Structural design for electrocatalytic water splitting to realize industrial-scale deployment: Strategies, advances, and perspectives

The green hydrogen generation powered by renewable electricity promises the potential decarbonization of the hard-to-abate sector and is essential for the fulfillment of the Paris Agreement that attempts to limit the global average temperature rise in the range of 1.5–2.0 ℃ above the pre-industrial level by the end of this century. Tremendous efforts have been devoted to the optimization of the electrocatalytic performance of the catalysts under industrial-relevant current densities via rational structure design,which induces a preferential electron distribution that favors the adsorption/desorption behavior of the key intermediates, thus accelerating the reaction kinetics. In this review, a brief introduction of the current energy status will be first presented to necessitate the importance of green hydrogen.Followed by the basic concepts and fundamental understanding of the reaction mechanisms, we present efficient strategies for the enhancement of the electrocatalytic performance of the catalysts to meet the rigorous requirement under industrial conditions and the in-depth understanding behind the reinforcement will be briefly discussed next. Then the recent advances regarding the rational design of electrocatalysts operating at an industrial scale will be summarized. Finally, the challenges and perspectives in this thriving field will be proposed from our point of view.

Adjusting the SnZn defects in Cu_(2)ZnSn(S,Se)_(4) absorber layer via Ge^(4+) implanting for efficient kesterite solar cells

The development of kesterite photovoltaic solar cells has been hindered by large open-circuit voltage(V_(oc))deficit.Recently,Snzn deep point defect and associative defect cluster have been recognized as the main culprit for the Voc losses.Therefore,manipulating the deep-level donor of Snzn antisite defects is crucial for breaking through the bottleneck of present Cu_(2) ZnSn(S,Se)_(4)(CZTSSe)photovoltaic technology.In this study,the Snzn deep traps in CZTSSe absorber layer are suppressed by incorporation of Ge.The energy levels and concentration of Snzn defects measured by deep-level transient spectroscopy(DLTS)decrease significantly.In addition,the grain growth of CZTSSe films is also promoted due to Ge implantation,yielding the high quality absorber layer.Consequently,the efficiency of CZTSSe solar cells increases from 9.15%to 11.48%,largely attributed to the 41 mV Voc increment.

Lithium-assisted synergistic engineering of charge transport both in GBs and GI for Ag-substituted Cu2ZnSn(S,Se)4 solar cells

Although silver(Ag) substitution offers several benefits in eliminating bulk defects and facilitating interface type inversion for Cu2ZnSn(S,Se)4(CZTSSe) photovoltaic(PV) technology, its further development is still hindered by the fairly low electrical conductivity due to the significant decrease of acceptors amount.In this work, a versatile Li–Ag co-doping strategy is demonstrated to mitigate the poor electrical conductivity arising from Ag through direct incorporating Li via postdeposition treatment(PDT) on top of the Ag-substituted CZTSSe absorber. Depth characterizations demonstrate that Li incorporation increases ptype carrier concentration, improves the carrier collection within the bulk, reduces the defects energy level as well as inverts the electric field polarity at grain boundaries(GBs) for Ag-substituted CZTSSe system. Benefiting from this lithium-assisted complex engineering of electrical performance both in grain interior(GI) and GBs, the power conversion efficiency(PCE) is finally increased from 9.21% to 10.29%. This systematic study represents an effective way to overcome the challenges encountered in Ag substitution,and these findings support a new aspect that the synergistic effects of double cation dopant will further pave the way for the development of high efficiency kesterite PV technology.

