetron co-sputtering of alloy libraries is employed to investigate mechanical properties of crystalline and amorphous alloys in a ternary palladium (Pd)-tungsten (W)-silicon (Si) system with the aim to reveal the difference in plastic deformation response and extract the relevant structure-property relationships of the alloys in the system. It was found that in contrast to crystalline alloys, the amorphous ones, i.e., metallic glasses, exhibited a much smaller fluctuation range in the plasticity parameters (E r 2/ H and W p / W t), indicating a significant difference in the plastic deformation mechanism controlling the mechanical properties for the respective alloys. We propose that the inhomogeneous deformation of amorphous alloys localized in thin shear bands is responsible for the weaker compositional dependence of both plasticity parameters, while dislocation gliding in crystalline materials is significantly more dependent on the exact structure, thus resulting in a larger scattering range. Based on the representative efficient cluster packing model, a set of composition-dependent atomic structural models is proposed to figure out the structure-property relationships of amorphous alloys in Pd-W-Si alloy system. [ABSTRACT FROM AUTHOR]

The development of electrocatalysts with high catalytic activity and resistant to chlorine has become crucial for the large-scale implementation of seawater electrolysis. Here, the strong metal support interaction (SMSI) between Pt and NiMoO4is enhanced by substitutional P atom-doping (P-Pt/NiMoO4@NF) to optimize the metal surrounding environment, realizing the efficient and anticorrosive seawater electrolysis. Density functional theory (DFT) reveals that substitutional P atom-doping can adjust the electronic structure to optimize the hydrogen adsorption free energy (ΔGH*) and decrease the adsorption energy of Cl-for the HER process. Benefiting from the SMSI caused by substitutional P atom-doping, the prepared P-Pt/NiMoO4@NF catalyst achieves a current density of 1.0Acm-2at an ultra-low overpotential of only 80mV, surpassing the most reported Pt-based electrocatalysts. More importantly, in the anion exchange membrane (AEM) electrolyzer, the catalyst used as the cathode can drive 500mAcm-2under industrial conditions with only 1.75V, while running steadily for 120h, and with high efficiency and low price of H2per gallon gasoline equivalent (GGE).

Synergistic monometallic nanocatalysts have attracted much attention due to their high intrinsic activity properties. However, current synergistic monometallic nanocatalysts tend to suffer from long reaction paths due to restricted nanoscale interfaces. In this paper, we synthesized the interstitial compound N-Pt/CNT with monometallic atomic interfaces. The catalysts are enriched with atomic interfaces between higher valence Ptδ+and Pt0, allowing the reaction to proceed synergistically within the same component with an ideal reaction pathway. Through ratio optimization, N2.42-Pt/CNT with a suitable ratio of Ptδ+and Pt0is synthesized. And the calculated turnover frequency of N2.42-Pt/CNT is about 37.4 s–1(−0.1 V vs reversible hydrogen electrode (RHE)), six times higher than that of the commercial Pt/C (6.58 s–1), which is the most intrinsically active of the Pt-based catalysts. Moreover, prepared N2.42-Pt/CNT exhibits excellent stability during the chronoamperometry tests of 200 h. With insights from comprehensive experiments and theoretical calculations, Pt with different valence states in monometallic atomic interfaces synergistically accelerates the H2O dissociation step and optimizes the Gibbs free energy of H* adsorption. And the existence of desirable hydrogen transfer paths substantially facilitates hydrogen evolution reaction kinetics.

The hydrogen evolution reaction (HER) is one of the most significant reactions in the electrolysis water process, and electrocatalysts which possess high mass activity and excellent stability are the most important driving factors to improve the efficiency of HER. As for the efficient commercially electrocatalyst, Pt/C is limited in development because of its high cost. Therefore, the study of non-Pt high-efficiency catalysts is particularly important at this moment. Here, we creatively report for the first time a kind of RuPdM (M= Ni, Co, Fe) ultrathin nanosheets (NSs), which exhibit extraordinary electrochemical properties for HER under alkaline conditions. The overpotential of optimized trimetallic Ru38Pd34Ni28ultrathin NSs is only 20 mV (10 mA cm–2), and the mass activity reaches 6.15 A mg–1noble metalat −0.07 V vs RHE. It can be compared to Pt-based electrocatalysts, which have the highest mass activity currently reported. The durability tests also prove that the stability of the electrocatalyst is outstanding. DFT calculations disclose that the flexible modulation of electronic structures of RuPd ultrathin NSs is achieved by utilizing the additional 3d transition metals Fe, Co, and Ni. In particular, the Ni-3d bands act as the continuous electron-supply center for Ru to ensure an efficient electron transfer toward the adsorbates. Meanwhile, the stable Pd sites are critical for coupling the O-2pπ orbital in the initial H2O splitting with a facile barrier. This work will open up a new era of non-Pt materials for alkaline hydrogen evolution toward practical application.

