Exploring the Cation Regulation Mechanism for Interfacial Water Involved in the Hydrogen Evolution Reaction by In Situ Raman Spectroscopy

Interfacial water molecules are the most important participants in the hydrogen evolution reaction(HER).Hence,understanding the behavior and role that interfacial water plays will ultimately reveal the HER mechanism.Unfortunately,investigating interfacial water is extremely challenging owing to the interference caused by bulk water molecules and complexity of the interfacial environment.Here,the behaviors of interfacial water in different cationic electrolytes on Pd surfaces were investigated by the electrochemistry,in situ core-shell nanostructure enhanced Raman spectroscopy and theoretical simulation techniques.Direct spectral evidence reveals a red shift in the frequency and a decrease in the intensity of interfacial water as the potential is shifted in the positively direction.When comparing the different cation electrolyte systems at a given potential,the frequency of the interfacial water peak increases in the specified order:Li+<Na^(+)<K^(+)<Ca^(2+)<Sr^(2+).The structure of interfacial water was optimized by adjusting the radius,valence,and concentration of cation to form the two-H down structure.This unique interfacial water structure will improve the charge transfer efficiency between the water and electrode further enhancing the HER performance.Therefore,local cation tuning strategies can be used to improve the HER performance by optimizing the interfacial water structure.

Cu/Mo2C synthesized through Anderson-type polyoxometalates modulate interfacial water structure to achieve hydrogen evolution at high current density

The development of efficient non-precious metal catalysts is important for the large-scale application of alkaline hydrogen evolution reaction(HER).Here,we synthesized a composite catalyst of Cu and Mo_(2)C(Cu/Mo_(2)C)using Anderson-type polyoxometalates(POMs)synthesized by the facile soaking method as precursors.The electronic interaction between Cu and Mo_(2)C drives the positive charge of Cu,alleviating the strong adsorption of hydrogen at the Mo site by modulating the d-band center of Mo_(2)C.By studying the interfacial water structure using in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy(ATR-SEIRAS),we determined that the positively charged Cu crystals have the function of activating water molecules and optimizing the interfacial water structure.The interfacial water of Cu/Mo_(2)C contains a large amount of free water,which could facilitate the transport of reaction intermediates.Due to activated water molecules and optimized interfacial water structure and hydrogen adsorption energy,the overpotential of Cu/Mo_(2)C is 24 mV at a current density of 10 mA·cm^(-2) and 178 mV at a current density of 1000 mA·cm^(-2).This work improves catalyst performance in terms of interfacial water structure optimization and deepens the understanding of water-mediated catalysis.

Self-Healing Hydrophilic Porous Photothermal Membranes for Durable and Highly Efficient Solar-Driven Interfacial Water Evaporation

It is highly desirable to develop a solar-driven interfacial water evaporatorwith a self-healing ability and high-efficiency water evaporation performance for water distillation and desalination;however,this process is considerably challenging.Herein,by exploiting the advantages of a self-healing hydrophilic polymer,a self-healing hydrophilic porous photothermal(SHPP)membrane was fabricated by curing a mixture of the polymer,carbon black,and NaCl,followed by removal of the NaCl from water.Since the SHPP membrane could serve as a photothermal layer and water transportation channel simultaneously,a solar-driven interfacial evaporator could be fabricated readily by assembling the SHPP membrane with polyethylene foam.We have shown that the SHPP membrane-based evaporator exhibited a water evaporation rate of 1.68 kg m^(−2) h^(−1) and an energy efficiency of 97.3%.These values are superior to those obtained using solar-driven interfacial evaporators with self-healing capability.Notably,by hydrogen bonds reformation between the fracture surfaces,the SHPP membrane could regain its structural integrity after breaking,making the SHPPmembrane-based evaporator the first to heal entirely and repeatedly from physical damage to sustain itswater evaporation capacity.Therefore,the potential of using SHPP membranes to develop stable,long-last ing,andhigh-efficiency solar-driven interfacial water evaporators is highlighted.