Photovoltaic-powered supercapacitors for driving overall water splitting:A dual-modulated 3D architecture

Due to the growing demand for clean and renewable hydrogen fuel,there has been a surge of interest in electrocatalytic water-splitting devices driven by renewable energy sources.However,the feasibility of self-driven water splitting is limited by inefficient connections between functional modules,lack of highly active and stable electrocatalysts,and intermittent and unpredictable renewable energy supply.Herein,we construct a dualmodulated three-dimensional(3D)NiCo_(2)O_(4)@NiCo_(2)S_(4)(denoted as NCONCS)heterostructure deposited on nickel foam as a multifunctional electrode for electrocatalytic water splitting driven by photovoltaic-powered supercapacitors.Due to a stable 3D architecture configuration,abundant active sites,efficient charge transfer,and tuned interface properties,the NCONCS delivers a high specific capacity and rate performance for supercapacitors.A twoelectrode electrolyzer assembled with the NCONCS as both the anode and the cathode only requires a low cell voltage of 1.47 V to achieve a current density of 10 mA cm^(−2) in alkaline electrolyte,which outperforms the state-of-the-art bifunctional electrocatalysts.Theoretical calculations suggest that the generated heterointerfaces in NCONCS improve the surface binding capability of reaction intermediates while regulating the local electronic structures,which thus accelerates the reaction kinetics of water electrolysis.As a proof of concept,an integrated configuration comprising a two-electrode electrolyzer driven by two series-connected supercapacitors charged by a solar cell delivers a high product yield with superior durability.

Eutectogel-based self-powered wearable sensor for health monitoring in harsh environments

Triboelectric nanogenerators(TENG)have emerged as a highly promising energy harvesting technology,attracting significant attention in recent years for their broad applications.Gel-based TENGs,with superior stretchability and sensitivity,have been widely reported as wearable sensors.However,the traditional hydrogel-based TENGs suffer from freezing at low temperatures and drying at high temperatures,resulting in malfunctions.In this study,we introduce an anti-freezing eutectogel,which uses a deep eutectic solvent(DES),to improve the stability and electrical conductivity of TENGs in harsh environmental conditions.The eutectogel-based TENG(E-TENG)produces an open-circuit voltage of 776 V,a short-circuit current of 1.54μA,and a maximum peak power of 1.1 mW.Moreover,the E-TENG exhibits exceptional mechanical properties with an elongation at a break of 476%under tension.Importantly,it maintains impressive performances across a wide temperature range from−18 to 60℃,with conductivities of 2.15 S/m at−10℃and 1.75 S/m at−18℃.Based on the excellent weight stability of the E-TENG sensor,motion sensing can be achieved in the air,and even underwater.Finally,the versatility of the E-TENG can serve as a wearable sensor,by integrating it with Bluetooth technology.The self-powered E-TENG can monitor various human motion signals in real-time and send the health signals directly to mobile phones.This research paves a new road for the applications of TENGs in harsh environments,offering wireless flexible sensors with real-time health signal monitoring capabilities.

Solvated metal complexes for balancing stability and activity of sulfur free radicals

Free radicals can improve the reaction rate,but most of them are unstable due to unpaired electrons.Simultaneously maintaining their stability and activity is challenging.Herein,taking sulfur(S)radicals as an example,we propose a strategy in which solvated metal complexes constructed by Al(acetylacetonate)_(3)and different solvents can stabilize high concentrations of S radicals with good activity through ion–dipole interactions.Based on this strategy,it is first demonstrated that S_(4)^(·-)is selectively stabilized by controlling the configurations of the solvated complexes.As a result,the reaction rate of S↔Li_(2)S is increased by 8 times,and the energy efficiency and rate capability of the Li–S batteries are significantly improved,especially the 5-fold increase in cell capacities at a low electrolyte/sulfur ratio.This work provides an important strategy in which solvated metal complexes balance the activity and stability of free radicals to accelerate reactions and their application in various fields.