Photocatalytic hydrogen production represents a promising strategy for clean, sustainable, and environmentfriendly energy supply. Up to now, great efforts have been devoted to designing the photocatalysts with noble metal as co-catalyst for visible-light-driven hydrogen evolution, while more efficient photocatalytic systems are still a major challenge. Herein, we report a facile strategy for synthesizing face-to-face ultrathin Pd nanosheets-amorphous carbon nitride (Pd NSs-ACN) structure with large contacting interface and short electronic transmission pathway, which can work as an efficient photocatalyst for hydrogen production. The synthesis starts with the growth of ultrathin Pd NSs, followed by assembly with the visible-light-response ACN through a simple stirring and annealing procedure. The resultant two dimensional face-to-face structures deliver an average hydrogen generation rate of 1.45 mmol h−1g−1at a temperature of 25°C, almost 2.6 times higher than that of Pd Nps-ACN with particle- to-face structural feature. The efficient photocatalytic activity is ascribed to the formation of high-density of active sites between ultrafine face-to-face contacted Pd NSs and the ACN, which cooperate more synergistically towards photocatalytic hydrogen production. The face-to-face engineered Pd NSs-ACN hybrids also offer a good stability revealed by photocatalytic hydrogen production measurements. The extraordinary performance highlights a powerful engineering model for designing other face-to-face contacting co-catalyst/photocatalysts, which will be a great impetus to optimize new catalytic transformations. 目前, 能源与环境问题已经成为影响人类可持续发展的主要矛盾. 为了实现人类社会的可持续发展, 研究者们一直致力于开发新的 储能技术. 半导体光催化制氢凭借其清洁、可持续、环境友好的优势成为研究热点. 传统的光催化制氢体系以贵金属为助催化剂, 宽带隙 半导体为光催化剂, 这种光催化系统的太阳能转换效率难以满足实际需求. 在本文中, 我们合成出一种具有较大接触界面和较短的电子传 递路径的共面型超薄钯纳米片/非晶氮化碳复合结构. 在室温25°C条件下, 该结构平均氢气生成速率为1.45 mmol mg−1h−1, 是钯纳米颗粒- 无定形碳化氮粒面型结构的2.6倍. 同时, 该共面型光催化剂具有优良的产氢稳定性. 该催化剂既充分利用了钯纳米片表面高密度的活性位 点, 又利用了无定型氮化碳宽的光谱响应. 本工作为可见光驱动的高效助催化剂和光催化剂界面设计提供了一种新的策略.

Despite its very high capacity (4200 mAh g–1), the widespread application of the silicon anode is still hampered by severe volume changes (up to 300%) during cycling, which results in electrical contact loss and thus dramatic capacity fading with poor cycle life. To address this challenge, 3D advanced Mxene/Si-based superstructures including MXene matrix, silicon, SiOxlayer, and nitrogen-doped carbon (MXene/Si@SiOx@C) in a layer-by-layer manner were rationally designed and fabricated for boosting lithium-ion batteries (LIBs). The MXene/Si@SiOx@C anode takes the advantages of high Li+ion capacity offered by Si, mechanical stability by the synergistic effect of SiOx, MXene, and N-doped carbon coating, and excellent structural stability by forming a strong Ti–N bond among the layers. Such an interesting superstructure boosts the lithium storage performance (390 mAh g–1with 99.9% Coulombic efficiency and 76.4% capacity retention after 1000 cycles at 10 C) and effectively suppresses electrode swelling only to 12% with no noticeable fracture or pulverization after long-term cycling. Furthermore, a soft package full LIB with MXene/Si@SiOx@C anode and Li[Ni0.6Co0.2Mn0.2]O2(NCM622) cathode was demonstrated, which delivers a stable capacity of 171 mAh g–1at 0.2 C, a promising energy density of 485 Wh kg–1based on positive active material, as well as good cycling stability for 200 cycles even after bending. The present MXene/Si@SiOx@C becomes among the best Si-based anode materials for LIBs.