Janus membrane with enhanced interfacial activation for solar evaporation

Low solar spectrum coverage,high evaporation enthalpy,and undesired salt deposition severely limited the solar-driven interfacial evaporation technology for further sewage purification and seawater desalination.To overcome these problems,we designed an amphiphilic Janus-structured polyaniline(PANI)/ZrC/cellulose acetate(CA)(J-PZCA) membrane.Firstly,the interfacial interaction between PANI and ZrC enhances the photoabsorption and photothermal conversion efficiency.Secondly,low thermal conductivity reduces the heat lost at the interface.Most importantly,ZrC could facilitate interfacial activation,which weakens the intermolecular forces of water by affecting the hydrogen bond.Under 1 solar irradiation(1 sun),the composite membrane exhibits a high evaporation rate of 1.31 kg m^(-2)h^(-1) and an excellent efficiency of 79.4%.In addition,the sewage purification and seawater desalination experiments reveal a remarkable purification capability of J-PZCA membrane.Especially for the treatment of high-concentration salt solution,it realizes a long-term stable evaporation performance due to the excellent salt deposition resistance.Therefore,the J-PZCA membrane constructed in this study provides a new perspective for the design of efficient interfacial evaporation devices.

Factors resisting protein adsorption on hydrophilic/hydrophobic self-assembled monolayers terminated with hydrophilic hydroxyl groups

The hydroxyl-terminated self-assembled monolayer(OH-SAM),as a surface resistant to protein adsorption,exhibits substantial potential in applications such as ship navigation and medical implants,and the appropriate strategies for designing anti-fouling surfaces are crucial.Here,we employ molecular dynamics simulations and alchemical free energy calculations to systematically analyze the factors influencing resistance to protein adsorption on the SAMs terminated with single or double OH groups at three packing densities(∑=2.0 nm^(-2),4.5 nm^(-2),and 6.5 nm^(-2)),respectively.For the first time,we observed that the compactness and order of interfacial water enhance its physical barrier effect,subsequently enhancing the resistance of SAM to protein adsorption.Notably,the spatial hindrance effect of SAM leads to the embedding of protein into SAM,resulting in a lack of resistance of SAM towards protein.Furthermore,the number of hydroxyl groups per unit area of double OH-terminated SAM at ∑=6.5 nm^(-2) is approximately 2 to 3 times that of single OH-terminated SAM at ∑=6.5 nm^(-2) and 4.5 nm^(-2),consequently yielding a weaker resistance of double OH-terminated SAM towards protein.Meanwhile,due to the structure of SAM itself,i.e.,the formation of a nearly perfect ice-like hydrogen bond structure,the SAM exhibits the weakest resistance towards protein.This study will complement and improve the mechanism of OH-SAM resistance to protein adsorption,especially the traditional barrier effect of interfacial water.

Harnessing overlapped temperature-salinity gradient in solar-driven interfacial seawater evaporation for efficient steam and electricity generation

Solar-driven interfacial water evaporation(SIWE)offers a superb way to leverage concentrated solar heat to minimize energy dissipation during seawater desalination.It also engenders overlapped temperaturesalinity gradient(TSG)between water-air interface and adjacent seawater,affording opportunities of harnessing electricity.However,the efficiency of conventional SIWE technologies is limited by significant challenges,including salt passivation to hinder evaporation and difficulties in exploiting overlapped TSG simultaneously.Herein,we report self-sustaining hybrid SIWE for not only sustainable seawater desalination but also efficient electricity generation from TSG.It enables spontaneous circulation of salt flux upon seawater evaporation,inducing a self-cleaning evaporative interface without salt passivation for stable steam generation.Meanwhile,this design enables spatial separation and simultaneous utilization of overlapped TSG to enhance electricity generation.These benefits render a remarkable efficiency of90.8%in solar energy utilization,manifesting in co-generation of solar steam at a fast rate of 2.01 kg m^(-2)-h^(-1)and electricity power of 1.91 W m^(-2)with high voltage.Directly interfacing the hybrid SIWE with seawater electrolyzer constructs a system for water-electricity-hydrogen co-generation without external electricity supply.It produces hydrogen at a rapid rate of 1.29 L h^(-1)m^(-2)and freshwater with 22 times lower Na+concentration than the World Health Organization(WHO)threshold.