Surface defect ordered Cu_(2)ZnSn(S,Se)_(4) solar cells with efficiency over 12% via manipulating local substitution

The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large open-circuit voltage deficit(V_(oc,deficit)) and significantly limit kesterite photovoltaics performance,primarily arising from the generated more recombination centers and insufficient p to n conversion at p-n junction. Herein, we establish a surface defects ordering structure in CZTSSe system via local substitution of Cu by Ag to suppress disordered Cu_(Zn) defects and generate benign n-type Zn_(Ag) donors. Taking advantage of the decreased annealing temperature of Ag F post deposition treatment(PDT), the high concentration of Ag incorporated into surface absorber facilitates the formation of surface ordered defect environment similar to that of efficient CIGS PV. The manipulation of highly doped surface structure could effectively reduce recombination centers, increase depletion region width and enlarge the band bending near p-n junction. As a result, the Ag F-PDT device finally achieves maximum efficiency of 12.34% with enhanced V_(oc) of 0.496 V. These results offer a new solution route in surface defects and energy-level engineering, and open the way to build up high quality p-n junction for future development of kesterite technology.

Highly sensitive room-temperature gas sensors based on hydrothermal synthesis of Cr_2O_3 hollow nanospheres

This paper reports that Cr2O3 hollow nanospheres （HNs） were synthesized via a hydrothermal approach and characterized by scanning electron microscopy, x-ray powder diffraction, transmission electron microscopy （TEM）, selective area electron diffraction and high resolution TEM, respectively. In addition, the room-temperature （RT） gas sensing properties of Cr2O3 HNs and conventional powders （CPs） were investigated by means of the surface photovoltage technique. The experimental data demonstrate that the RT gas sensor of the as-fabricated HNs reaches below 5 ppm whereas that of the CPs is about 40 ppm, which results from there being much more adsorbed and desorbed oxygen in HNs than in CPs at RT. The as-prepared Cr2O3 HNs could have potential applications as RT nanosensors.

Decomposition pathway and stabilization of ether-based electrolytes in the discharge process of Li-O_(2) battery

Ether-based electrolytes with relatively high stability are widely used in Li-O_(2) batteries (LOBs) with high energy density.However,they are still prone to be attacked by reactive oxygen species.Understanding the degradation chemistry of ether-based solvent induced by reactive oxygen species is significant importance toward selection of stable electrolytes for LOBs.Herein,we demonstrate that a great amount of H_(2) gas evolves on the Li anode during the long-term discharge process of LOBs,which is due to the electrolyte decomposition at the oxygen cathode.By coupling with in-situ and ex-situ characterization techniques,it is demonstrated that O_(2)^(-) induces the H-abstraction of tetraethylene glycol dimethyl ether(TEGDME) to produce a large amount of H_(2)O at cathode,and this H_(2)O migrates to Li anode and produce H_(2) gas.Based on the established experiments and spectra,a possible decomposition pathway of TEGDME caused by O_(2)^(-)at the discharge process is proposed.And moreover,three types of strategies are discussed to inhibit the decomposition of ether-based electrolytes,which should be highly important for the fundamental and technical advancement for LOBs.

Synthesis and Crystal Structure of 2-(3,3'-Bithiophen-2,2'-yl)dibenzothiazole (BTDB) and 2-(Dithieno[2,3-b:3',2' -d]thiophen-2,5-yl)dibenzothiazole (DTTDB)

The title compounds, 2-（3,3＇-bithiophen-2,2＇-yl）dibenzothiazole （BTDB） and 2-（dithieno[2,3-b：3＇,2＇-d]thiophen-2,5-yl）dibenzothiazole （DTTDB）, have been synthesized and characterized by FT-IR, NMR, MS, HRMS and X-ray single-crystal diffraction. The crystal of BTDB crystallizes in triclinic, space group P1 with a = 9.2207（17）, b = 10.453（2）, c = 10.969（2） A, V= 981.2（3） A3 and Z = 2. Crystal data of DTTDB： orthorhombic system, space group Pbcn with a = 4.5290（8）, b = 13.576（3）, c = 32.033（6） A, V= 1969.6（6） A3 and Z = 4.