Tuning reactive metal-support interaction (RMSI) is a promising approach to optimizing catalytic active sites viathe electronic, geometric and compositional effects. In general, the RMSI is conducted on the reducible oxides viaa high-temperature reaction (>550 °C). Herein we report a strong RMSI between Pt single atom (PtSA) and non-oxide-based g-C3N4built by an in-situphotocatalytic reduction method at a sub-zero temperature. The experimental observation confirms that the rich N vacancies in g-C3N4produce an obvious electron-deficient effect, which greatly enhances the RMSI. This strong RMSI contributes to the highest PtSA coverage density of 0.35 mg m−2reported to date in carbon-based materials and outstanding H2-evolution activity of 174.5 mmol g−1h−1perPtSA relative to those on the electron-rich g-C3N4. The structure simulation reveals that the RMSI can not only stabilize the PtSA on the electron-deficient g-C3N4viathe strong chemical bond between PtSA and the two-coordinated C (C2C) sites caused by the N vacancies, but also promises the PtSA with an optimized electronic and geometric structures for capturing photogenerated electrons and producing H2. This finding opens a new channel for designing and manipulating single atom-loaded photocatalyst viathe RMSI at a sub-zero low temperature.

Photocatalytic technology holds great promise in renewable energy and environmental protection. Herein, we report the synthesis of a class of polyaniline-sensitized BiOCl core/shell nanosheets with visible-light photocatalytic activity by a one-step oxidative polymerization method and show how the hybrid nanosheet boosts the photocatalytic activity and stability for degradation of Rhodamine B (RhB). In this unique structure, the ultrathin polyaniline (PANI) as a shell with the thickness of about 1–2 nm, can widen the response of the catalyst to visible light to boost photocatalysis and the BiOCl core can promote the separation of photogenerated carriers from the PANI. We demonstrate that the optimized BiOCl/PANI core/shell photocatalyst shows nearly three times higher photocatalytic activity for the degradation of RhB than pure BiOCl and also shows high stability. This work provides a new strategy for the design of a highly efficient hybrid photocatalyst driven by visible light. 光催化技术在可再生能源和环境保护方面有巨大的潜力. 本文通过一步氧化聚合法合成了一种超薄聚苯胺壳敏化氯氧化铋核纳米片结构. 该结构中约1–2纳米厚的超薄聚苯胺壳可以促进催化剂对可见光的响应, 氯氧化铋核可以促进聚苯胺中光生载流子的分离, 在可见光驱动下对于降解罗丹明B具有较高的光催化活性和稳定性. 优化后的氯氧化铋/超薄聚苯胺核壳催化剂的光催化降解罗丹明B的活性比纯氯氧化铋高出近三倍, 且稳定性更高. 本工作为设计可见光驱动的高效混合光催化剂提供了一种新的策略.

The molecular-level design and controlled synthesis of materials are of key importance for advancing their applications. Based on the special structure of 3-aminophenol, containing both phenol and amine groups, a facile synthesis of highly monodisperse poly(benzoxazine-co-resol)-based polymer spheres was first reported by the autocatalysis polymerization of 3-aminophenol and formaldehyde without using any catalyst, surfactants, templates, and/or functional dopants at low temperature. The sizes of polymer spheres can be widely tuned from 372 to 1030 nm by changing the initial reaction temperatures and the concentrations of monomers. Based on FTIR, NMR, XPS, and EDX analysis, 3-amoniaphenol was evidenced not only to participate in the polymerization and form the structure of polybenzoxazine but also to catalyze the polymerization. Furthermore, they can be pseudomorphically and uniformly converted to the corresponding carbon spheres in high yield due to the excellent thermal stability of 3-aminophenol–formaldehyde resin.