Fabrication of stable MWCNT bucky paper for solar-driven interfacial evaporation by coupling c-ray irradiation with borate crosslinking

Herein,we report a facile solution process for preparing multi-walled carbon nanotube(MWCNT)bucky paper for solar-driven interfacial water evaporation.This process involves vacuum filtrating a dispersion of MWCNTs that was modified by polyvinyl alcohol(PVA)under c-ray irradiation on a cellulose acetate microporous membrane,followed by borate crosslinking.Fourier transform infrared spectroscopy,Raman spectroscopy,and thermogravimetry confirmed the success of PVA grafting onto MWCNTs and borate crosslinking between modified MWCNT nanoyarns.The as-prepared crosslinked MWCNT bucky papers(BBP membranes)were used as a solar absorber,by placing them on a paper-wrapped floating platform,for interfacial water evaporation under simulated solar irradiation.The BBP membranes showed good water tolerance and mechanical stability,with an evaporation rate of 0.79 kg m^(-2)h^(-1)and an evaporation efficiency of 56%under 1 sun illumination in deionized water.Additionally,the BBP membranes achieved an evaporation rate of 0.76 kg m^(-2)h^(-1)in both NaCl solution(3.5 wt%)and sulfuric acid solution(1 mol L-1),demonstrating their impressive applicability for water reclamation from brine and acidic conditions.An evaporation rate of 0.70 kg m-2 h-1(very close to that from deionized water)was obtained from the solar evaporation of saturated NaCl solution,and the BBP membrane exhibited unexpected stability without the inference of salt accumulation on the membrane surface during long-term continuous solar evaporation.

An experimental and numerical study of chemically enhanced water alternating gas injection

In this work, an experimental study combined with numerical simulation was conducted to investigate the potential of chemically enhanced water alternating gas （CWAG） injection as a new enhanced oil recovery method. The unique feature of this new method is that it uses alkaline, surfactant, and polymer additives as a chemical slug which is injected during the water alternating gas （WAG） process to reduce the interfacial tension （IFT） and simultaneously improve the mobility ratio. In essence, the proposed CWAG process involves a combination of chemical flooding and immiscible carbon dioxide （CO2） injection and helps in IFT reduction, water blocking reduction, mobility control, oil swelling, and oil viscosity reduction due to CO2 dissolution. Its performance was compared with the conventional immiscible water alter- nating gas （I-WAG） flooding. Oil recovery utilizing CWAG was better by 26 % of the remaining oil in place after waterflooding compared to the recovery using WAG conducted under similar conditions. The coreflood data （cumulative oil and water production） were history mat- ched via a commercial simulator by adjusting the relative permeability curves and assigning the values of the rock and fluid properties such as porosity, permeability, and the experimentally determined IFT data. History matching ofthe coreflood model helped us optimize the experiments and was useful in determining the importance of the parameters influencing sweep efficiency in the CWAG process. The effectiveness of the CWAG process in pro- viding enhancement of displacement efficiency is evident in the oil recovery and pressure response observed in the coreflood. The results of sensitivity analysis on CWAG slug patterns show that the alkaline-surfactant-polymer injection is more beneficial after CO2 slug injection due to oil swelling and viscosity reduction. The CO2 slug size analysis shows that there is an optimum CO2 slug size, around 25 % pore volume which leads to a maximum oil recovery in the CWAG process. This study shows that the ultralow IFT system, i.e., IFT equaling 10 2 or 10 3 mN/ m, is a very important parameter in CWAG process since the water blocking effect can be minimized.

Hydration lubrication modulated by water structure at TiO2–aqueous interfaces

The nature of solid-liquid interfaces is of great significance in lubrication.Remarkable advances have been made in lubrication based on hydration effects.However,a detailed molecular-level understanding is still lacking.Here,we investigated water molecule behaviors at the TiO2-aqueous interfaces by the sum-frequency generation vibrational spectroscopy(SFG-VS)and atomic force microscope(AFM)to elucidate the fundamental role of solid-liquid interfaces in lubrication.Combined contributions of water structures and hydration effects were revealed,where water structures played the dominant role in lubrication for TiO2 surfaces of varying hydrophilicity,while hydration effects dominated with the increasing of ion concentrations.Superior lubrication is observed on the initial TiO2 surfaces with strongly H-bonded water molecules compared to the hydrophilic TiO2 surfaces with more disordered water.The stable ordered water arrangement with strong hydrogen bonds and the shear plane occurring between the ordered water layer and subsequent water layer may play a significant role in achieving lower friction.More adsorbed hydrated molecules with the increasing ionic concentration perturb ordered water but lead to the enhancement of hydration effects,which is the main reason for the improved lubrication for both TiO2.This work provides more insights into the detailed molecular-level understanding of the mechanism of hydration lubrication.