High-performance triboelectric nanogenerator based on theoretical analysis and ferroelectric nanocomposites and its high-voltage applications

With the growing economy and technology,disease prevention and individual health are becoming more and more important.It is highly urgent to develop a non-toxic,self-powered,and safe high-voltage power source to prevent diseases spread by mosquitoes,especially in isolated or remote areas.Herein,we reported a high-performance rotary triboelectric nanogenerator(R-TENG)based on customized theoretical simulations and a ferroelectric nanocomposite intermediate layer.The customized theoretical simulations based on gradient electrode gaps were established to optimize gap angles and segment numbers of the electrodes,which could prevent air breakdown and enhance the R-TENG output energy by at least 1.5 times.Meanwhile,the electrical output performance of the TENG was further enhanced with a highly oriented BaTiO3(BTO)nanoparticles intermediate layer by about 2.5 times.The open-circuit voltage of R-TENG reached more than 6 kV and could continuously light 3420 light-emitting devices(LEDs)or 4 serially connected 36 W household fluorescent lamps.Therefore,a self-powered high-voltage disease prevention system is developed based on the high-performance R-TENG to reduce the risk of disease transmission.This work provides a prospective strategy for the further development of TENGs and expands practical applications of self-powered and high-voltage systems.

应用于高效雾气收集的润滑微沟槽锥

液滴在不对称一维表面的定向输送具有广泛应用,包括雾气收集、油水分离、海水淡化及传感等.液滴所受的驱动力和阻力共同作用决定液滴的运动性能,为提高液滴的运动性能,常见的策略是通过在运动方向引入各种不对称结构以增加驱动力,或者构建光滑表面以减少阻力.然而,到目前为止将增强驱动力和降低阻力同时整合到一个体系中的策略仍未见报道,这主要是由于传统的液体填充润滑表面所需的润滑油很难在物理或化学不对称的表面上稳定存在.本研究中,我们提出在具有微沟槽结构的锥表面接枝柔性聚合物分子刷,即通过协同表面结构和化学修饰来增大液滴在锥结构表面拉普拉斯驱动力并减小粘滞阻力.结果表明,与仅具有微沟槽结构的锥和仅具有聚合物分子刷的光滑锥相比,润滑微沟槽锥可显著提高液滴的运动性能,本研究为开发高效液滴运输智能表面提供了新思路.

平衡三阳离子钙钛矿中带隙和电荷传输以实现高效的室内光伏

带隙可调的钙钛矿材料在室内光伏(IPVs)领域具有广阔的应用前景.然而,与室内光相匹配的宽带隙钙钛矿通常导电性较差,缺陷密度较高,往往不利于电荷提取和传输,限制了其光伏特性.在这里,我们通过调节Br/I比,探究了不同带隙三阳离子钙钛矿的IPVs特性.研究表明,宽带隙钙钛矿能充分利用室内光,在低照度下能获得较高的开路电压,但高Br/I比的钙钛矿具有较高的缺陷密度,不利于获得高短路电流密度和填充因子.通过进一步研究不同带隙钙钛矿的结晶动力学、缺陷密度和电荷传输特性,我们发现主流观念中高效IPVs着重考虑室内光伏材料的带隙是不全面的,我们证明了通过适当降低宽带隙晶体中的Br含量可以获得室内光伏特性更优异的器件.也就是说,室内光伏晶体材料的制备需要兼顾带隙和电荷传输特性.在此工作中,平衡带隙和电荷传输的器件(Br 0.23,1.62 eV)在1035 lux的LED灯照射下取得了40.71%的最佳效率.我们的研究为高效室内光伏的设计提供了新思路.

Rational design of novel ultra-small amorphous Fe_(2)O_(3)nanodots/graphene heterostructures for all-solid-state asymmetric supercapacitors