3D porous carbonaceous electrodes have attracted extensive attention as advanced electrocatalysts for electrocatalytic applications. Here, the latest progress in the design and fabrication strategies of various 3D porous carbonaceous electrodes and their relevant electrocatalytic applications is provided. Effective approaches to design carbonaceous substrates, recent important advances in the design of carbonaceous electrocatalysts, and a summary of the synthesis methods of free-standing carbonaceous electrodes are presented together with their relevant electrocatalytic applications. Finally, some perspectives on the design and applications of 3D porous carbonaceous electrodes are discussed.

The dehydrogenation and conversion of methanol into 1,1-dimethoxymethane (DMM) was achieved over noble metal-free photocatalyst CdS/Ni2P under visible light. This photocatalytic process for methanol-to-H2and DMM conversion is efficient and atom economic, with an optimal rate and selectivity of DMM of 188.42 mmol g−1h−1and 82.93%, respectively. This work supplies a new green approach for the direct efficient conversion of methanol into DMM and provides a promising avenue for sustainable bio-methanol applications.

Most luminescent glucose sensors based on the interaction of glucose with organic boric acids or borates. Herein, a new luminescent glucose sensor is designed using thioglycolic acid-capped CdTe quantum dots in the presence of cheap inorganic boric acid. Both peak position and intensities change upon the addition of glucose because of the interaction of boric acid with glucose and thioglycolic acid-capped CdTe quantum dots, which enables glucose detection by either color change or intensity change. The luminescent intensities change linearly with glucose concentrations in the ranges from 0.03 to 1 mM and 1–25 mM with a detection limit of 10 µM (S/N= 3). Moreover, glucose concentrations can be conveniently detected by color change in the range from 1 mM–25 mM. It displays a highly selective response to glucose over other interfering but biologically important saccharides, amino acids, and common ions. A thioglycolic acid-capped CdTe QD-based sensor can detect glucose with wide linear range by change in intensity or color in the presence of cheap inorganic boric acid.

Under the condition of industrial ampere-level current density seawater splitting, the electrocatalyst for hydrogen production needs two characteristics of superb activity and long-term durability. In this work, P vacancies enriched CoxPv@NC with unique multilevel structure was synthesized and applied to ampere-level current density for seawater splitting process. The coupled CoxPv@NC seawater electrolyzer requires low voltages of 1.88 and 1.74 V to provide 1.0 A cm−2in 1.0 M KOH seawater solution at room temperature and 6.0 M KOH seawater solution at 60 °C, respectively, exhibiting no obvious decline over 100 h test at 1.0 A cm−2. In-situ Raman spectra and theoretical calculations uncover that the outstanding catalytic performance originates from the P vacancy induced optimization of intermediate adsorption energy for HER and rapid reconstruction of active species for OER. The electrocatalyst devised in this work supplies an effective way to settle the insufficient of ampere-level current-density-tolerant bifunctional electrocatalysts in industrial seawater splitting.

The built-in electric field (BEF) has become an effective means of adjusting the electronic structure and hydrogen spillover to influence the adsorption of intermediates. However, the previously reported BEF cannot be tuned continuously and precisely. Herein, a series of nanocatalysts with interstitial BEF were successfully synthesized, and the effect of precisely tuned interstitial BEF on the intermediate’s adsorption and hydrogen spillover was systematically investigated using changing the insertion of interstitial B. Three catalysts with different BEF strengths were obtained by changing the interstitial content (B0.22-Cu/NC, B0.30-Cu/NC, B0.41-Cu/NC), and it was demonstrated that B0.30-Cu/NC gave the best catalytic performance for hydrogen evolution reactions (HERs). The turnover frequency (TOF) value is shown to reach 0.36 s–1at just −0.1 V vs. RHE, which is about 3 times that of Cu (0.12 s–1). For the HER, it is one of the best Cu-based catalysts reported to date (Table S3). Besides, when the catalyst was applied to the cathode of the PEM water electrolyzer, B0.30-Cu/NC exhibited long-time stability at a water-splitting current density of 500 mA cm–2. Density functional theory and in situ Raman spectroscopy suggest that a suitable interstitial BEF can not only optimize the intermediate’s adsorption but also promote hydrogen spillover.