Sequential reactant water management by complementary multisite catalysts for surpassing platinum hydrogen evolution activity

Alkaline hydrogen evolution reaction(HER)offers a near-zero-emission approach to advance hydrogen energy.However,the activity limited by the multiple reaction steps involving H_(2)O molecules transfer,absorption,and activation still unqualified the thresholds of economic viability.Herein,we proposed a multisite complementary strategy that incorporates hydrophilic Mo and electrophilic V into Ni-based catalysts to divide the distinct steps on atomically dispersive sites and thus realize sequential regulation of the HER process.The Isotopic labeled in situ Raman spectroscopy describes 4-coordinated hydrogen bonded H_(2)O to be free H_(2)O passing the inner Helmholtz plane in the vicinity of the catalysts under the action of hydrophilic Mo sites.Furthermore,potential-dependent electrochemical impedance spectroscopy(EIS)reveals that electrophilic V sites with abundant 3d empty orbitals could activate the lone-pair electrons in the free H_(2)O molecules to produce more protic hydrogen,and dimerize into H_(2) at the Ni sites.By the sequential management of reactive H_(2)O molecules,NiMoV oxides multisite catalysts surpass Pt/C hydrogen evolution activity(49 mV@10 mA∙cm^(-2) over 140 h).Profoundly,this study provides a tangible model to deepen the comprehension of the catalyst–electrolyte interface and create efficient catalysts for diverse reactions.

The Top of the Biomimetic Triangle

There is increasing observational evidence indicating that crystalline interfacial water layers play a central role in evolution and biology. For instance in cellular recognition processes, in particular during first contact events, where cells decide upon survival or entering apoptosis. Understanding water layers is thus crucial in biomedical engineering, specifically in the design of biomaterials inspired by biomimetic principles. Whereas there is ample experimental evidence for crystalline interfacial water layers on surfaces in air, their subaquatic presence could not be verified directly, so far. Analysing a polarity dependent asym- metry in the surface conductivity on hydrogenated nanocrystalline diamond, we show that crystalline interfacial water layers persist subaquatically. Nanoscopic interfacial water layers with an order different from that of bulk water have been identified at room temperature on both hydrophilic and hydrophobic model surfaces - in air and subaquatically. Their generalization and systematic inclusion into the catalogue of physical and chemical determinants of biocompatibility complete the biomimetic triangle.

Biomass-based biomimetic-oriented Janus nanoarchitecture for efficient heavy-metal enrichment and interfacial solar water sanitation

Interfacial solar steam generation(ISSG),involving the use of solar energy to evaporate water at the water-to-vapor interface,has presented prospects for the desalination and purification of water due to high energy conversion efficiency and low-cost freshwater generation.Herein,inspired by the aligned nanostructure of plants for efficiently transporting nutrient ions,we optimally design and construct a biomass-based Janus architecture evaporator with an oriented nanostructure for ISSG,using the ice template method,followed by biomimetic mineralization with the resource-abundant and low-cost biomass of the carboxymethyl cellulose and sodium alginate as the raw materials.Taking advantage of the oriented nanostructure allowing efficient transportation of water and coordination capacity of sodium alginate for effective enrichment of heavy-metal ions,the biomass-based Janus architecture shows much lower thermal conductivity and an ultrahigh steam regeneration rate of 2.3 kg m−2 h−1,considerably surpassing those of previously reported oriented biomass-based evaporators.Moreover,the biomass precursor materials are used for this Janus evaporator,guaranteeing minimum impact on the water ecology and environment during the regeneration process of clean drinking water.This study presents an efficient,green,and sustainable pathway for ISSG to effectively achieve heavy-metal-free drinking water.