Constructing graphene-based heterostructures with large interfacial area is an efficient approach to enhance the electrochemical performance of supercapacitors but remains great challenges in their synthesis.Herein,a novel ultra-small amorphous Fe_(2)O_(3)nanodots/graphene heterostructure(a-Fe_(2)O_(3)NDs/RGO)aerogel was facilely synthesized via excessive metal-ion-induced self-assembly and subsequent calcination route using Prussian blue/graphene oxide(PB/GO)composite aerogel as precursors.The deliberately designed a-Fe_(2)O_(3)NDs/RGO heterostructure offers a highly interconnected porous conductive network,large heterostructure interfacial area,and plenty of accessible active sites,greatly facilitating the electron transfer,electrolyte diffusion,and pseudocapacitive reactions.The obtained a-Fe_(2)O_(3)NDs/RGO aerogel could be used as flexible free-standing electrodes after mechanical compression,which exhibited a significantly enhanced specific capacitance of 347.4 F·g^(-1)at 1 A·g^(-1),extraordinary rate capability of 184 F·g^(-1)at 10 A·g^(-1),and decent cycling stability.With the as-prepared a-Fe_(2)O_(3)NDs/RGO as negative electrodes and the Co_(3)O_(4)NDs/RGO as positive electrodes,an all-solid-state asymmetric supercapacitor(a-Fe_(2)O_(3)NDs/RGO//Co_(3)O_(4)NDs/RGO asymmetric supercapacitor(ASC))was assembled,which delivered a high specific capacitance of 69.1 F·g^(-1)at 1 A·g^(-1)and an impressive energy density of 21.6 W·h·k·g^(-1)at 750 W·k·g^(-1),as well as good cycling stability with a capacity retention of 94.3%after 5,000 cycles.This work provides a promising avenue to design high-performance graphene-based composite electrodes and profound inspiration for developing advanced flexible energy-storage devices.

Two-dimensional polymer nanosheets for efficient energy storage and conversion

As a promising graphene analogue,two-dimensional(2D)polymer nanosheets with unique 2D features,diversified topological structures and as well as tunable electronic properties,have received extensive attention in recent years.Here in this review,we summarized the recent research progress in the preparation methods of 2D polymer nanosheets,mainly including interfacial polymerization and solution polymerization.We also discussed the recent research advancements of 2D polymer nanosheets in the fields of energy storage and conversion applications,such as batteries,supercapacitors,electrocatalysis and photocatalysis.Finally,on the basis of their current development,we put forward the existing challenges and some personal perspectives.

Breaking the periodic arrangement of atoms for the enhanced electrochemical reduction of nitrogen and water oxidation

The development of cost-effective and highperformance electrocatalysts has been increasingly studied to mitigate upcoming energy and environmental challenges.Amorphization and heterointerface engineering have played significant roles in the rational design of electrocatalysts and modulation of their electrocatalytic activities.However,the synergistic effect between amorphization and heterointerfaces has been scarcely reported.As a proof-of-concept attempt,we develop amorphous FeMo(a-FeMo)electrocatalysts with an abundance of heterointerfaces that are composed of amorphous components and evaluate their electrocatalytic performances toward the nitrogen reduction reaction and oxygen evolution reaction(OER).Benefitting from the synergistic effect between the amorphous nature of the a-FeMo electrocatalysts,which offer a high density of active sites,and significant electron redistribution at the heterointerfaces,the electrocatalysts exhibit a high Faradaic efficiency of 29.15%,an elevated yield rate of 71.78μg_(NH_(3)) mg_(cat.)^(-1) h^(-1) with long-term stability at a potential of-0.1V vs.reversible hydrogen electrode and excellent electrocatalytic activity toward the OER.This study provides a promising and effective method for the rational design of low-cost heterogeneous catalysts with desirable efficiency,selectivity,and stability.

Ultra-high temperature tolerant flexible transparent electrode with embedded silver nanowires bundle micromesh for electrical heater

To realize high performance flexible transparent electronics with extreme environmental adaptivity,Ag nanowires(Ag NWs)electrodes should simultaneously meet the requirements of high-temperature tolerance,chemical and mechanical robustness.Herein,a scalable Ag NWs bundle micro-meshes embedded in polyimide(Ag BMs/ePI)conducting film via a facile spray coating and transfer method is reported.Due to the synergistic effect of bundle micromesh and embedded architecture,the Ag BMs/ePI electrode exhibits high thermal stability(370℃ and 400℃ under ambient and nitrogen atmosphere conditions,respectively),low sheet resistance variation(<4%),good corrosion and deformation resistance.As an electrical heater,the Ag BMs/ePI can achieve~204℃ with the fast thermal response time of~8 s at 8 V,and exhibits good heating stability under bent condition.This work offers a promising platform for the emerging flexible transparent electronics to adapt extreme environments,especially for those devices which require high-temperature processing.