Aerogels, as three-dimensional porous materials, have attracted much attention in almost every field owing to their unique structural properties. Designing high-entropy alloy aerogels (HEAAs) to quinary and above remains an enormous challenge due to the different reduction potentials and nucleation/growth kinetics of different constituent metals. Herein, a novel and universal chelating co-reduction strategy to prepare HEAAs at room temperature in the water phase is proposed. The addition of chelators (ethylenediaminetetraacetic acid tetrasodium salt, sodium citrate, salicylic acid, and 4,4′-bipyridine) with a certain strong coordination capacity can adjust the reduction potential of different metal components, which is the key to synthesize single-phase solid solution alloys successfully. The optimized AgRuPdAuPt HEAA can be an excellent electrocatalyst for hydrogen evolution reaction (HER) with an ultrasmall overpotential of 22 mV at 10 mA cm–2and excellent stability for 24 h in an alkaline solution. In situRaman spectroscopy unveils the enhanced hydrogen evolution reaction mechanism of HEAAs. Overall, this work provides a novel chelating co-reduction strategy for the facile and versatile synthesis and design of advanced HEAAs and broadens the development and utilization of multi-elemental alloy electrocatalysts.

Seawater electrolysis is a potential way to realize the large-scale hydrogen production without relying on freshwater resources, but limited by the chlorine evolution reaction (ClER) on the anode and high potential for seawater electrolysis. In this work, MOF-derived Ru, Fe dual-doped Ni2P nanosheets (RuFe-Ni2P@NF) is constructed to serve as bifunctional catalyst for chlorine-free hydrogen production by hybrid hydrogen evolution reaction (HER) coupled with hydrazine oxidation reaction (HzOR) in seawater. As an ideal bifunctional electrocatalyst for overall hydrazine splitting (OHzS) in seawater, RuFe-Ni2P@NF catalyst only needs 0.69 V to achieve 1000 mA cm−2. Moreover, the energy-saving H2production is realized by utilizing OHzS unit, which can save 4.70 W · h of electricity compared with the N2H4-free unit for producing 1.0 L of H2. Moreover, the direct hydrazine fuel cell (DHzFC) is assembled to drive OHzS to realize the self-powered H2production. The industrial hydrazine sewage can serve as feed for the above eletrolysis system, which has been degraded to ∼ 8 ppb rapidly. DFT calculations demonstrate that the Ru and Fe dual-doping can not only realize the thermoneutral ΔGH*for HER but also decrease the free energy of dehydrogenation of *N2H3to *N2H2for HzOR, realizing the intrinsically enhanced dehydrogenation kinetics.

Convex hexoctahedral nanocrystals have been synthesized through fast growth kinetics and the use of cetylpyridinium chloride as a capping agent. Monodisperse convex hexoctahedral Pd@Au core–shell nanocrystals with {431} high-index facets are obtained at high reaction rates by using high concentrations of ascorbic acid in the presence of cetylpyridinium chloride. In contrast, octahedral nanocrystals with {111} low-index facets and their {100}-truncated counterparts are formed at low ascorbic acid concentrations. The substitute of cetylpyridinium chloride with cetyltrimethylammonium chloride leads to the generation of concave trisoctahedral Pd@Au core–shell nanocrystals with {331} high-index facets, indicating that cetylpyridinium plays an important role in the formation of convex hexoctahedral nanocrystals. The as-prepared convex hexoctahedral Pd@Au core–shell nanocrystals exhibit remarkable catalytic performances toward electrochemiluminescence compared with truncated octahedral and concave trisoctahedral Pd@Au core–shell nanocrystals.

The high-valence metal catalysts show extraordinary talent in various electrochemical reactions. However, there is no facile method to synthesize high-valence noble metal-based materials. Herein, we synthesized the different high valence noble metal M-incorporated PdCu nanoparticles (M = Ir, Ru, Rh) by the assistant of Fe3+and exhibit excellent performance for water electrolysis. In 0.1 M KOH, the OER and HER mass activities of Ir16–PdCu/C were 50.5 and 16.5 times as much as PdCu/C, and achieved a current density of 10 mA cm–2at 1.63 V when worked for overall water splitting. DFT calculation revealed that the incorporating of high valence Ir could optimize the binding energy of the intermediate products, and promote the evolution of oxygen and hydrogen. Ex situXPS shows that the huge amount of oxidized Ir (V) formed in OER could promote the formation of O—O bonds.