Formation mechanism for stable system of nanoparticle/protein corona and phospholipid membrane

In the physiological environment, nanoparticles(NPs) interact with proteins to form a protein-rich layer on the surface which is called "protein corona". Understanding and analyzing the formation process of protein corona and protein corona-nanoparticles is of great significance for biological related nano research. Many separation techniques have been used to analyze the composition of protein corona, but in situ analysis of protein corona is still absent. With the development of detection technology, sum frequency generation(SFG) is an effective instrument to analyze the surface protein structure and dynamic changes of protein corona in situ. In this work the molecular mechanism and surface structure effect of the interaction between nanoparticles with surface protein corona(S-NPP) and phospholipid membrane were studied. When S-NPP interacts with phospholipid membrane, the bond affinity network formed by the binding water can stabilize S-NPP around the lipid bilayer. In this process, S-NPP can be found wrapped in the hydration shell. This ultimately leads to a more moderate interaction between particles and phospholipid membrane.

Electrochemical converting ethanol to hydrogen and acetic acid for large scale green hydrogen production

Electrochemical coupling hydrogen evolution with biomass reforming reaction(named electrochemical hydrogen and chemical cogeneration(EHCC)),which realizes green hydrogen production and chemical upgrading simultaneously,is a promising method to build a carbon-neutral society.Herein,we analyze the EHCC process by considering the market assessment.The ethanol to acetic acid and hydrogen approach is the most feasible for large-scale hydrogen production.We develop AuCu nanocatalysts,which can selectively oxidize ethanol to acetic acid(>97%)with high long-term activity.The isotopic and in-situ infrared experiments reveal that the promoted water dissociation step by alloying contributes to the enhanced activity of the partial oxidation reaction path.A flow-cell electrolyzer equipped with the AuCu anodic catalyst achieves the steady production of hydrogen and acetic acid simultaneously in both high selectivity(>90%),demonstrating the potential scalable application for green hydrogen production with low energy consumption and high profitability.

The contribution of water molecules to the hydrogen evolution reaction

Traditionally,water molecules act as solvents in most chemical reactions,whereas they act as solvents and reactants in the alkaline electrolyte for the hydrogen evolution reaction(HER).It is well known that there is a current plateau in the linear potential–current dependence for HER in neutral or near-neutral electrolytes,showing that the HER is governed by the mass transport of reactive hydronium species at a given overpotential.The sharp rise in the current signal after the plateau at a slightly higher overpotential indicates that HER is supported by a new reactant,namely the water molecules rather than the limited hydronium species.Herein,in combination with our own research experience in water electrolysis,we review the relevant literature in these years about the HER activity descriptor and mainly focus on the contribution of water molecules to the HER,including their dissociation,configuration,and composition in regulating the pH-dependent HER.Finally,we try to provide new insights into understanding the mechanism of the HER in terms of interfacial water enrichment,orientation,and configuration with the electric field strength of electrode/electrolyte interface and electrode compositions.

Surface-ligand protected reduction on plasmonic tuning of one-dimensional MoO_(3−x)nanobelts for solar steam generation

Sub-stoichiometric MoO_(3−x)nanostructures with plasmonic absorption via creating oxygen vacancies have attracted extensive attentions for many intriguing applications.However,the synthesis of one-dimensional(1D)plasmonic MoO_(3−x)nanostructures with widely tunable plasmonic absorption has remained a significant challenge because of their serious morphological destruction and phase change with increasing the concentration of oxygen vacancies.Here we demonstrate a surface-ligand protected reduction strategy for the synthesis of 1D MoO_(3−x)nanobelts with tunable plasmonic absorption in a wide wavelength range from 200 to 2,500 nm.Polyethylene glycol(PEG-400)is used as both the reductant to produce oxygen vacancies and the surface protected ligands to maintain 1D morphology during the formation process of MoO_(3−x)nanobelts,enabling the widely tunable plasmonic absorption.Owing to their broad plasmonic absorption and unique 1D nanostructure,we further demonstrate the application of 1D MoO_(3−x)nanobelts as photothermal film for interfacial solar evaporator.The surface-ligand protected reduction strategy provides a new avenue for the developing plasmonic semiconductor oxides with maintained particle morphology and thus enriching their wide applications.