液态/准固态界面抑制锂硫电池中多硫化物在高极性电解质中的穿梭

“穿梭效应”是锂硫电池基础研发和实际应用中最主要的挑战之一,特别是在富含多硫化物的高极性电解质中.本文展示了一项抑制穿梭效应的概念性研究,通过构建一个由高极性准固态电解质和弱极性液体电解质组成的液态/准固态两相界面来解决该问题.弱极性电解质对多硫化物具有不溶解性,并且与锂金属具有良好的相容性,使锂对称电池的循环稳定性显著提升1400小时以上.此外,富含多硫化物的液态/准固态电解质的锂硫电池可实现超过300次的循环,表明液态/准固态电解质能有效抑制电解质组分与金属锂的副反应.液态/准固态两相电解质的概念为高极性溶剂在能源转换器件中的应用提供了一种新的可能性.

Solvothermal synthesis of CdS nanorods and photovoltaic characteristics of CdS/PVK composite system

Large quantities of CdS nanorods are successfully synthesized through Cd(CH3COO)2·2H2O reacting with Na2S·9H2O and EDA in aqueous solution. XRD result shows that the sample is of hexagonal structure. And TEM result shows that the morphologies of the resulting CdS are mainly in three-armed rod-like structure with a diameter of 10―15 nm and a length of 100 nm. The nanocomposites of CdS/PVK with different molar ratios are prepared by spin coating method on tin-doped indium oxide (ITO) substrate. A notable decrease of photoluminescence (PL) efficiency and a significant enhance-ment of surface photovoltage signal have been observed in CdS/PVK composites when the molar frac-tion of CdS increases. We interpret these results as the energy level matching between CdS and PVK in nanocomposites. This energy level matching facilitates fast interfacial charge transfer then increases the separation efficiency of electron-hole pairs and the carrier generation efficiency. The detailed charge transfer process has also been demonstrated.

Regulating electronic structure of two-dimensional porous Ni/Ni_(3)N nanosheets architecture by Co atomic incorporation boosts alkaline water splitting

Interfacial engineering is a powerful method to improve the bifunctional electrocatalytic performance of pure phase catalysts.While it is expected to further optimize the electronic configuration of heterojunctions to boost the reaction kinetics in hydrogen/oxygen evolution reaction(HER/OER),but remains a challenge.Herein,a novel in situ hybrid heterojunction strategy is developed to construct 2D porous Co-doped Ni/Ni_(3)N heterostructure nanosheets(Co-Ni/Ni_(3)N)by pyrolysis of partially cobalt substituted nickel-zeolitic imidazolate framework(CoNi-ZIF)nanosheets under NH3 atmosphere.A combined experimental and theoretical studies manifest that the hybrid heterostructures can display regulative electronic states and downshift d-band center from the Fermi level,as well as optimize the adsorption energy of reaction intermediates,thus reducing the thermodynamic energy barriers and accelerating the catalytic kinetics.Consequently,benefitting from the optimized electronic configuration,hierarchical hollow nanosheets architecture,and abundant doped heterojunctions,the hybrid Co-Ni/Ni_(3)N heterostructure catalyst exhibits efficient catalytic activity for both HER(60 mV)and OER(322 mV)at 10 mA cm^(-2)in alkaline media,which is 105 and 47 mV lower than that of pure Ni_(3)N,respectively.The electrochemically active surface area of Co-Ni/Ni_(3)N is two times higher than that of Ni3N.Furthermore,the coupled practical water electrolyzer requires a low voltage of 1.575 V to reach 10 mA cm^(-2),and it can be driven by a 1.5 V battery.This work highlights the interface engineering guidance for the rational establishment of hybrid interfaces by electronic modulation of interfacial effect for alkaline water splitting.